CN108631004B - A kind of lead-acid battery electrolyte and preparation method thereof - Google Patents
A kind of lead-acid battery electrolyte and preparation method thereof Download PDFInfo
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- CN108631004B CN108631004B CN201810383019.7A CN201810383019A CN108631004B CN 108631004 B CN108631004 B CN 108631004B CN 201810383019 A CN201810383019 A CN 201810383019A CN 108631004 B CN108631004 B CN 108631004B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
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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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Abstract
The present invention provides a kind of lead-acid battery electrolyte and preparation method thereof, it is related to Lead-acid Battery Technology field, the lead-acid battery electrolyte is by base fluid, conversion zone and protective layer are composed, the conversion zone is prepared by polyurethane-modified resin liquid, the polyurethane-modified resin liquid includes following raw material: 4-methyl-1-pentene monomer, paraffin oil, catalyst, sea-island fibre, base polyurethane prepolymer for use as, 3, 3 '-two chloro- 4, 4 '-diaminodiphenyl-methanes, initiator, sodium bicarbonate, the protective layer includes following raw material: acrylic resin, amino resins, polyethylene terephthalate, auxiliary agent；The preparation method of the lead-acid battery electrolyte the following steps are included: S1, lead-acid accumulator shell pretreatment；The preparation of S2, conversion zone；The preparation of S3, protective layer glue；S4, it assembles.Electrolyte proposed by the present invention, it is applied widely, effectively prevent electrolyte solution loss, and preparation method is simple.
Description
Technical field
The present invention relates to Lead-acid Battery Technology field more particularly to a kind of lead-acid battery electrolyte and its preparation sides
Method.
Background technique
Lead-acid accumulator is widely used in the places such as communications and transportation, telecommunication power, school, bank, tourist recreation.Make at present
Lead-acid accumulator is broadly divided into two kinds, one kind for aqueous sulfuric acid non-enclosed lead-acid accumulator as main component,
Another kind is closed maintenance-free type lead-acid accumulator, wherein non-enclosed lead-acid accumulator is because of its simple production process, production
The advantages such as production cost is low more occupy advantage on the market.But the problem that non-enclosed lead-acid accumulator often occurs is exactly to make
It is shorter with the service life, the reduction of Chang Yinwei electrolyte, and lead to the reduction of battery capacity, to reduce the use longevity of lead-acid accumulator
Life.The reason of Electrolyte of Plumbic Acerbic High Battery is reduced is probed into, we can be found that the reduction of lead-acid accumulator electrolyte mainly has
Following reason: contain a certain amount of metal ion and lead in water used in equipment fault, lead-acid accumulator electrolyte
The frequent overcharge of acid accumulator so that the water in lead-acid accumulator electrolyte hydrolyzes, and hydrolyzes the hydrogen and oxygen generated
It is overflowed from electrolyte, the amount of electrolyte is caused to gradually decrease, even up to dry state.Based on it is of the existing technology not
Foot, the invention proposes the lead-acid battery electrolytes and preparation method thereof that one kind can effectively inhibit electrolyte reduction.
Summary of the invention
Big, production hardly possible that the purpose of the present invention is to solve lead-acid accumulator electrolyte loss lates existing in the prior art
A kind of lead-acid battery electrolyte and preparation method thereof spending high problem, and proposing.
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of lead-acid battery electrolyte is composed of base fluid, conversion zone and protective layer, and the base fluid is with sulfuric acid
Conventional electrolysis liquid based on aqueous solution, the conversion zone are prepared by polyurethane-modified resin liquid, the polyurethane-modified tree
Rouge liquid includes the raw material of following parts by weight: 100 parts of 4-methyl-1-pentene monomer, 30~40 parts of paraffin oil, 8~10 parts of catalyst,
3~5 parts of sea-island fibre, 3,3 '-two 3~8 parts of chloro- 4,4 '-diaminodiphenyl-methanes, draws 15~35 parts of base polyurethane prepolymer for use as
0.5~1.5 part of agent, 1~3 part of sodium bicarbonate are sent out, the protective layer includes the raw material of following parts by weight: acrylic resin 90~
110 parts, 70~80 parts of amino resins, 32~76 parts of polyethylene terephthalate, 2~4 parts of auxiliary agent.
