CN113224394A - Low-temperature lead-carbon battery electrolyte - Google Patents
Low-temperature lead-carbon battery electrolyte Download PDFInfo
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- CN113224394A CN113224394A CN202110426539.3A CN202110426539A CN113224394A CN 113224394 A CN113224394 A CN 113224394A CN 202110426539 A CN202110426539 A CN 202110426539A CN 113224394 A CN113224394 A CN 113224394A
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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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- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
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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
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Abstract
The invention relates to a low-temperature lead-carbon battery electrolyte, belonging to the technical field of lead-acid storage batteries. The low-temperature lead-carbon battery electrolyte comprises the following raw materials in percentage by mass: 30-35% of sulfuric acid, 60-66% of deionized water, 0.05-0.2% of hydrogen bond inhibitor, 0.01-0.05% of modified sodium lignosulfonate and 0.5-1% of anhydrous sodium sulfate. The low-temperature lead-carbon battery electrolyte provided by the invention obviously reduces the viscosity of sulfuric acid under a low-temperature condition, improves the diffusion efficiency of molecules in battery separators and electrode micropores, and greatly improves the low-temperature discharge performance of the battery.
Description
Technical Field
The invention relates to a low-temperature lead-carbon battery electrolyte, belonging to the technical field of lead-acid storage batteries.
Background
Due to the fact that the low-temperature environment not only reduces the charge and discharge performance of the lead-carbon battery, but also limits the application field of the lead-carbon battery, researchers continuously develop low-temperature performance research works of the lead-acid battery applied to the fields of automobile starting, energy storage, power and the like for many years. The negative electrode active material has a specific surface area (BET) that is an order of magnitude lower than that of the positive electrode active material, resulting in that passivation of the negative electrode lead sulfate is easily caused, and thus the negative electrode plate becomes a main factor for limiting the discharge performance of the battery in a low temperature environment.
Researchers think that optimizing the connection mode of the grid structure and the electrode group is beneficial to reducing the internal resistance of the battery, thereby improving the low-temperature discharge performance of the battery, and meanwhile, the improvement of the content of the carbon material is pointed out to have certain help to improve the low-temperature performance. But the addition of the carbon material can reduce the hydrogen evolution potential of the cathode and increase the water loss of the battery. The internal resistance of the lead-acid battery is rapidly increased in a low-temperature environment, so that the ohmic polarization and concentration polarization effects of the electrode are suddenly increased, and the current utilization rate in the charging process is reduced. Meanwhile, the nucleation process of the instantaneous three-dimensional growth of the lead sulfate under the low-temperature condition is considered to be controlled by the diffusion of the electrolyte in the porous electrode. In the prior art, sodium lignosulfonate, humic acid, tannin extract and carbon materials are added into a negative active substance, which plays a certain role in improving low-temperature performance, but the action mechanisms of the additives are basically consistent, taking sodium lignosulfonate as an example:
since the negative electrode active material is spongy lead, it gradually shrinks during charge and discharge. The shrinkage of the negative plate can be prevented by adding lignin or lignosulfonate into the negative plate, and the specific action mechanism is as follows:
a. adsorbing Pb formed by discharge2+The supersaturation is reduced, thereby reducing the polarization of the electrode.
b. Inhibiting PbSO in the process of charging and discharging4Growth of crystals, prevention of coarsening of crystals, making discharge easier to proceed, andthe low-temperature high-rate discharge performance of the battery is remarkably improved.
However, the above method does not select additives from the viewpoint of reducing the viscosity of sulfuric acid. The diffusion speed of sulfuric acid in the micropores of the polar plate and the separator is influenced by temperature and viscosity, the lower the temperature, the higher the viscosity, the lower the diffusion speed, concentration polarization and electrochemical polarization are generated, and the specific resistance is increased, so that the discharge, particularly the large-current discharge characteristic and the utilization rate of active substances of the battery under the low-temperature condition are directly influenced. While the viscosity of sulfuric acid is mainly due to the strengthening or increasing of the sulfuric acid molecules and hydrogen bonds between the molecules. Therefore, it is necessary to study the viscosity reduction of sulfuric acid.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a low-temperature lead-carbon battery electrolyte which obviously reduces the viscosity of sulfuric acid under a low-temperature condition, improves the diffusion efficiency of molecules in battery separators and electrode micropores and greatly improves the low-temperature discharge performance of batteries.
