CN112240874B - Screening method of high-temperature stable lignin for storage battery - Google Patents
Screening method of high-temperature stable lignin for storage battery Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000003860 storage Methods 0.000 title claims abstract description 26
- 238000012216 screening Methods 0.000 title claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000012360 testing method Methods 0.000 claims abstract description 34
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- 238000002835 absorbance Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012086 standard solution Substances 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 238000004088 simulation Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
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- 229920005552 sodium lignosulfonate Polymers 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
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- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229940077388 benzenesulfonate Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FWVCSXWHVOOTFJ-UHFFFAOYSA-N 1-(2-chloroethylsulfanyl)-2-[2-(2-chloroethylsulfanyl)ethoxy]ethane Chemical compound ClCCSCCOCCSCCCl FWVCSXWHVOOTFJ-UHFFFAOYSA-N 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for screening high-temperature stable lignin for a storage battery. Belongs to the technical field of lead-acid storage battery additives. The method mainly solves the problems that the high-temperature resistance of lignin can only be detected after the battery is assembled, time and labor are consumed, and the relevance between the lignin and the high-temperature resistance of the battery cannot be accurately judged. It is mainly characterized in that: the method comprises the steps of simulating a battery formation environment and a high-temperature service life testing environment, detecting the dissolving amount and the stably existing residual amount of a quantitative lignin sample in sulfuric acid electrolyte, calculating the amount lost due to degradation and inactivation of lignin in the high-temperature sulfuric acid electrolyte through an ultraviolet standard curve equation, drawing a high-temperature daily dissolving-out amount curve and a high-temperature daily decomposition rate curve of the lignin, and screening out the type of the lignin which can stably exist in the high-temperature environment for a long time through data and spectrogram comparison, thereby providing a high-efficiency, stable and wide-application-range high-temperature-resistant lignin screening method for the storage battery industry.
Description
Technical Field
The invention belongs to the technical field of lead-acid storage battery additives, and particularly relates to a method for testing the high-temperature stability of a lignin additive for lead plaster of a lead-acid storage battery in sulfuric acid electrolyte.
Background
The molecular structure of lignin mainly takes phenylpropyl alkyl as a basic skeleton, active groups such as alcoholic hydroxyl, phenolic hydroxyl, methoxyl, carboxyl, carbonyl and the like exist to occupy different positions in a material structure, and meanwhile, the active functional groups influence physical, chemical, electrochemical and crystallization processes involved in the formation and disintegration processes of the active material structure in different ways. Therefore, on the premise that the same lignin can not ensure the complete consistency of the physicochemical properties, the hydrophilic and lipophilic properties and the stability under the high-temperature condition of different types of lignin have great difference; the testing method can complete the rapid discrimination of high-temperature stable lignin types on the premise of low cost, and is of great importance for the technical breakthrough of improving the high-temperature cycle life and the cold start performance after the high-temperature cycle life in the field of storage batteries.
At present, in the field of lead-acid storage batteries, lignin is mainly added into a negative electrode plate to play a role in a paste mixing process, and the lignin has the main defects that the solubility in a formed electrolyte is high, the lignin is easy to degrade or decompose and lose activity in a high-temperature circulation process, and the loss is easy to cause. In the use process of the start-stop battery and the outdoor battery, the battery can be in a high-temperature environment for a long time, the high-temperature cycle life of the battery and the cold start performance after high temperature are attenuated quickly, and the difference of the lignin types is far more obvious than the influence caused by the change of the addition amount, so that the lignin types stably existing at high temperature are selected as much as possible in the production of the raw material lignin, and the lignin can bear the challenge brought by the complex use environment (frequent charge and discharge, high and low temperature, severe pH change, strong polarization, gassing reaction and the like) while serving as a negative electrode expanding agent, so that the high-temperature resistance performance of the battery is improved.