Preferably, the polyurethane-modified resin liquid is prepared by the following method: first sea-island fibre is cut off, it is spare,
4-methyl-1-pentene monomer and base polyurethane prepolymer for use as are stirred evenly again, then by paraffin oil, initiator, sodium bicarbonate, catalyst
It is added with the sea-island fibre after cutting, continues to be stirred until homogeneous to get polyurethane-modified resin liquid.
Preferably, marine origin is divided into water-soluble polyester in the sea-island fibre.
Preferably, in the protective layer acrylic resin and amino resins mass ratio are as follows: 1.2~1.5:1, gather to benzene two
Formic acid second diester accounts for the 20%~40% of acrylic resin and amino resins gross mass.
The invention also provides a kind of preparation methods of lead-acid battery electrolyte, comprising the following steps:
The pretreatment of S1, lead-acid accumulator shell: first uniformly smearing lubricant in lead-acid accumulator shell inner surface, i.e., complete
At the pretreatment of lead-acid accumulator shell；
The preparation of S2, conversion zone: polyurethane-modified resin liquid is added to the lead-acid accumulator that step S1 pretreatment is completed
In shell, lead-acid accumulator is heated, to the expansion of polyurethane-modified resin liquid and after curing completely, is obtained polyurethane-modified
Resin layer, then add water into lead-acid accumulator shell, remove the sea component in polyurethane-modified resin layer, and guarantee polyurethane
Modified resin layer is completely sunk in the water in sea component stripping process, will be in lead-acid accumulator shell after the completion of sea component removing
Water pour out, then be rinsed with water and be in neutrality several times to the water lotion being poured out, that is, complete the preparation of conversion zone；
The preparation of S3, protective layer glue: acrylic resin, amino resins, polyethylene terephthalate and auxiliary agent are mixed
It closes uniformly to get protective layer glue；
S4, it assembles: base fluid being added in the lead-acid accumulator shell in step S2 with conversion zone, conversion zone is floated
It uniformly brushes on base fluid, then by protective layer glue prepared by step S3 in reaction layer surface, layer glue completion of cure to be protected
Complete assembling for lead-acid battery electrolyte.
Preferably, the lubricant is soluble oil, and the soluble oil includes the raw material of following parts by weight:
5~10 parts of glycerol, 2~5 parts of magnesium laurylsulfate, 3~8 parts of sucrose, 100 parts of water.
Preferably, the thickness of the conversion zone is not less than 0.5cm.
The present invention provides a kind of lead-acid battery electrolyte, and advantage is compared with prior art:
1, electrolyte proposed by the present invention, it is applied widely, it can satisfy non-enclosed lead-acid accumulator and use, using base
The mode that liquid, conversion zone and protective layer are combined can effectively solve the water electrolysis that lead-acid accumulator occurs in use
Problem, base fluid can satisfy the normal use of lead-acid accumulator, and the base fluid of various concentration can be with conversion zone and protective layer
Match use, the use scope of further expansion lead-acid accumulator proposed by the present invention；
2, conversion zone used in the present invention is prepared by polyurethane-modified resin liquid, is uniformly divided in obtained conversion zone
Cloth catalyst, and cellular is presented in conversion zone, after the water in electrolyte is electrolysed, the hydrogen and oxygen of generation can slowly overflow
Base fluid out reaches conversion zone, and is continued up by the cavity in conversion zone and diffuse to protective layer, in the barrier action of protective layer
Under, hydrogen, oxygen and vapor cannot penetrate protective layer, therefore hydrogen and oxygen rest on conversion zone, in conversion zone, position
Hydrogen and oxygen can be promoted to react in the catalyst in porous structure, be again converted into water, and along anti-after water condensation
It answers the cavity in layer to flow in electrolyte, supplements the amount for the water being electrolysed in electrolyte, keep water quantity holding in electrolyte constant, with