The low-temperature lead-carbon battery electrolyte comprises the following raw materials in percentage by mass:
30-35% of sulfuric acid, 60-66% of deionized water, 0.05-0.2% of hydrogen bond inhibitor, 0.01-0.05% of modified sodium lignosulfonate and 0.5-1% of anhydrous sodium sulfate.
Preferably, the mass concentration of sulfuric acid is 34%.
The hydrogen bond inhibitor is urea, dimethyl sulfoxide, SCN-Salt or I-A mixture of two or more of the salts.
The preparation steps of the modified sodium lignosulphonate are as follows:
(1) dissolving sodium lignosulfonate powder in deionized water, wherein the mass fraction of the sodium lignosulfonate powder is more than 10%;
(2) adding carbon particle loaded Pd catalyst powder, and magnetically stirring;
(3) introducing hydrogen, and reacting at 10-40 ℃ for 2-6 h;
(4) filtering catalyst particles, and taking supernatant;
(5) adding 30-50% of sulfuric acid solution, and standing for 1-2 h;
(6) separating to obtain the precipitate of sodium lignosulphonate;
(7) washing the precipitate with absolute ethanol, drying at 80 deg.C under vacuum for 1h, and grinding to obtain the modified sodium lignosulfonate.
In the hydrogen bond inhibitor of the invention, urea, dimethyl sulfoxide and SCN-、I-Is an effective additive for reducing the formation of hydrogen bonds, and has no side effect on the charge-discharge reaction of the lead-carbon battery. The substances are ions with strong polarity, and when hydrogen bonds exist in the electrolyte, the electrostatic acting force in hydrogen bond molecules can be weakened, so that the function of reducing the performance of the hydrogen bonds is achieved.
On the basis of normally adding sodium lignosulfonate and other expanding agents in a negative electrode formula, carbon-carbon double bonds outside a benzene ring of the traditional sodium lignosulfonate are hydrogenated to remove pi bonds with polarity, so that the polarity of branched chain functional groups is increased, and the method has an important effect of reducing hydrogen bond combination.
Compared with the prior art, the invention has the following beneficial effects:
the invention combines the hydrogen bond characteristics and the influence factors, selects various additives with strong polarity for optimization research, simultaneously carries out addition reaction on the double bonds of the traditional sodium lignosulfonate, eliminates the pi bonds outside the benzene rings of the sodium lignosulfonate, improves the polarity of branched chain functional groups, and adds the branched chain functional groups into the electrolyte. The invention obviously reduces the viscosity of sulfuric acid under the low-temperature condition, improves the diffusion efficiency of molecules in battery separators and electrode micropores, and greatly improves the low-temperature discharge performance of batteries.
Drawings
FIG. 1 is a graph showing the internal resistance changes of a sample 3DB210 battery according to the present invention at different temperatures from a reference battery in example 1;
FIG. 2 is a graph showing the internal resistance change at different temperatures of the sample 6-DZM-10 cell of example 2 of the present invention and the reference cell.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
Firstly, preparing modified sodium lignosulfonate: the preparation method comprises the following steps:
(1) dissolving 50g of Norwegian sodium lignosulfonate powder into 200mL of deionized water in a 500mL beaker, and stirring to completely dissolve the Norwegian sodium lignosulfonate powder to obtain a sodium lignosulfonate solution with the mass fraction of 20%;
(2) adding 10g of powder of a carbon particle-loaded Pd catalyst which is purchased from market into the solution in the step (1), starting magnetic stirring, and rotating at the speed of 100 r/min;
(3) uniformly distributing 3 hydrogen pipes with the flow of 20mL/min in the container of (1), and reacting for 6 hours at the temperature of 40 ℃;
(4) filtering catalyst particles, and taking supernatant;
(5) adding 50% of sulfuric acid solution in mass fraction, and standing for 2 hours;
(6) standing and separating to obtain a precipitate of sodium lignosulphonate;
(7) and (3) washing the precipitate in the step (6) by using absolute ethyl alcohol, drying the precipitate for 1h in a vacuum drying oven at the temperature of 80 ℃, and grinding the dried precipitate and sieving the ground precipitate by using a 40-mesh sieve to obtain the modified sodium lignosulfonate.