For judging the high-temperature stability of lignin, a unified detection method does not exist in the industry at present, the traditional method for detecting the high-temperature resistance of lignin by assembling the lignin into a battery and then performing high-temperature charge-discharge circulation is time-consuming and labor-consuming, other influence factors in the battery are numerous, and the correlation between the change of the lignin and the high-temperature resistance of the battery cannot be scientifically judged. Then, a method for determining the high-temperature resistance of the sodium lignosulfonate by utilizing the fact that the sodium lignosulfonate has sulfonic groups and forms a colloid in an acidic solution and detecting the difference of the average particle size of the colloid of the sodium lignosulfonate before and after high-temperature treatment appears, but the method only aims at the detectable sodium lignosulfonate sample and has short high-temperature treatment time, the lignin samples which are put into the market at present in the field of storage batteries are various (comprising sodium lignosulfonate, sulfonated alkali lignin, artificially synthesized benzene sulfonate, naphthalene sulfonate and the like), and the high-temperature stability has a certain change trend according to the time length of the lignin in a high-temperature environment, so that the high-temperature-resistant lignin screening method which is efficient, stable and wide in application range is a problem to be solved urgently in the storage battery industry at present.
Disclosure of Invention
In order to overcome the defects in the background art, the invention provides a method for screening high-temperature stable lignin, which can screen out the lignin types which can stably exist at high temperature on the premise of not producing experimental batteries, thereby avoiding the blindness of the storage battery industry on the selection of the high-temperature lignin, and obviously prolonging the high-temperature cycle life of the storage battery and the cold start performance after high-temperature cycle through the compounding of one or more high-temperature lignin.
The technical solution of the invention is as follows: a screening method of high-temperature stable lignin for storage batteries is characterized by comprising the following steps:
(1) Preparing a lignin sample to be tested into a series of standard solutions with different concentrations in a solvent in which lignin can be completely dissolved, carrying out ultraviolet full-wavelength absorbance test, drawing an ultraviolet standard curve according to the absorbance at the position of the maximum absorption peak, and simultaneously generating a standard curve equation A = aC + b, wherein A is the absorbance, C is the concentration, and a and b are values obtained by linear simulation;
(2) Respectively dissolving more than 4 parts of the lignin samples to be detected in the sulfuric acid solution with the same density and volume, and completely sealing and placing in a water bath environment at 23-26 ℃ for 20-28 hours in a dark place;
(3) Taking out one solution, transferring the rest solutions to a high-temperature water bath environment, sealing and keeping out of the sun, and taking out after respectively standing for different days; the environment temperature of the high-temperature water bath is 40-75 ℃;
(4) Filtering each solution, placing quantitative filtrate in a quantitative lignin full solvent, carrying out ultraviolet full-wavelength absorbance test, substituting the tested absorbance data into a standard curve equation A = aC + b to obtain the concentration of lignin, and recording the concentration of the lignin to obtain a lignin sample to be tested dissolved in sulfuric acid; soaking filter paper and filter residues in a lignin full solvent for redissolution, filtering after full dissolution, then carrying out ultraviolet full-wavelength absorbance test, substituting the tested absorbance data into a standard curve equation A = aC + b to obtain the concentration of lignin, and recording the concentration of the lignin to obtain a lignin sample to be tested, which is not dissolved in sulfuric acid;
(5) Subtracting the lignin sample to be detected from the lignin sample to be detected, wherein the lignin sample to be detected is dissolved in sulfuric acid, and the lignin sample to be detected is not dissolved in the sulfuric acid, so as to obtain the lignin sample to be detected, wherein the lignin sample to be detected is degraded or decomposed to be ineffective in the sulfuric acid; then according to the high-temperature shelf days, the daily dissolution amount and the daily decomposition rate of the lignin sample to be detected can be respectively calculated; therefore, the high-temperature stability of the lignin sample to be tested can be obtained.
The standard curve equation is different according to different types, batches and test solvents of lignin, and corresponding standard curve tests need to be carried out before the standard curve equation is used each time, so that no fixed specific numerical expression exists, but the expression form can be determined to be A = aC + b, A is absorbance, C is concentration, and a and b are coefficients obtained by linear simulation.
In the step (1) of the technical solution of the invention, the series of different concentrations are all less than 100mg/L.