Drop effectively prevent the reduction of electrolyte, keeps the battery capacity of lead-acid accumulator, and then electrolyte is avoided to reduce caused battery
The phenomenon that service life reduces；
3, the polyurethane-modified resin liquid that the present invention uses is gathered jointly by 4-methyl-1-pentene monomer and base polyurethane prepolymer for use as
It closes, and passes through and paraffin oil, catalyst, sea-island fibre, 3 is added, 3 '-two chloro- 4,4 '-diaminodiphenyl-methanes, initiation
Agent and sodium bicarbonate, so that the polyurethane-modified resin layer after solidifying can have loose and porous structure, it is easier to swim in
On base fluid, and catalyst is evenly distributed in polyurethane-modified resin layer, then by the immersion of water, so that polyurethane-modified resin
Sea component in layer in sea-island fibre is gradually dissolved in water, and conversion zone is become by the polyurethane-modified resin layer for being originally used for sealing end
Open porous structure had not only guaranteed that passing freely through for hydrogen, oxygen and water, but also decrease hydrogen and oxygen rushed protective layer
It hits, also facilitates pouring out for removing water, carry out the preparation of conversion zone directly in lead-acid accumulator shell, simplify production stream
Journey saves production cost, and the present invention removes the sea component in sea-island fibre using water, to lead-acid accumulator electrolyte
Constituent without influence；
4, the protection glue that the present invention uses is reacted by the acrylic resin and amino resins of rational proportion, acrylic acid
Hydroxyl in resin can quickly be crosslinked with the amino in amino resins to react, so that the film formation time of protection glue
Short, the resin film retractility of formation is good, and the polyethylene terephthalate by adding rational proportion is modified resin film,
While guaranteeing that resin film has excellent retractility, assigns resin film excellent gas barrier property, be conducive to protective layer to plumbic acid
The barrier of the hydrogen and oxygen that generate in battery use process is converted into hydrogen and oxygen as much as possible in conversion zone
Water is revert in electrolyte, reduces the loss amount of electrolyte；
5, the application method of electrolyte proposed by the present invention is simple, and the curing time of conversion zone and protective layer is fast, Jin Erjia
The production efficiency of fast lead-acid accumulator, first uniformly smears water in lead-acid accumulator shell before polyurethane-modified resin liquid is added
Property lubricant, can be convenient conversion zone removing sea-island fibre sea component when, can be separated with lead-acid accumulator inner walls, with side
Just conversion zone smoothly swims in base fluid surface after base fluid is added, and when carrying out the sea component in ratio sea-island fibre, aqueous
Lubricant can also be dissolved in water and pour out together with the sea component removed, and reduce the influence that water-based lubricant generates base fluid, protect
The performance for holding lead-acid accumulator electrolyte is constant.
Specific embodiment
Combined with specific embodiments below the present invention is made further to explain.
Embodiment 1
A kind of lead-acid battery electrolyte proposed by the present invention, is composed of base fluid, conversion zone and protective layer, described
Base fluid is the conventional electrolysis liquid based on aqueous sulfuric acid, and the conversion zone is prepared by polyurethane-modified resin liquid, described
Polyurethane-modified resin liquid includes the raw material of following parts by weight: 100 parts of 4-methyl-1-pentene monomer, 30 parts of paraffin oil, catalyst
8 parts, 3 parts of sea-island fibre, 15 parts of base polyurethane prepolymer for use as, 3,3 '-two 3 parts of chloro- 4,4 '-diaminodiphenyl-methanes, initiator 0.5
Part, 1 part of sodium bicarbonate, the protective layer includes the raw material of following parts by weight: 90 parts of acrylic resin, gathers 70 parts of amino resins
32 parts of ethylene terephthalate, 2 parts of auxiliary agent；
Preparation method includes the following steps:
The pretreatment of S1, lead-acid accumulator shell: water-soluble lubricating is uniformly first smeared in lead-acid accumulator shell inner surface