The operations (1) to (7) were repeated to obtain the amount of the electrode solution described in this example required for the subsequent test.
The obtained modified sodium lignosulfonate is prepared by using 30% sulfuric acid solution according to the concentration of 0.01%, and the following components are also added into the solution: 0.01% of urea, 0.02% of KSCN, 0.02% of KI and 0.5% of anhydrous sodium sulfate.
Welding electrode groups of the positive plate and the negative plate of the lead-acid storage battery for the externally formed 3DB210 tractor, wherein the lead dioxide content in the positive electrode is 82.5 wt%, and the spongy lead content in the negative electrode is 79 wt%, so that the production requirement is met. The welded electrode group was placed in a cell jar, 3200g of the prepared electrolyte prepared in this example was poured in, and the level of the electrolyte was determined to be below the busbar. And carrying out a capacity test after primary charging, and carrying out a low-temperature-20 ℃ discharge test and an internal resistance test at different temperatures after the capacity test is qualified.
The initial charging method comprises the following steps: 15A for 3 h.
The normal charging method comprises the following steps: the 30A charge to 2.4V and the 15A charge for 1.15 times the discharge capacity based on the total charge.
Initial capacity testing was performed at a current of 42A (5hr) with a final voltage of 1.7V, and the discharge time was recorded at 25 ℃ room temperature and compared to a cell filled with pure sulfuric acid electrolyte (reference cell). The test structure shows that the discharge capacity of the reference battery is 218Ah, and the discharge capacity of the sample battery is 217Ah, which shows that the capacity of the sample battery does not obviously decrease when the battery is discharged at normal temperature, i.e. the battery performance is not influenced by the electrolyte formula described in the embodiment.
And during low-temperature discharge, placing the fully charged battery in an environment with the low temperature of-20 ℃ and-40 ℃ for 24 hours, then discharging at 42A, and recording the discharge time. The effect of reducing the viscosity of the sulfuric acid electrolyte with the electrolyte formulation described in this example was examined by comparing the low temperature discharge time. The test results are shown in Table 1.
TABLE 1
When measuring the internal resistance, the fully charged battery is placed on an Arbin charge-discharge instrument, and the static resistance of the battery is measured according to the pulse current of 50A and the time of 5 ms. The measurement results are shown in FIG. 1.
Example 2
Firstly, preparing modified sodium lignosulfonate: the preparation method comprises the following steps:
(1) dissolving 100g of Norwegian sodium lignosulfonate powder into 400mL of deionized water in a 1000mL beaker, and stirring to completely dissolve the Norwegian sodium lignosulfonate powder to obtain a sodium lignosulfonate solution with the mass fraction of 20%;
(2) adding 20g of powder of a carbon particle-loaded Pd catalyst which is purchased from market into the solution in the step (1), starting magnetic stirring, and rotating at the speed of 200 r/min;
(3) uniformly distributing 3 hydrogen pipes with the flow of 30mL/min in the container in the step (1), and reacting for 3 hours at the temperature of 40 ℃;
(4) filtering catalyst particles, and taking supernatant;
(5) adding a sulfuric acid solution with the mass fraction of 30%, and standing for 2 hours;
(6) standing and separating to obtain a precipitate of sodium lignosulphonate;
(7) and (3) washing the precipitate in the step (6) by using absolute ethyl alcohol, drying the precipitate for 1h in a vacuum drying oven at the temperature of 80 ℃, and grinding the dried precipitate and sieving the ground precipitate by using a 40-mesh sieve to obtain the modified sodium lignosulfonate.
The operations (1) to (7) were repeated to obtain the amount of the electrolyte described in this example required for the subsequent tests.
The obtained modified sodium lignosulfonate is prepared by using 35% sulfuric acid solution according to the concentration of 0.05%, and the following components are also added into the solution: 0.05% of urea, 0.1% of KSCN, 0.05% of KI and 1% of anhydrous sodium sulfate.
