CN107359312A - A kind of preparation method of lead plaster and its detection method of carbon material dispersion effect - Google Patents
A kind of preparation method of lead plaster and its detection method of carbon material dispersion effect Download PDFInfo
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- CN107359312A CN107359312A CN201710459761.7A CN201710459761A CN107359312A CN 107359312 A CN107359312 A CN 107359312A CN 201710459761 A CN201710459761 A CN 201710459761A CN 107359312 A CN107359312 A CN 107359312A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
Abstract
The present invention relates to lead-acid accumulator manufacturing field, and in particular to a kind of preparation method of lead plaster and its detection method of carbon material dispersion effect.A kind of preparation method of lead plaster comprises the following steps:After carbon material is pre-processed lead plaster finished product is obtained after the mixed processing of water and the mixed processing of acid.A kind of detection method of the carbon material dispersion effect of lead plaster provided by the invention is that green plate surface is coated in after lead plaster is ground, standing makes it be sampled after solidifying, then sample is placed among test position, then the temperature and characteristic peak collection of illustrative plates of heat analysis acquisition sample are carried out with differential scanning calorimeter, testing result is obtained after analysis.The beneficial effects of the present invention are technical scheme provide a kind of finely dispersed lead plaster of carbon material preparation method and a kind of process it is quick, accurate, cost is low, and the detection method of the carbon material dispersion effect of lead plaster that visual result easily compares.
Description
Technical field
The present invention relates to lead-acid accumulator manufacturing field, and in particular to the preparation method and its carbon material of a kind of lead plaster are disperseed
The detection method of effect.
Background technology
The automobile-used lead carbon battery of electrical salf-walking, its production process is mainly manufactured by grid, the preparation of lead plaster, coated plate, solidification are dry
Dry, battery assembling and pole plate are melted into and waited process.The preparation process of lead plaster is important in lead carbon battery production process and compared
Process more complicated, more rambunctious, in this process deployment conditions of additive, sulfuric acid, the addition manner of water and addition
Amount can have influence on the performance of lead carbon battery.If the performance of a whole set of lead carbon battery group has big difference, lead carbon battery is easily caused
That organizes is discrete, easily causes lead carbon battery group premature failure, influences service life.Therefore the uniformity of lead carbon battery need to be carried out
Lifting, to improve the performance of whole lead carbon battery group and life-span.Because the deployment conditions of lead carbon battery internal additives are to influence
To the principal element of the overall performance of lead carbon battery, and carbon material dispersiveness is poor, the problem of easy reunion be present, therefore improve electricity
The scattered situation of pond internal additives particularly carbon material is to improve the important channel of battery performance.
A lead carbon battery cathode lead plasters of Chinese patent CN 103811752 and preparation method thereof, lead carbon battery negative plate and lead
Carbon battery announces following technical scheme：Take 100 parts of lead powder, 0.1~2 part of barium sulfate, 0.01~2 part of liberation of hydrogen inhibitor, oxidation stone
Black 50~100 parts of alkene, 0.05~1 part of acetylene black, 1~4 part of humic acid, 5~15 parts of red lead, 0.1~0.2 part of chopped fiber are poured into
In container, mixture is uniformly mixing to obtain, 12~21 parts of water is added in the mixture, again in stirring condition after stirring
It is lower addition 4~100 parts of sulfuric acid, stir 10~20 minutes, it is described it is sulfuric acid-treated after mixture in add binding agent 0.1~
8 parts, the apparent density for stirring and controlling colloid mixture is 3.5~4.5g/ml, obtains lead carbon battery cathode lead plaster.The invention
The shortcomings that be：In the technical scheme, additive especially carbon material is possible to scattered uneven, has influence on lead carbon battery
Performance, easily the performance of a whole set of lead carbon battery group is had big difference, the discrete of lead carbon battery group is caused, so as to have influence on lead carbon
The performance of battery pack and life-span.
Dispersion effect detection of the carbon material in lead-acid accumulator at present is mainly using metallography microscope sem observation or thick
The methods of data that rugosity tester is measured are shown indirectly, and the dispersion effect of method detection carbon material is present as use
Check-Out Time is grown, and accuracy in detection is low and can not intuitively go to embody dispersion effect of the carbon material in lead plaster etc.