In the step (4) of the technical solution of the invention, the quantitative filtrate is 5ml, and the quantitative lignin complete solvent is 50ml.
In the step (1) of the technical solution of the present invention, the solvent in which the lignin is completely soluble includes sulfuric acid, water, an alkaline solution solvent and an organic solvent.
The alkaline solution solvent in the technical scheme of the invention comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium cyanide.
The organic solvent in the technical solution of the present invention includes one or more of ethanol, acetone, isopropanol, dimethyl sulfoxide, dimethylformamide and tetrahydrofuran.
In the step (2) of the technical solution of the invention, the density of the sulfuric acid solution is 1.05-1.40g/cm 3 And controlling the concentration of the lignin sample to be detected in the sulfuric acid solution to be 100-200mg/L.
In the step (1) of the technical scheme, the standard solution is accurately prepared by adopting a volumetric flask, the concentration of a series of standard solutions needs to be reduced in a certain gradient, a lignin sample to be tested is completely dissolved in a lignin complete solvent, and the number of points of the tested concentration is not less than 6.
In the high-temperature water bath environment of the step (3) of the technical scheme, the shelf days need to be gradually increased in a certain gradient, and the shortest shelf time needs to be more than 5 days.
In the step (1) of the technical solution of the invention, the concentrations of the series of standard solutions are respectively 100mg/L, 80gm/L, 60mg/L, 40mg/L, 20mg/L, 10mg/ml, 5mg/L and 2.5mg/L; in the step (2), taking more than 4 parts of the lignin sample (m) to be detected quantitatively as 9 parts; in the step (3), standing for 1 day, 3 days, 6 days, 10 days, 13 days, 16 days, 20 days, 25 days and 30 days respectively; and (4) in the steps (1) and (4), carrying out ultraviolet full-wavelength absorbance test by using an ultraviolet spectrophotometer.
According to the invention, through accurate test of the elution amount and the residual amount of quantitative lignin in acid, the amount of lignin which is degraded or decomposed and failed at high temperature is indirectly calculated, so that the advantages and disadvantages of high temperature resistance of different lignin types can be known. The research of the invention shows that after high-temperature treatment, the less the amount of lignin which is degraded or decomposed to lose efficacy is, the better the high-temperature stability of the lignin is, and the better the high-temperature cycle life and the cold start performance after high temperature of the lead-acid storage battery assembled by using the lignin are, and vice versa. The method can be applied to the model selection of the high-temperature-resistant expanding agent of the negative electrode of the lead-acid storage battery, and the rapid evaluation of the high-temperature stability of the high-temperature-resistant expanding agent of the negative electrode lignin series and the high-temperature stability of the high-temperature-resistant expanding agent of the artificially synthesized naphthalene sulfonate/benzene sulfonate series.
The method adopts an ultraviolet spectrophotometer to test the main content of the lignin, and the concentration of the lignin can be obtained by substituting the tested absorbance data into the standard curve equation A = aC + b, and the amount of the lignin can be obtained under the condition that the measurement volume is known. Note that background solution UV absorbance was removed before each test.
The invention has the beneficial effects that: (1) The high-temperature resistance of all organic expanding agent types can be efficiently and accurately evaluated on the premise of not assembling the battery; (2) The method can keep the lignin to be tested continuously in the high-temperature environment, can evaluate the stage change process of the lignin in the high-temperature environment more comprehensively, and can evaluate the high-temperature stability of the lignin more accurately.
The method is mainly used for testing the high-temperature stability of the lignin for the lead paste of the lead-acid storage battery and screening the types of the lignin.
Drawings
FIG. 1 is a standard curve chart and a standard curve equation of lignin G in example 1 of the present invention.
FIG. 2 is a standard curve chart and a standard curve equation of lignin H in example 1 of the present invention.
FIG. 3 is a graph showing the relationship between the daily elution amounts of lignin G and lignin H in example 1 of the present invention.
FIG. 4 is a graph showing the relationship between the daily decomposition rates of lignin G and lignin H in example 1 of the present invention.