Welding electrode groups on positive and negative plates of a 12V lead-acid storage battery of the formed dry electric bicycle 6-DZM-10, wherein the content of lead dioxide in the positive electrode is 85.5 wt%, and the content of spongy lead in the negative electrode is 82 wt%, so that the production requirement is met. And (3) placing the welded 6 grids of the electrode group into a battery jar, welding the 6 grids through the wall, sealing the jar cover, and filling 96mL of the electrolyte described in the embodiment into each grid. And carrying out a capacity test after primary charging, and carrying out a low-temperature-20 ℃ discharge test and an internal resistance test at different temperatures after the capacity test is qualified.
The initial charging method comprises the following steps: 1A for 2 h.
The normal charging method comprises the following steps: 2.5A/2.4V for 6 h; 1A for 1h at room temperature.
Initial capacity testing was performed with a discharge current of 5A (2hr) at 10.5V end, and the discharge time was recorded at 25 c room temperature and compared to a cell filled with pure sulfuric acid electrolyte (reference cell). The test structure shows that the discharge capacity of the reference battery is 12.1Ah, and the discharge capacity of the sample battery is 12.2Ah, which shows that the capacity of the sample battery does not obviously change when the battery is discharged at normal temperature, namely, the electrolyte formula described in the embodiment does not influence the battery performance.
And during low-temperature discharge, placing the fully charged battery in an environment with the low temperature of-20 ℃ and-40 ℃ for 24 hours, then discharging at 5A, and recording the discharge time. The effect of reducing the viscosity of the sulfuric acid electrolyte with the electrolyte formulation described in this example was examined by comparing the low temperature discharge time. The test results are shown in Table 2.
TABLE 2
Sample (I) | Discharge at-20 deg.C | Discharge at-40 deg.C |
Sample cell | 8.7Ah | 4.8Ah |
Reference cell | 7.5Ah | 3.2Ah |
When measuring the internal resistance, the fully charged battery is placed on an Arbin charge-discharge instrument, and the static resistance of the battery is measured according to the pulse current of 10A and the time of 5 ms. The measurement results are shown in FIG. 2.
Example 3
Firstly, preparing modified sodium lignosulfonate: the preparation method comprises the following steps:
(1) dissolving 100g of Norwegian sodium lignosulfonate powder into 400mL of deionized water in a 1000mL beaker, and stirring to completely dissolve the Norwegian sodium lignosulfonate powder to obtain a sodium lignosulfonate solution with the mass fraction of 20%;
(2) adding 20g of powder of a carbon particle-loaded Pd catalyst which is purchased from market into the solution in the step (1), starting magnetic stirring, and rotating at the speed of 200 r/min;
(3) uniformly distributing 3 hydrogen pipes with the flow of 30mL/min in the container of (1), and reacting for 3 hours at the temperature of 30 ℃;
(4) filtering catalyst particles, and taking supernatant;
(5) adding 32% sulfuric acid solution in mass fraction, and standing for 1.5 h;
(6) standing and separating to obtain a precipitate of sodium lignosulphonate;
(7) and (3) washing the precipitate in the step (6) by using absolute ethyl alcohol, drying the precipitate for 1h in a vacuum drying oven at the temperature of 80 ℃, and grinding the dried precipitate and sieving the ground precipitate by using a 40-mesh sieve to obtain the modified sodium lignosulfonate.
The operations (1) to (7) were repeated to obtain the amount of the electrolyte described in this example required for the subsequent tests.
The obtained modified sodium lignosulfonate is prepared by using 32% sulfuric acid solution according to the concentration of 0.35%, and the following components are also added into the solution: 0.03 percent of urea, 0.08 percent of KSCN, 0.03 percent of KI and 0.8 percent of anhydrous sodium sulfate.
Welding electrode groups on positive and negative plates of a 12V lead-acid storage battery of the formed dry electric bicycle 6-DZM-10, wherein the content of lead dioxide in the positive electrode is 85.7 wt%, and the content of spongy lead in the negative electrode is 83.5 wt%, so that the production requirement is met. And (3) placing the welded 6 grids of the electrode group into a battery jar, welding the 6 grids through the wall, sealing the jar cover, and filling 96mL of the electrolyte described in the embodiment into each grid. And carrying out a capacity test after primary charging, and carrying out a low-temperature-20 ℃ discharge test and an internal resistance test at different temperatures after the capacity test is qualified.
The initial charging method comprises the following steps: 1A for 2 h.