Problem.The detection method of a kind of carbon materials of the A of Chinese patent CN 106353352 dispersion effect in lead-acid accumulator, by right
Mode that pole plate electron microscope picture after the electron microscope power spectrum elemental map of pole plate before processing and processing is combined is observed
Dispersion effect of the carbon material in lead plaster, although the distribution situation of carbon material can accurately be characterized, but in the process
Cost time length, and high is required to laboratory apparatus, cost is higher.
Therefore the preparation method of the finely dispersed lead plaster of carbon material in a kind of additive especially additive is needed at present
It is quick with a kind of process, accurate, cost is low, and the detection method of the carbon material dispersion effect of lead plaster that visual result easily compares.
The content of the invention
It is uneven in order to solve to disperse existing for the carbon material of current lead carbon battery lead plaster, have influence on the property of lead carbon battery
Can, easily the performance of a whole set of lead carbon battery group is had big difference, cause the discrete of lead carbon battery group, so as to have influence on lead carbon electricity
The problem of performance of pond group and life-span, while in order to solve the detection method of the carbon material dispersion effect of current lead carbon battery lead plaster
Existing Check-Out Time length, cost is high, and accuracy in detection is low and can not intuitively go to embody point of the carbon material in lead plaster
The problem of dissipating effect etc., there is provided the preparation method and a kind of process of a kind of finely dispersed lead plaster of carbon material be quick, it is accurate,
Cost is low, and the detection method of the carbon material dispersion effect of lead plaster that visual result easily compares.The present invention uses following technical side
Case：
A kind of preparation method of lead plaster, comprises the following steps：
(1) carbon material pre-processes：Dispersant and carbon material are successively put into organic solvent, make described carbon material with it is described
Dispersant is infiltrated completely, obtains mixture, is then carried out ultrasound bath processing to described mixture, is obtained dispersion liquid,
Described dispersion liquid is subjected to good pressure distribution processing with good pressure distribution equipment instrument afterwards, obtains polymer dispersion liquid, then will be described
Polymer dispersion liquid stirs 0.5~1.2 hour under conditions of 85~95 DEG C, the dispersion liquid stablized, by described stabilization
Dispersion liquid filtering, collect sediment, after water washing dry, obtain powder；
(2) the mixed processing of water：Chopped fiber is put into after described powder is mixed with water, carries out shear agitation 1~2 minute, is mixed
Solution is closed, mixed solution is added in lead powder, obtains lead plaster semi-finished product；
(3) the mixed processing of acid：Add sulfuric acid while stirring in above-mentioned lead plaster semi-finished product, lead plaster finished product is obtained after acid is mixed.
Ultrasound bath is carried out to mixture in the preprocessing process of step (1) carbon material, ultrasonic wave is with more than people
, penetration power strong the characteristics of short with the high wavelength of frequency, is conducted in fluctuation more than class sense of hearing audio frequency in a liquid, and this causes ultrasonic wave
With higher-energy.When sound wave is propagated in described mixture, because sound wave is a kind of compressional wave, the work of compressional wave promotion medium
Produced countless slight vacuums with pressure change in liquid can be made and steeped, be referred to as " void effect ".In the present invention, when steam bubble by
When pressing explosion, powerful impulse energy can be produced, the carbon material wherein to stick together can be broken up, can so prevent due to one
A little carbon dusts mutually bind because of surface reaction forces causes the carbon material situation pockety in lead plaster to occur, so as to increase
By force in lead plaster carbon material dispersion effect.
Generally, chopped fiber is put into pure water to be stirred, can be intuitively to find fiber in dispersed
State, and place for a long time all without there is too big change；But often exist without the chopped fiber being processed, these chopped fibers
Dispersity in water is poor, occurs to disperse after agitation, but will float after a while, forms batt layer.This phenomenon meeting
The dispersity for the additive having influence in lead plaster is uneven, influences the performance of battery, therefore the present invention mixes in the water of step (2)
In step, shear agitation is carried out to chopped fiber, in the presence of shearing force, chopped fiber and additive can disperse in water
It is even, compared with the dry stirring that presently, there are, can solve the problems, such as that various powder stirrings are uneven, while can also shorten and stir
Mix the time, improve production efficiency.
Preferably, described dispersant is lignin sulfonate, sulfonated polystyrene, naphthalene sulfonic acid-formaldehyde condensation product, ten
One or more kinds of combinations in sodium dialkyl sulfate, neopelex, PVP or polyacrylic acid.