Agent, soluble oil include the raw material of following parts by weight: 10 parts of glycerol, 5 parts of magnesium laurylsulfate, 8 parts of sucrose, 100 parts of water,
The pretreatment of lead-acid accumulator shell is completed after smearing；
The preparation of S2, conversion zone: polyurethane-modified resin liquid is added to the lead-acid accumulator that step S1 pretreatment is completed
In shell, lead-acid accumulator is heated, to the expansion of polyurethane-modified resin liquid and after curing completely, is obtained polyurethane-modified
Resin layer, then add water into lead-acid accumulator shell, remove the sea component in polyurethane-modified resin layer, and guarantee polyurethane
Modified resin layer is completely sunk in the water in sea component stripping process, will be in lead-acid accumulator shell after the completion of sea component removing
Water pour out, then be rinsed with water and be in neutrality several times to the water lotion being poured out, that is, complete the preparation of conversion zone, the thickness of conversion zone
Degree is 0.7cm；
The preparation of S3, protective layer glue: acrylic resin, amino resins, polyethylene terephthalate and auxiliary agent are mixed
It closes uniformly to get protective layer glue；
S4, it assembles: base fluid being added in the lead-acid accumulator shell in step S2 with conversion zone, conversion zone is floated
It uniformly brushes on base fluid, then by protective layer glue prepared by step S3 in reaction layer surface, layer glue completion of cure to be protected
Complete assembling for lead-acid battery electrolyte.
Embodiment 2
A kind of lead-acid battery electrolyte proposed by the present invention, is composed of base fluid, conversion zone and protective layer, described
Base fluid is the conventional electrolysis liquid based on aqueous sulfuric acid, and the conversion zone is prepared by polyurethane-modified resin liquid, described
Polyurethane-modified resin liquid includes the raw material of following parts by weight: 100 parts of 4-methyl-1-pentene monomer, 40 parts of paraffin oil, catalyst
10 parts, 5 parts of sea-island fibre, 35 parts of base polyurethane prepolymer for use as, 3,3 '-two 8 parts of chloro- 4,4 '-diaminodiphenyl-methanes, initiator
1.5 parts, 3 parts of sodium bicarbonate, the protective layer includes the raw material of following parts by weight: 110 parts of acrylic resin, amino resins 80
Part, 76 parts of polyethylene terephthalate, 4 parts of auxiliary agent；
Preparation method includes the following steps:
The pretreatment of S1, lead-acid accumulator shell: water-soluble lubricating is uniformly first smeared in lead-acid accumulator shell inner surface
Agent, soluble oil include the raw material of following parts by weight: 5 parts of glycerol, 2 parts of magnesium laurylsulfate, 3 parts of sucrose, 100 parts of water,
The pretreatment of lead-acid accumulator shell is completed after smearing；
The preparation of S2, conversion zone: polyurethane-modified resin liquid is added to the lead-acid accumulator that step S1 pretreatment is completed
In shell, lead-acid accumulator is heated, to the expansion of polyurethane-modified resin liquid and after curing completely, is obtained polyurethane-modified
Resin layer, then add water into lead-acid accumulator shell, remove the sea component in polyurethane-modified resin layer, and guarantee polyurethane
Modified resin layer is completely sunk in the water in sea component stripping process, will be in lead-acid accumulator shell after the completion of sea component removing
Water pour out, then be rinsed with water and be in neutrality several times to the water lotion being poured out, that is, complete the preparation of conversion zone, the thickness of conversion zone
Degree is 0.7cm；
The preparation of S3, protective layer glue: acrylic resin, amino resins, polyethylene terephthalate and auxiliary agent are mixed
It closes uniformly to get protective layer glue；
S4, it assembles: base fluid being added in the lead-acid accumulator shell in step S2 with conversion zone, conversion zone is floated
It uniformly brushes on base fluid, then by protective layer glue prepared by step S3 in reaction layer surface, layer glue completion of cure to be protected
Complete assembling for lead-acid battery electrolyte.