FIG. 5 is a graph showing the relationship between the daily elution amounts of lignin W and lignin J in example 2 of the present invention.
FIG. 6 is a graph showing the relationship between the daily decomposition rates of lignin W and lignin J in example 2 of the present invention.
FIG. 7 is a graph showing the relationship between the daily elution amounts of the synthetic swelling agent T and the synthetic swelling agent N in example 3 of the present invention.
FIG. 8 is a graph showing the relationship between the daily decomposition rates of a synthetic swelling agent T and a synthetic swelling agent N in example 3 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings for better understanding of the present invention, but the following examples are only preferred embodiments of the present invention, and not all of them. Other embodiments obtained by persons skilled in the art without making creative efforts based on the embodiments in the implementation belong to the protection scope of the invention.
The invention relates to a screening method of high-temperature stable lignin for a storage battery, which comprises the following steps:
(1) Preparing a lignin sample to be tested into a series of standard solutions with different concentrations and concentrations less than 100mg/L in a lignin total solvent, performing ultraviolet full-wavelength (200-800 nm) absorbance test by using an ultraviolet spectrophotometer, respectively recording the absorbance A at the position of the maximum absorption peak, drawing an ultraviolet standard curve according to the test result and simultaneously generating a standard curve equation A = aC + b; wherein A is an absorbance value, C is a concentration, and a and b are values obtained by linear simulation;
the measurable lignin types comprise lignin series products such as lignosulfonate, alkali lignin, sulfonated alkali lignin, enzymatic lignin and the like, lignin modified products, artificially synthesized naphthalene sulfonate, benzene sulfonate and other novel synthetic expanding agents;
the lignin complete solvent comprises sulfuric acid, water, an alkaline solution solvent and an organic solvent, and the types of the solvents which can be completely dissolved are found out; wherein the alkaline solution solvent comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium cyanide; the organic solvent comprises one or more of ethanol, acetone, isopropanol, dimethyl sulfoxide, dimethylformamide and tetrahydrofuran;
the standard solution is accurately prepared by a volumetric flask, the concentration of the series of standard solutions needs to be reduced in a certain gradient, for example, the concentration can be respectively 100mg/L, 80mg/L, 60mg/L, 40mg/L, 20mg/L, 10mg/L, 5mg/L and 2.5mg/L, the lignin sample to be tested is completely dissolved in the lignin total solvent, and the number of test concentration points is not less than 6;
(2) Respectively dissolving more than 4 parts of the lignin sample m to be detected in sulfuric acid solution with the same density and volume, wherein the density of the sulfuric acid solution is 1.05-1.40g/cm 3 Controlling the concentration of the lignin sample to be detected in the sulfuric acid solution to be 100-200mg/L, and completely sealing and placing in a water bath environment at 23-26 ℃ for 24-28h in a dark place;
the lignin sample m to be detected, which is more than 4 parts in quantity, can be 9 parts;
(3) Taking out one solution, transferring the rest solutions to a high-temperature water bath environment, sealing and keeping out of the sun, and taking out after respectively standing for different days; the temperature of the high-temperature water bath environment is 40-75 ℃;
the shelf days can gradually increase in a certain gradient, and the shortest shelf time needs to be more than 5 days;
the shelf life can be 1 day, 3 days, 6 days, 10 days, 13 days, 16 days, 20 days, 25 days, 30 days;
(4) Filtering each solution, putting 5ml of quantitative filtrate into 50ml of quantitative lignin total solvent for complete dissolution, carrying out ultraviolet full-wavelength absorbance test by adopting an ultraviolet spectrophotometer, substituting the tested absorbance data into a standard curvilinear equation to obtain the concentration of lignin, and recording the concentration to obtain a lignin sample m1 to be tested, wherein the lignin sample is dissolved in sulfuric acid; soaking filter paper and filter residues in a lignin complete solvent for redissolution, filtering after complete dissolution, performing ultraviolet full-wavelength absorbance test by using an ultraviolet spectrophotometer, substituting the tested absorbance data into a standard curve equation to obtain the concentration of lignin, and recording the concentration to obtain a lignin sample m2 to be tested, which is not dissolved in sulfuric acid;
(5) Subtracting the lignin sample m to be detected from the lignin sample m to be detected by the lignin sample m1 to be detected dissolved in sulfuric acid and the lignin sample m2 to be detected not dissolved in the sulfuric acid to obtain a lignin sample m3 to be detected, wherein the lignin sample m is degraded or decomposed to be invalid in the sulfuric acid; then according to the days of high-temperature shelf, the daily dissolution amount and the daily decomposition rate of the lignin sample to be detected can be respectively calculated; therefore, the high-temperature stability of the lignin sample to be tested can be obtained.