Carbon material can be helped to be better dispersed in solvent using the combination of these materials, improve the scattered effect of carbon material
Fruit.
Preferably, described organic solvent is one or more kinds of combinations in methanol, ethanol, acetone or ether.
Preferably, bath temperature is 58~70 DEG C during the ultrasound bath described in step (1) is handled, surpass
The sound time is 0.3~1 hour.
Preferably, in the good pressure distribution processing described in described step (1) in the condition that atmospheric pressure value is 103~125MPa
Lower progress, good pressure distribution processing procedure repeat 2~3 times, and the time per treatment is 3~5min.
Handled first by the good pressure distribution of 2~3 repetitions, carbon material can be made to be well dispersed in dispersant, so as in
Polymer is formed, prevents polymer from forming incomplete situation and occurring, makes the scattered more uniform of carbon material.
Preferably, the mixed solution described in step (2) is added in lead powder by the way of spraying, spraying adds
Rate of acceleration is 0.17~0.33ml/s.
Preferably, during step (3) acid is mixed, the adding rate of sulfuric acid is as follows：
A controls the initial adding rate of sulfuric acid in 0.17~0.22L/s when lead plaster semi-finished product temperature is in less than 48 DEG C,
B when lead plaster semi-finished product temperature be in 48~57 DEG C between when, by the adding rate of sulfuric acid be adjusted to initial flow rate 70~
85%,
C when lead plaster semi-finished product temperature be in 57~68 DEG C between when, by the adding rate of sulfuric acid be adjusted to initial flow rate 50~
60%,
D reduces flow velocity to maintain lead plaster semi-finished product temperature when lead plaster semi-finished product temperature rises to 68~70 DEG C, keep 3~
5min,
E continues stirring 5~8 minutes after sulfuric acid is added, until lead plaster semi-finished product temperature is down to 43~50 DEG C, obtain lead plaster into
Product.
In the solution of the present invention, reacted first using the adding rate of higher sulfuric acid, now react more acute
Strong, sulfuric acid reacts to form lead sulfate with the lead oxide in lead plaster semi-finished product, simultaneous reactions heat release, causes temperature to raise, works as temperature
When between reaching 48~57 DEG C, lead sulfate further reacts generation tribasic lead sulfate caused by reaction, because this process has
These accessory substances of the stereoisomer accessory substance of side reaction generation generation tribasic lead sulfate can destroy tribasic lead sulfate crystals
Structure so as to have influence on the performance of battery, should now slow down the adding speed of sulfuric acid, so on the one hand can reduce sulfuric acid
The formation speed of lead, prevent excessive sulfuric acid leading crystal from producing,；On the other hand, lead sulfate can be reduced in this stage of reaction
Amount, the amount of lead sulfate is reduced in this stage of reaction can prevent side reaction from being favorably improved the pure of tribasic lead sulfate
Degree, when temperature is risen to 68~70 DEG C, further generation tribasic lead sulfate is reacted, and tribasic lead sulfate crystals increase
Greatly, now further reduce flow velocity and control temperature, prevent from because temperature is too high make it that crystal is excessive, make caused crystal fine and closely woven
It is stable, and continue to stir after the completion of reaction, it on the one hand can promote the generation of fine crystals, on the other hand can also make carbon materials
Material is homogeneously mixed in crystal, ensure that being uniformly dispersed for carbon material.The program is no in use to use heating
Device, cost-effective effect on the one hand can be played, on the other hand increases the reaction time, contributes to controlling reaction temperature,
Make the obtained tiny densification of crystal, can so improve the service life cycle of battery.
A kind of detection method of the carbon material dispersion effect of lead plaster, comprises the following steps：
(1) sample preparation：Green plate surface is coated in after lead plaster is ground, standing makes its solidification；
(2) sample：The lead plaster on the green plate after solidification is chosen using standard sample method, sampling is included with piece green plate difference position
The sample on sample and the different green plates for applying the cream period put, is then placed in test position by green plate sample active
Among；
(3) DSC heat analysis：The temperature and characteristic peak collection of illustrative plates of heat analysis acquisition sample are carried out by differential scanning calorimeter, after analysis
The differential thermal analysis curve of lead plaster is obtained, the energy variation that acquisition exothermic process is then analyzed by line integral obtains detection knot
Fruit.