Embodiment 3
A kind of lead-acid battery electrolyte proposed by the present invention, is composed of base fluid, conversion zone and protective layer, described
Base fluid is the conventional electrolysis liquid based on aqueous sulfuric acid, and the conversion zone is prepared by polyurethane-modified resin liquid, described
Polyurethane-modified resin liquid includes the raw material of following parts by weight: 100 parts of 4-methyl-1-pentene monomer, 35 parts of paraffin oil, catalyst
9 parts, 4 parts of sea-island fibre, 25 parts of base polyurethane prepolymer for use as, 3,3 '-two 6 parts of chloro- 4,4 '-diaminodiphenyl-methanes, initiator 1
Part, 2 parts of sodium bicarbonate, the protective layer includes the raw material of following parts by weight: 100 parts of acrylic resin, gathers 80 parts of amino resins
54 parts of ethylene terephthalate, 3 parts of auxiliary agent；
Preparation method includes the following steps:
The pretreatment of S1, lead-acid accumulator shell: water-soluble lubricating is uniformly first smeared in lead-acid accumulator shell inner surface
Agent, soluble oil include the raw material of following parts by weight: 8 parts of glycerol, 3 parts of magnesium laurylsulfate, 5 parts of sucrose, 100 parts of water,
The pretreatment of lead-acid accumulator shell is completed after smearing；
The preparation of S2, conversion zone: polyurethane-modified resin liquid is added to the lead-acid accumulator that step S1 pretreatment is completed
In shell, lead-acid accumulator is heated, to the expansion of polyurethane-modified resin liquid and after curing completely, is obtained polyurethane-modified
Resin layer, then add water into lead-acid accumulator shell, remove the sea component in polyurethane-modified resin layer, and guarantee polyurethane
Modified resin layer is completely sunk in the water in sea component stripping process, will be in lead-acid accumulator shell after the completion of sea component removing
Water pour out, then be rinsed with water and be in neutrality several times to the water lotion being poured out, that is, complete the preparation of conversion zone, the thickness of conversion zone
Degree is 0.7cm；
The preparation of S3, protective layer glue: acrylic resin, amino resins, polyethylene terephthalate and auxiliary agent are mixed
It closes uniformly to get protective layer glue；
S4, it assembles: base fluid being added in the lead-acid accumulator shell in step S2 with conversion zone, conversion zone is floated
It uniformly brushes on base fluid, then by protective layer glue prepared by step S3 in reaction layer surface, layer glue completion of cure to be protected
Complete assembling for lead-acid battery electrolyte.
In above-described embodiment 1~3, polyurethane-modified resin liquid is prepared by the following method: first sea-island fibre is cut off,
It is spare, then 4-methyl-1-pentene monomer and base polyurethane prepolymer for use as are stirred evenly, then by paraffin oil, initiator, sodium bicarbonate,
Sea-island fibre after catalyst and cutting is added, and continues to be stirred until homogeneous to get polyurethane-modified resin liquid, and in sea-island fibre
Marine origin is divided into water-soluble polyester.
Comparative example 1
By the conversion zone and protection composition of layer removal in embodiment 3, other conditions are the same as embodiment 3.
The production technology of conventional non-enclosed lead-acid accumulator carries out production lead-acid accumulator, then to embodiment 1 and comparison
The lead-acid accumulator that example obtains carries out charge-discharge test 300 times of overvoltage 40%, calculates electrolyte solution loss rate.
According to the electrolyte prescription of Examples 1 to 3 and comparative example 1, preparation method in conjunction with common lead-acid accumulator
Production technology produces lead-acid accumulator respectively, and detects the capacity of lead-acid accumulator, chooses and matches with the battery capacity of measurement
Commercially available common lead-acid accumulator and commercially available maintenance-free lead accumulator carry out charge and discharge cycles experiment respectively, and in charge and discharge
In cyclic process, into lead-acid accumulator, persistently input is higher than charge-discharge test 300 times of assigned voltage 40%, then calculates lead
The reduced rate of acid accumulator capacity and the slip of electrolyte, the results are shown in Table 1.