The UV spectrophotometer used in the examples was a UV-7000 UV-visible spectrophotometer.
The method is mainly characterized in that a battery formation environment and a high-temperature service life testing environment are simulated, the dissolving amount and the stably existing residual amount of a quantitative lignin sample in sulfuric acid electrolyte are regularly monitored and quantitatively detected, the loss amount of lignin in the high-temperature sulfuric acid electrolyte due to degradation and inactivation can be calculated according to an ultraviolet standard curve equation, a high-temperature daily dissolving amount curve and a high-temperature daily decomposition rate curve of the lignin are drawn, and the type of the lignin which can stably exist in the high-temperature environment for a long time is screened out through data and spectrogram comparison, so that a high-efficiency, stable and wide-application-range high-temperature-resistant lignin screening method is provided for the storage battery industry.
Example 1
(1) Selecting two lignosulfonate products H and G, preparing a series of standard solutions with lignin concentrations of 100mg/L, 50mg/L, 25mg/L, 12.5mg/L, 6.25mg/L, 3.125mg/L and 1.5625mg/L from 4G/L of NaOH solution respectively, wherein the balance adopts an analytical balance and adopts a volumetric flask for constant volume; the standard curve chart is shown in attached figures 1 and 2;
(2) Performing ultraviolet full-wavelength test by using an ultraviolet visible spectrophotometer, recording an ultraviolet absorption value A at the maximum absorption wavelength, drawing a standard curve A = aC + b of the lignin in an alkaline solvent by using the concentration and the light absorption value, and requiring R 2 >99.9%, wherein A is absorbance, C is concentration in mg/L, and a and b are values obtained by linear simulation;
the standard curve equation of lignin G in this UV standard curve test is: a =0.01097+0.01273C, where A denotes absorbance value and C denotes substance concentration in mg/L; the standard curve equation of lignin H in this UV standard curve test is: a =0.01360+0.01311C, where A denotes absorbance values and C denotes substance concentration in mg/L;
(3) The temperature is 60 ℃, and the density of sulfuric acid is 1.19g/cm 3 For testing the electrolyte environment at high temperature, 6 parts of 30 mg lignin are weighed into 6 containers containing 1.19g/cm 3 Weighing the total weight of the system in a 200mL volumetric flask of sulfuric acid;
(4) Placing in 25 deg.C water bath, sealing, keeping out of the sun, standing for 24 hr, placing in 60 deg.C water bath, and standing 6 parts samples for 1 day, 3 days, 6 days, 10 days, 13 days, and 16 days; after each beaker is kept stand for a set time, taking out the beaker from a water bath tank for weighing, supplementing water to the initial weight, stirring and uniformly mixing the beaker with a glass rod, and filtering the beaker with slow quantitative filter paper;
(5) Dissolving 5mL of filtrate in 4g/L NaOH, metering the volume to 50mL, and recording the absorbance value of the test solution as A1-A6; soaking filter paper and filter residues in 200mL of 4g/L NaOH solution, completely dissolving, filtering, and testing the absorbance value of the filtrate, and marking as A10-A15; calculating concentration values corresponding to the absorbances according to the standard curve measured in the step (2);
(6) The daily elution amount and daily decomposition rate data were calculated from the concentration values, and the results are shown in Table 1 and FIGS. 3 and 4.