The present invention may then pass through by the differential thermal analysis curve of drafting and more different samples to be compared to obtain result
Standard deviation rate can intuitively be quickly obtained the result of carbon material dispersity, more facilitate and be accurately easy to compared with prior art
Compare.
Preferably, described step (3) DSC heat analysis process is carried out in a nitrogen atmosphere, heating rate is 15~22
DEG C/min, end temp is 700~1100 DEG C.
The end temp used in the present invention is 700~1000 degree Celsius, it is ensured that carbon material is burned out completely, is made
It is more accurate to obtain result.
Preferably, the quality of the sample and blank sample in described step (2) sampling process is 50~600 millis
Gram.
The beneficial effects of the present invention are：(1) lead plaster carbon material provided by the invention be uniformly dispersed (2) production battery make
With the detection method process of the carbon material dispersion effect of the lead plaster of long lifespan (2) present invention is quick, accurate, low (3) this hair of cost
The detection method testing result of the carbon material dispersion effect of bright lead plaster intuitively easily compares.
Embodiment
The present invention is further explained with reference to specific implementation case：
Embodiment 1
A kind of preparation method of lead plaster, step are as follows：
(1) carbon material pre-processes：Lignin sulfonate and carbon material are successively put into acetone, make described carbon material with it is wooden
Plain sulphonic acid ester is infiltrated completely, obtains mixture, then carries out ultrasound bath processing, ultrasound bath to described mixture
Bath temperature is 58 DEG C during processing, and ultrasonic time is 0.3 hour, obtains dispersion liquid, after by described dispersion liquid height
Dispersing apparatus instrument is pressed to carry out good pressure distribution processing, good pressure distribution processing procedure is repeated 2 times, atmospheric pressure value 103MPa, per treatment
Time is 3min, obtains polymer dispersion liquid, then described polymer dispersion liquid is stirred 0.5 hour under conditions of 85 DEG C,
The dispersion liquid stablized, the dispersion liquid of described stabilization is filtered, collect sediment, dried after water washing, obtain powder；
(2) the mixed processing of water：It is put into chopped fiber after described powder is mixed with water, carries out shear agitation 1 minute, obtains mixing molten
Liquid, by mixed solution using spraying by the way of be added in lead powder, the adding rate of spraying be 0.17ml/s, obtain lead plaster partly into
Product；
(3) the mixed processing of acid：Add sulfuric acid while stirring in above-mentioned lead plaster semi-finished product, the adding rate of sulfuric acid is as follows：
A controls the initial adding rate of sulfuric acid in 0.17L/s when lead plaster semi-finished product temperature is in less than 48 DEG C,
The adding rate of sulfuric acid is adjusted to the 70% of initial flow rate by b when lead plaster semi-finished product temperature is between 48~57 DEG C,
The adding rate of sulfuric acid is adjusted to the 50% of initial flow rate by c when lead plaster semi-finished product temperature is between 57~68 DEG C,
D reduces flow velocity to maintain lead plaster semi-finished product temperature, keeps 3min when lead plaster semi-finished product temperature rises to 68~70 DEG C,
E continues stirring 5 minutes after sulfuric acid is added, until lead plaster semi-finished product temperature is down to 43 DEG C, obtains lead plaster finished product.
Then the carbon material dispersion effect of the lead plaster finished product to obtaining detects, and step is as follows：
(1) sample preparation：Green plate surface is coated in after lead plaster is ground, standing makes its solidification；
(2) sample：The lead plaster on the green plate after solidification is chosen using standard sample method, samples each sample 500mg, each sample
Product include the sample on sample and the different green plates for applying the cream period with piece green plate diverse location, and then green plate is lived
Property material sample is placed among test position；
(3) DSC heat analysis：Heat analysis is carried out by differential scanning calorimeter, DSC heat analysis process is carried out in a nitrogen atmosphere, is risen
Warm speed is 22 DEG C/min, and end temp is 1000 DEG C.
The temperature and characteristic peak collection of illustrative plates of sample are obtained, the differential thermal analysis curve of lead plaster is obtained after analysis, then by linear
The energy variation that integral analysis obtains exothermic process obtains testing result.