Table 1:
| Detection project | Battery capacity reduced rate % | Electrolyte slip % |
| Embodiment 1 | 32.3 | 6.3 |
| Embodiment 2 | 34.2 | 6.7 |
| Embodiment 3 | 30.1 | 6.1 |
| Comparative example 1 | 70.9 | 38.1 |
| Common lead-acid accumulator | 71.4 | 38.4 |
| Maintenance-free lead accumulator | 32.7 | 6.6 |
1 experimental result of table shows that the lead-acid accumulator obtained using Examples 1 to 3 is under the conditions of by ultra-voltage 40%
After circulation 300 times, battery capacity reduced rate and electrolyte slip are close with maintenance-free lead accumulator, and Examples 1 to 3
Common lead-acid accumulator and comparative example are significantly lower than with the capacity reduced rate and electrolyte slip of maintenance-free lead accumulator
1, show that the conversion zone of lead-acid accumulator electrolyte proposed by the present invention and protective layer can effectively solve the problem that common lead-acid accumulator
The big problem of electrolyte solution loss amount, and then extend the service life of lead-acid accumulator；And electrolyte proposed by the present invention is only logical
It crosses simple preparation and the production of lead-acid accumulator can be completed in the combination of common lead-acid accumulator production technology, compared to commercially available
Maintenance-free lead accumulator, operation is more simple, and low production cost, maintenance difficulties are significantly reduced.
The thickness of conversion zone in embodiment 3 is changed to the corresponding thickness of table 2 by embodiment 4~12 respectively, and other conditions are same
Embodiment 3, same charge-discharge test 300 times for carrying out overvoltage 40%, calculates electrolyte solution loss rate, and whether observe protective layer
Rupture, the results are shown in Table 2.
Table 2:
| Embodiment | Reaction layer thickness cm | Electrolyte solution loss rate % | Whether protective layer ruptures |
| 4 | 0.1 | 31.2 | Rupture |
| 5 | 0.2 | 26.8 | Rupture |
| 6 | 0.3 | 18.4 | It does not rupture |
| 7 | 0.4 | 14.5 | It does not rupture |
| 8 | 0.5 | 6.8 | It does not rupture |
| 9 | 0.6 | 6.1 | It does not rupture |
| 10 | 0.8 | 5.2 | It does not rupture |
| 11 | 0.9 | 5.0 | It does not rupture |
| 12 | 1.0 | 5.0 | It does not rupture |
2 experimental result of table is shown, with the increase of reaction layer thickness, the loss amount of lead-acid accumulator electrolyte gradually drops
It is low, after more than 0.8cm loss amount reduce it is unobvious, and reaction layer thickness be lower than 0.3cm when, protective layer is easily rupturable, therefore
The thickness of conversion zone needs that place could be provided in 0.5cm or more for the reaction of catalyst hydrogen and oxygen, and effectively subtracts
The hydrogen and oxygen generated in slow electrolyte prevents protective layer from rupturing, electrolyte is caused largely to lose to the impact force of protective layer.
The pre-treatment step omission of lead-acid accumulator shell in embodiment 3 is directly added into polyurethane-modified tree by comparative example 2
Rouge liquid, other conditions are with embodiment 3, it can be found that the interior firm connection of conversion zone and lead-acid accumulator shell after solidifying, is added
After base fluid, base fluid surface cannot be swum in.
Water-based lubricant in embodiment 3 is changed to non-aqueous lubricant by comparative example 3, and other conditions, can with embodiment 3
To find that base fluid before lead-acid accumulator shell is added and after being added to the lead-acid accumulator shell containing conversion zone, has in base fluid
A large amount of residuals of non-aqueous lubricant, and the battery capacity of lead-acid accumulator reduces, and in testing on an equal basis, the base fluid of embodiment 3
Middle no water-based lubricant residual, battery capacity remain unchanged, therefore even more ideal using water-based lubricant.
Embodiment 13~21, by embodiment 3 acrylic resin and amino resins replace according to proportionate relationship in table 3
It changes, and carries out protective layer using the preparation method of lead-acid accumulator electrolyte in obtained protective layer glue simulation embodiment 3
Preparation, records the film formation time of protective layer in embodiment 3 and embodiment 13~20, and is measured to the performance of protective layer,
It the results are shown in Table 3.