The H lignin is easier to dissolve out at high temperature than the G lignin, and the decomposition rate is lower, and the result shows that the H lignin is more stable than the G lignin at the high temperature of 60 ℃.
Example 2
Selecting two alkali lignin products W and J, measuring standard curves of the alkali lignin products W and J in a DMF (dimethyl formamide) full-solution, and selecting 1.19g/cm for testing the density of the electrolyte at high temperature 3 The environment temperature is 75 ℃, the testing period is 30 days, and other operation steps are the same as those of the embodiment 1; the daily elution amount and daily decomposition rate data were calculated from the concentration values, and the results are shown in Table 2 and FIGS. 5 and 6.
W lignin is easier to dissolve at high temperature than J lignin, and the decomposition rate is lower, and the result shows that the W lignin is more stable than the J lignin at the high temperature of 75 ℃.
Example 3
Selecting a benzene sulfonate swelling agent product T and a naphthalene sulfonate swelling agent product N, and measuring the contents in the total solvent of the products in a range of 1.19g/cm 3 Standard curve in sulfuric acid solution, high temperature test electrolyte density selection 1.19g/cm 3 Selecting the environment temperature to be 60 ℃, selecting the test period to be 15 days, and carrying out the other operation steps as in the example 1; the daily elution amount and daily decomposition rate data were calculated from the concentration values, and the results are shown in Table 3 and FIG. 4.
The daily dissolution rate of the T synthetic expanding agent is close to that of the N synthetic expanding agent, and the decomposition rate of the T synthetic expanding agent is higher than that of the N synthetic expanding agent under the same test environment, and the result shows that the N synthetic expanding agent is more stable than the T synthetic expanding agent under the environment of high temperature of 60 ℃.
Finally, the above embodiments and drawings are only intended to illustrate the technical solution of the present invention and not to be limiting, and although the present invention has been described in detail by the above embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention defined by the appended claims.
Claims (7)
1. A screening method of high-temperature stable lignin for storage batteries is characterized by comprising the following steps:
(1) Preparing a lignin sample to be tested into a series of standard solutions with different concentrations in a solvent in which lignin can be completely dissolved, carrying out ultraviolet full-wavelength absorbance test, drawing an ultraviolet standard curve according to the absorbance A at the position of the maximum absorption peak, and simultaneously generating a standard curve equation A = aC + b, wherein A is the absorbance, C is the concentration, and a and b are values obtained by linear simulation;
(2) Respectively dissolving more than 4 parts of the lignin sample to be detected in mass m into sulfuric acid solution with the same density and volume, and completely sealing and placing in a water bath environment at 23-26 ℃ for 20-28 hours in a dark place;
(3) Taking out one solution, transferring the rest solutions to a high-temperature water bath environment, sealing and standing in a dark place, and taking out after standing for different days; the environment temperature of the high-temperature water bath is 40-75 ℃; the shelf days are gradually increased in a certain gradient, and the shortest shelf time is more than 5 days;
(4) Filtering each solution, placing quantitative filtrate in a quantitative lignin full solvent, carrying out ultraviolet full-wavelength absorbance test, substituting the tested absorbance data into a standard curve equation A = aC + b to obtain the concentration of lignin, and recording the concentration to obtain the mass m1 of a lignin sample to be tested dissolved in sulfuric acid; soaking filter paper and filter residues in a solvent in which lignin can be completely dissolved for redissolution, filtering after complete dissolution, then carrying out ultraviolet full-wavelength absorbance test, substituting the tested absorbance data into a standard curve equation A = aC + b to obtain the concentration of the lignin, and recording the concentration of the lignin to obtain the mass m2 of the lignin sample to be tested which is not dissolved in sulfuric acid;
(5) Subtracting the mass m1 of the lignin sample to be detected dissolved in sulfuric acid and the mass m2 of the lignin sample to be detected not dissolved in sulfuric acid from the mass m of the lignin sample to be detected to obtain the mass m3 of the lignin sample to be detected, wherein the lignin sample to be detected is degraded or decomposed to be invalid in sulfuric acid; then according to the high-temperature shelf days, the daily dissolution amount and the daily decomposition rate of the lignin sample to be detected can be respectively calculated; therefore, the high-temperature stability of the lignin sample to be tested can be obtained.