Embodiment 2
A kind of preparation method of lead plaster, step are as follows：
(1) carbon material pre-processes：Lignin sulfonate and carbon material are successively put into acetone, make described carbon material with it is wooden
Plain sulphonic acid ester is infiltrated completely, obtains mixture, then carries out ultrasound bath processing, ultrasound bath to described mixture
Bath temperature is 70 DEG C during processing, and ultrasonic time is 1 hour, obtains dispersion liquid, after by described dispersion liquid high pressure
Dispersing apparatus instrument carries out good pressure distribution processing, and atmospheric pressure value 103MPa, good pressure distribution processing procedure is repeated 3 times, when per treatment
Between be 5min, obtain polymer dispersion liquid, then described polymer dispersion liquid is stirred 1.2 hours under conditions of 95 DEG C, obtain
To stable dispersion liquid, the dispersion liquid of described stabilization is filtered, collects sediment, is dried after water washing, obtains powder；
(2) the mixed processing of water：It is put into chopped fiber after described powder is mixed with water, carries out shear agitation 2 minutes, obtains mixing molten
Liquid, by mixed solution using spraying by the way of be added in lead powder, the adding rate of spraying be 0.33ml/s, obtain lead plaster partly into
Product；
(3) the mixed processing of acid：Add sulfuric acid while stirring in above-mentioned lead plaster semi-finished product, the adding rate of sulfuric acid is as follows：
A controls the initial adding rate of sulfuric acid in 0.22L/s when lead plaster semi-finished product temperature is in less than 48 DEG C,
The adding rate of sulfuric acid is adjusted to the 85% of initial flow rate by b when lead plaster semi-finished product temperature is between 48~57 DEG C,
The adding rate of sulfuric acid is adjusted to the 60% of initial flow rate by c when lead plaster semi-finished product temperature is between 57~68 DEG C,
D reduces flow velocity to maintain lead plaster semi-finished product temperature, keeps 5min when lead plaster semi-finished product temperature rises to 68~70 DEG C,
E continues stirring 8 minutes after sulfuric acid is added, until lead plaster semi-finished product temperature is down to 50 DEG C, obtains lead plaster finished product.
Then the carbon material dispersion effect of the lead plaster finished product to obtaining detects, and step is as follows：
(1) sample preparation：Green plate surface is coated in after lead plaster is ground, standing makes its solidification；
(2) sample：The lead plaster on the green plate after solidification is chosen using standard sample method, samples each sample 500mg, each sample
Product include the sample on sample and the different green plates for applying the cream period with piece green plate diverse location, and then green plate is lived
Property material sample is placed among test position；
(3) DSC heat analysis：Heat analysis is carried out by differential scanning calorimeter, DSC heat analysis process is carried out in a nitrogen atmosphere, is risen
Warm speed is 22 DEG C/min, and end temp is 1000 DEG C.
The temperature and characteristic peak collection of illustrative plates of sample are obtained, the differential thermal analysis curve of lead plaster is obtained after analysis, then by linear
The energy variation that integral analysis obtains exothermic process obtains testing result.
Embodiment 3
A kind of preparation method of lead plaster, step are as follows：
(1) carbon material pre-processes：Lignin sulfonate and carbon material are successively put into acetone, make described carbon material with it is wooden
Plain sulphonic acid ester is infiltrated completely, obtains mixture, then carries out ultrasound bath processing, ultrasound bath to described mixture
Bath temperature is 70 DEG C during processing, and ultrasonic time is 1 hour, obtains dispersion liquid, after by described dispersion liquid high pressure
Dispersing apparatus instrument carries out good pressure distribution processing, and atmospheric pressure value 103MPa, good pressure distribution processing procedure is repeated 2 times, when per treatment
Between be 4min, obtain polymer dispersion liquid, then described polymer dispersion liquid is stirred 1 hour under conditions of 90 DEG C, obtain
Stable dispersion liquid, the dispersion liquid of described stabilization is filtered, collect sediment, dried after water washing, obtain powder；
(2) the mixed processing of water：It is put into chopped fiber after described powder is mixed with water, carries out shear agitation 2 minutes, obtains mixing molten
Liquid, by mixed solution using spraying by the way of be added in lead powder, the adding rate of spraying be 0.25ml/s, obtain lead plaster partly into
Product；
(3) the mixed processing of acid：Add sulfuric acid while stirring in above-mentioned lead plaster semi-finished product, the adding rate of sulfuric acid is as follows：
A controls the initial adding rate of sulfuric acid in 0.21L/s when lead plaster semi-finished product temperature is in less than 48 DEG C,
The adding rate of sulfuric acid is adjusted to the 78% of initial flow rate by b when lead plaster semi-finished product temperature is between 48~57 DEG C,
The adding rate of sulfuric acid is adjusted to the 55% of initial flow rate by c when lead plaster semi-finished product temperature is between 57~68 DEG C,
D reduces flow velocity to maintain lead plaster semi-finished product temperature, keeps 4min when lead plaster semi-finished product temperature rises to 68~70 DEG C,
E continues stirring 7 minutes after sulfuric acid is added, until lead plaster semi-finished product temperature is down to 45 DEG C, obtains lead plaster finished product.