Table 3:
In table 3,1) A:B is the mass ratio of acrylic resin and amino resins；2) elongation according to GBB022-91 standard into
Row detection；3) it is detected according to GB/T 13519-2016 standard；4) whether rupture and refer to and give conversion zone 0.5MPa for 24 hours
Pressure simultaneously observes protective layer rupture event.
Table 1 the results show that the obtained protective layer of embodiment 3 and embodiment 13~20 0.5MPa pressure for 24 hours not
It can rupture, and as the ratio of acrylic resin in acrylic resin and amino resins increases elongation, shrinking percentage is in
Existing growth trend, after the ratio of acrylic resin in acrylic resin and amino resins is more than 1:1, elongation be can achieve
200% or more, shrinking percentage can achieve 20% or more, however film formation time is but with propylene in acrylic resin and amino resins
The ratio of acid resin increases the raised trend that first reduces again that presents, the mass ratio of acrylic resin and amino resins 1.2~
Film formation time is in 7h hereinafter, and the film formation time when the mass ratio of acrylic resin and amino resins is 1.4:1 between 1.5:1
It touching the bottom as 3.7h, film formation time is suitable for when the mass ratio for showing acrylic resin and amino resins is 1.2~1.5:1,
Comprehensively consider the expansion and contraction that the mass ratio of acrylic resin and amino resins in the present invention is the protective layer that 1.2~1.5:1 is obtained
It is preferable with film formation time, and be not easily broken.
Polyethylene terephthalate in embodiment 3 is accounted for acrylic resin and the total matter of amino resins by embodiment 21~31
The specific gravity of amount is converted according to table 4, and other conditions use lead in obtained protective layer glue simulation embodiment 3 with embodiment 3
The preparation of the preparation method progress protective layer of electrolyte of lead-acid accumulator, the film formation time of record protection layer, and to the property of protective layer
It can be carried out measurement, the results are shown in Table 4.
Table 4:
In table 4, a) elongation is detected according to GBB022-91 standard；B) shrinking percentage is marked according to GB/T 13519-2016
Standard is detected；C) Air permenbility is to be measured using GB/T1038-2000 standard using pressure differential method, the transmission of corresponding gas interior for 24 hours
Amount.
The results show that the content with polyethylene terephthalate increases, the film formation time of conversion zone is shown to be tended to table 4
Gentle increase increases after more than 35% and increases, and then needs 9h or more that could form a film after super more 40%, and with poly-
The content of ethylene terephthalate increases, and the variation of elongation and shrinking percentage is unobvious, but in polyethylene terephthalate
Content it is lower when hydrogen and oxygen transit dose it is larger, can make water electrolysis generate hydrogen and oxygen through protective layer overflow
Out, the protective effect for reducing protective layer, comprehensively considers, and the content of polyethylene terephthalate is between 20%~40%
Now preferable protective effect.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of lead-acid battery electrolyte, which comprises the following steps:
The pretreatment of S1, lead-acid accumulator shell: first uniformly smearing lubricant in lead-acid accumulator shell inner surface, i.e. completion lead
The pretreatment of acid accumulator shell；
The preparation of S2, conversion zone: polyurethane-modified resin liquid is added to the lead-acid accumulator shell that step S1 pretreatment is completed
It is interior, lead-acid accumulator is heated, to the expansion of polyurethane-modified resin liquid and after curing completely, obtains polyurethane-modified resin
Layer, then add water into lead-acid accumulator shell, remove the sea component in polyurethane-modified resin layer, and guarantee polyurethane-modified
Resin layer is completely sunk in the water in sea component stripping process, by the intracorporal water of lead-acid accumulator shell after the completion of sea component removing
It pours out, then is rinsed with water and is in neutrality several times to the water lotion being poured out, that is, complete the preparation of conversion zone；
The preparation of S3, protective layer glue: acrylic resin, amino resins, polyethylene terephthalate and auxiliary agent are mixed equal
It is even to get protective layer glue；
S4, it assembles: base fluid being added in the lead-acid accumulator shell in step S2 with conversion zone, conversion zone is made to swim in base
On liquid, then protective layer glue prepared by step S3 is uniformly brushed and is reacting layer surface, layer glue completion of cure to be protected, that is, complete
At assembling for lead-acid battery electrolyte.