2. The method for screening high-temperature stable lignin for storage batteries according to claim 1, wherein the method comprises the following steps: in the step (1), the concentration of the series of different concentrations is less than 100mg/L.
3. The method for screening high-temperature stable lignin for storage batteries according to claim 2, wherein: in the step (4), the quantitative filtrate is 5ml, and the solvent capable of completely dissolving the quantitative lignin is 50ml.
4. The method for screening high-temperature stable lignin for storage batteries according to claim 3, wherein the method comprises the following steps: in the step (1), the solvent in which the lignin can be completely dissolved comprises an alkaline solution solvent; the alkaline solution solvent comprises one or more of sodium hydroxide and potassium hydroxide.
5. The method for screening high-temperature stable lignin for storage batteries according to any one of claims 1 to 4, wherein: in the step (2), the density of the sulfuric acid solution is 1.05-1.40g/cm 3 And controlling the concentration of the lignin sample to be detected in the sulfuric acid solution to be 100-200mg/L.
6. The method for screening high-temperature stable lignin for storage batteries according to any one of claims 1 to 4, wherein: in the step (1), the standard solution is accurately prepared by a volumetric flask, the concentration of the series of standard solutions needs to be reduced in a certain gradient, the lignin sample to be tested is completely dissolved in the lignin full solvent, and the number of the test concentration points is not less than 6.
7. The method for screening high-temperature stable lignin for storage batteries according to any one of claims 1 to 4, wherein: in the step (1), the concentrations of the series of standard solutions are respectively 100mg/L, 80mg/L, 60mg/L, 40mg/L, 20mg/L, 10mg/L, 5mg/L and 2.5mg/L; in the step (2), taking more than 4 parts of the lignin sample (m) to be detected quantitatively as 9 parts; in the step (3), standing for 1 day, 3 days, 6 days, 10 days, 13 days, 16 days, 20 days, 25 days and 30 days respectively; and (4) in the steps (1) and (4), carrying out ultraviolet full-wavelength absorbance test by using an ultraviolet spectrophotometer.
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| JP2006351254A (en) * | 2005-06-14 | 2006-12-28 | Shin Kobe Electric Mach Co Ltd | Quantitative determination method of lignin |
| CN104089912A (en) * | 2014-06-30 | 2014-10-08 | 浙江天能电池(江苏)有限公司 | Method for determining dissolved quantity of lignin |
| CN104819948A (en) * | 2015-05-19 | 2015-08-05 | 山东大学 | Method for measuring content of dissoluble lignin by utilizing Coomassie brilliant blue G-250 |
| CN105758773A (en) * | 2016-04-14 | 2016-07-13 | 天能电池集团有限公司 | Detection method of high-temperature resistance of sodium lignosulphonate |
| CN107664618A (en) * | 2017-07-20 | 2018-02-06 | 山东金科力电源科技有限公司 | The method of testing of lignosulphonic acid sodium content in lead-acid accumulator green plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006351254A (en) * | 2005-06-14 | 2006-12-28 | Shin Kobe Electric Mach Co Ltd | Quantitative determination method of lignin |
| CN104089912A (en) * | 2014-06-30 | 2014-10-08 | 浙江天能电池(江苏)有限公司 | Method for determining dissolved quantity of lignin |
| CN104819948A (en) * | 2015-05-19 | 2015-08-05 | 山东大学 | Method for measuring content of dissoluble lignin by utilizing Coomassie brilliant blue G-250 |
| CN105758773A (en) * | 2016-04-14 | 2016-07-13 | 天能电池集团有限公司 | Detection method of high-temperature resistance of sodium lignosulphonate |
| CN107664618A (en) * | 2017-07-20 | 2018-02-06 | 山东金科力电源科技有限公司 | The method of testing of lignosulphonic acid sodium content in lead-acid accumulator green plate |
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