Then the carbon material dispersion effect of the lead plaster finished product to obtaining detects, and step is as follows：
(1) sample preparation：Green plate surface is coated in after lead plaster is ground, standing makes its solidification；
(2) sample：The lead plaster on the green plate after solidification is chosen using standard sample method, samples each sample 500mg, each sample
Product include the sample on sample and the different green plates for applying the cream period with piece green plate diverse location, and then green plate is lived
Property material sample is placed among test position；
(3) DSC heat analysis：Heat analysis is carried out by differential scanning calorimeter, DSC heat analysis process is carried out in a nitrogen atmosphere, is risen
Warm speed is 22 DEG C/min, and end temp is 1000 DEG C.
] temperature and the characteristic peak collection of illustrative plates of sample are obtained, the differential thermal analysis curve of lead plaster is obtained after analysis, then by linear
The energy variation that integral analysis obtains exothermic process obtains testing result.
The testing result detected to the pole plate sample of embodiment 1-3 same period is as follows：
For the sample comparative result of same pole plate diverse location, we can see that the standard deviation rate of loss of weight result is smaller,
So as to draw the preferable result of the carbon material dispersion results on each piece of pole plate, and for existing between not plates of similar polarity
The larger situation of carbon material content difference, because influence of the carbon material content difference for battery performance be not between not plates of similar polarity
Greatly, therefore can be ignored.Generally speaking, method of the invention can be uniformly distributed the carbon material in lead plaster, so as to improve
The service life of battery, and whether detection method provided by the invention intuitively can easily reflect in lead plaster carbon material distribution
Uniformly, the goal of the invention of the present invention has been reached.
Claims (10)
1. a kind of preparation method of lead plaster, it is characterised in that comprise the following steps：
（1）Carbon material pre-processes：Dispersant and carbon material are successively put into organic solvent, make described carbon material with it is described
Dispersant is infiltrated completely, obtains mixture, is then carried out ultrasound bath processing to described mixture, is obtained dispersion liquid,
Described dispersion liquid is subjected to good pressure distribution processing with good pressure distribution equipment instrument afterwards, obtains polymer dispersion liquid, then will be described
Polymer dispersion liquid stirs 0.5~1.2 hour under conditions of 85~95 DEG C, the dispersion liquid stablized, by described stabilization
Dispersion liquid filtering, collect sediment, after water washing dry, obtain powder；
（2）The mixed processing of water：Chopped fiber is put into after described powder is mixed with water, carries out shear agitation 1~2 minute, is mixed
Solution is closed, mixed solution is added in lead powder, obtains lead plaster semi-finished product；
（3）The mixed processing of acid：Add sulfuric acid while stirring in above-mentioned lead plaster semi-finished product, lead plaster finished product is obtained after acid is mixed.
A kind of 2. preparation method of lead plaster according to claim 1, it is characterised in that：Described dispersant is sulfomethylated lignin
Acid esters, sulfonated polystyrene, naphthalene sulfonic acid-formaldehyde condensation product, lauryl sodium sulfate, neopelex, polyvinyl pyrrole
One or more kinds of combinations in pyrrolidone or polyacrylic acid.
A kind of 3. preparation method of lead plaster according to claim 1, it is characterised in that：Described organic solvent be methanol,
One or more kinds of combinations in ethanol, acetone or ether.
A kind of 4. preparation method of lead plaster according to claim 1, it is characterised in that：In step（1）Described in ultrasound
Bath temperature is 58~70 DEG C during ripple water bath processing, and ultrasonic time is 0.3~1 hour.