2. a kind of preparation method of lead-acid battery electrolyte according to claim 1, which is characterized in that the lubrication
Agent is soluble oil, and the soluble oil includes the raw material of following parts by weight: 5~10 parts of glycerol, laruyl alcohol sulfuric acid
2~5 parts of magnesium, 3~8 parts of sucrose, 100 parts of water.
3. a kind of preparation method of lead-acid battery electrolyte according to claim 1, which is characterized in that the reaction
The thickness of layer is not less than 0.5cm.
4. a kind of lead-acid battery electrolyte is obtained using preparation method described in claim 1-3 any claim, special
Sign is that the lead-acid battery electrolyte is composed of base fluid, conversion zone and protective layer, and the base fluid is with sulfuric acid water
Conventional electrolysis liquid based on solution, the conversion zone are prepared by polyurethane-modified resin liquid, the polyurethane-modified resin
Liquid includes the raw material of following parts by weight: 100 parts of 4-methyl-1-pentene monomer, 30~40 parts of paraffin oil, 8~10 parts of catalyst, sea
3~5 parts of island fiber, 3,3 '-two 3~8 parts of chloro- 4,4 '-diaminodiphenyl-methanes, causes 15~35 parts of base polyurethane prepolymer for use as
0.5~1.5 part of agent, 1~3 part of sodium bicarbonate, the protective layer include the raw material of following parts by weight: acrylic resin 90~110
Part, 70~80 parts of amino resins, 32~76 parts of polyethylene terephthalate, 2~4 parts of auxiliary agent.
5. a kind of lead-acid battery electrolyte according to claim 4, which is characterized in that the polyurethane-modified resin
Liquid is prepared by the following method: first sea-island fibre cut off, it is spare, then by 4-methyl-1-pentene monomer and polyurethane prepolymer
Body stirs evenly, then the sea-island fibre after paraffin oil, initiator, sodium bicarbonate, catalyst and cutting is added, and continues stirring extremely
Uniformly to get polyurethane-modified resin liquid.
6. a kind of lead-acid battery electrolyte according to claim 4 or 5, which is characterized in that in the sea-island fibre
Marine origin is divided into water-soluble polyester.
7. a kind of lead-acid battery electrolyte according to claim 4, which is characterized in that acrylic acid in the protective layer
The mass ratio of resin and amino resins are as follows: 1.2~1.5:1, polyethylene terephthalate account for acrylic resin and amino resins
The 20%~40% of gross mass.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1750312A (en) * | 2005-09-23 | 2006-03-22 | 周明明 | Colloidal electrolyte of lead acid accumulator |
| CN107799833A (en) * | 2017-10-30 | 2018-03-13 | 杨昌恩 | A kind of battery liquid |
| CN107959063A (en) * | 2016-10-14 | 2018-04-24 | 现代自动车株式会社 | Lead accumulator electrolyte composition and the lead accumulator using said composition |
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| US5352545A (en) * | 1992-01-31 | 1994-10-04 | Yuasa Corporation | Battery containing foam polyurethane resin and method of making |
| JP2003151618A (en) * | 2001-11-09 | 2003-05-23 | Tagawa Kazuo | Lead-acid battery and additive for lead-acid battery |
| CN101882694B (en) * | 2010-06-21 | 2012-06-20 | 冯家齐 | Electrolyte of lead-acid accumulator and preparation method thereof |
| CN102468517A (en) * | 2010-11-12 | 2012-05-23 | 陈清利 | Novel electrolyte for storage battery and preparation method of novel electrolyte |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1750312A (en) * | 2005-09-23 | 2006-03-22 | 周明明 | Colloidal electrolyte of lead acid accumulator |
| CN107959063A (en) * | 2016-10-14 | 2018-04-24 | 现代自动车株式会社 | Lead accumulator electrolyte composition and the lead accumulator using said composition |
| CN107799833A (en) * | 2017-10-30 | 2018-03-13 | 杨昌恩 | A kind of battery liquid |
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