A kind of 5. preparation method of lead plaster according to claim 1, it is characterised in that：In described step（1）Described
Good pressure distribution processing is carried out in the case where atmospheric pressure value is 103 ~ 125MPa, and good pressure distribution processing procedure repeats 2~3 times, when per treatment
Between be 3 ~ 5min.
A kind of 6. preparation method of lead plaster according to claim 1, it is characterised in that：In step（2）Described in mixing
Solution is added in lead powder by the way of spraying, and the adding rate of spraying is 0.17~0.33ml/s.
A kind of 7. preparation method of lead plaster according to claim 1, it is characterised in that：In step（3）During acid is mixed, sulphur
The adding rate of acid is as follows：
A controls the initial adding rate of sulfuric acid in 0.17~0.22L/s when lead plaster semi-finished product temperature is in less than 48 DEG C,
B when lead plaster semi-finished product temperature be in 48~57 DEG C between when, by the adding rate of sulfuric acid be adjusted to initial flow rate 70~
85%,
C when lead plaster semi-finished product temperature be in 57~68 DEG C between when, by the adding rate of sulfuric acid be adjusted to initial flow rate 50~
60%,
D reduces flow velocity to maintain lead plaster semi-finished product temperature when lead plaster semi-finished product temperature rises to 68~70 DEG C, keep 3~
5min,
E continues stirring 5~8 minutes after sulfuric acid is added, until lead plaster semi-finished product temperature is down to 43~50 DEG C, obtain lead plaster into
Product.
A kind of 8. detection method of the carbon material dispersion effect of lead plaster according to one of claim 1-7, it is characterised in that
Comprise the following steps：
（1）Sample preparation：Green plate surface is coated in after lead plaster is ground, standing makes its solidification；
（2）Sampling：The lead plaster on the green plate after solidification is chosen using standard sample method, sampling is included with piece green plate difference position
The sample on sample and the different green plates for applying the cream period put, is then placed in test position by green plate sample active
Among；
（3）DSC heat analysis：The temperature and characteristic peak collection of illustrative plates of heat analysis acquisition sample are carried out by differential scanning calorimeter, after analysis
The differential thermal analysis curve of lead plaster is obtained, the energy variation that acquisition exothermic process is then analyzed by line integral obtains detection knot
Fruit.
A kind of 9. detection method of the carbon material dispersion effect of lead plaster according to claim 8, it is characterised in that：Described
Step（3）DSC heat analysis process is carried out in a nitrogen atmosphere, and heating rate is 15~22 DEG C/min, end temp 700-
1100℃。
A kind of 10. detection method of the carbon material dispersion effect of lead plaster according to claim 8, it is characterised in that：It is described
The step of（2）The quality of sample and blank sample in sampling process is 50~600 milligrams.
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| CN108919130A (en) * | 2018-06-12 | 2018-11-30 | 风帆有限责任公司 | The detection method of additive dispersing uniformity in lead-acid storage battery negative lead plaster |
| CN111525195A (en) * | 2019-02-01 | 2020-08-11 | 骆驼集团蓄电池研究院有限公司 | Maintenance-free lead-acid storage battery with excellent deep cycle life and production method thereof |
| CN114558490A (en) * | 2022-02-24 | 2022-05-31 | 天能电池集团(马鞍山)新能源科技有限公司 | Negative mixing paste emulsified slurry adding method and mixing method applying negative mixing paste emulsified slurry |
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| CN103682329A (en) * | 2013-11-15 | 2014-03-26 | 超威电源有限公司 | Internal formation lead plaster preparation process |
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| CN108919130A (en) * | 2018-06-12 | 2018-11-30 | 风帆有限责任公司 | The detection method of additive dispersing uniformity in lead-acid storage battery negative lead plaster |
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| CN111525195A (en) * | 2019-02-01 | 2020-08-11 | 骆驼集团蓄电池研究院有限公司 | Maintenance-free lead-acid storage battery with excellent deep cycle life and production method thereof |
| CN114558490A (en) * | 2022-02-24 | 2022-05-31 | 天能电池集团(马鞍山)新能源科技有限公司 | Negative mixing paste emulsified slurry adding method and mixing method applying negative mixing paste emulsified slurry |
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