The normal charging method comprises the following steps: 2.5A/2.4V for 6 h; 1A for 1h at room temperature.
Initial capacity testing was performed with a discharge current of 5A (2hr) at 10.5V end, and the discharge time was recorded at 25 c room temperature and compared to a cell filled with pure sulfuric acid electrolyte (reference cell). The test structure shows that the discharge capacity of the reference battery is 12.6Ah, and the discharge capacity of the sample battery is 11.9Ah, which shows that the capacity of the sample battery does not obviously change when the battery is discharged at normal temperature, namely, the electrolyte formula described in the embodiment does not influence the performance of the battery.
And during low-temperature discharge, placing the fully charged battery in an environment with the low temperature of-20 ℃ and-40 ℃ for 24 hours, then discharging at 5A, and recording the discharge time. The effect of reducing the viscosity of the sulfuric acid electrolyte with the electrolyte formulation described in this example was examined by comparing the low temperature discharge time. The test results are shown in Table 3.
TABLE 3
Sample (I) | Discharge at-20 deg.C | Discharge at-40 deg.C |
Sample cell | 8.5Ah | 4.6Ah |
Reference cell | 7.5Ah | 3.2Ah |
Comparative example 1
Firstly, preparing modified sodium lignosulfonate: the preparation method comprises the following steps:
(1) dissolving 100g of Norwegian sodium lignosulfonate powder into 400mL of deionized water in a 1000mL beaker, and stirring to completely dissolve the Norwegian sodium lignosulfonate powder to obtain a sodium lignosulfonate solution with the mass fraction of 20%;
(2) adding 20g of powder of a carbon particle-loaded Pd catalyst which is purchased from market into the solution in the step (1), starting magnetic stirring, and rotating at the speed of 200 r/min;
(3) uniformly distributing 3 hydrogen pipes with the flow of 30mL/min in the container of (1), and reacting for 3 hours at the temperature of 30 ℃;
(4) filtering catalyst particles, and taking supernatant;
(5) adding 32% sulfuric acid solution in mass fraction, and standing for 1.5 h;
(6) standing and separating to obtain a precipitate of sodium lignosulphonate;
(7) and (3) washing the precipitate in the step (6) by using absolute ethyl alcohol, drying the precipitate for 1h in a vacuum drying oven at the temperature of 80 ℃, and grinding the dried precipitate and sieving the ground precipitate by using a 40-mesh sieve to obtain the modified sodium lignosulfonate.
The operations (1) to (7) were repeated to obtain the amount of the electrolyte described in this example required for the subsequent tests.
The obtained modified sodium lignosulfonate is prepared by using 32% sulfuric acid solution according to the concentration of 0.35%, and the following components are also added into the solution: KI 0.14%, anhydrous sodium sulfate 0.8%.
Welding electrode groups on positive and negative plates of a 12V lead-acid storage battery of the formed dry electric bicycle 6-DZM-10, wherein the content of lead dioxide in the positive electrode is 85.9 wt%, and the content of spongy lead in the negative electrode is 84.5 wt%, so that the production requirement is met. And (3) placing the welded 6 grids of the electrode group into a battery jar, welding the 6 grids through the wall, sealing the jar cover, and filling 96mL of the electrolyte described in the embodiment into each grid. And carrying out a capacity test after primary charging, and carrying out a low-temperature-20 ℃ discharge test and an internal resistance test at different temperatures after the capacity test is qualified.
The initial charging method comprises the following steps: 1A for 2 h.
The normal charging method comprises the following steps: 2.5A/2.4V for 6 h; 1A for 1h at room temperature.
Initial capacity testing was performed with a discharge at a set current of 5A (2hr), a final voltage of 10.5V, and a discharge time at room temperature of 25 ℃ was recorded and compared with the battery of example 3.
And during low-temperature discharge, placing the fully charged battery in an environment with the low temperature of-20 ℃ and-40 ℃ for 24 hours, then discharging at 5A, and recording the discharge time. The effect of reducing the viscosity of the sulfuric acid electrolyte with the electrolyte formulation described in this example was examined by comparing the low temperature discharge time. The test results are shown in Table 4.
TABLE 4
Sample (I) | Discharge at-20 deg.C | Discharge at-40 deg.C |
EXAMPLE 3 sample cell | 8.5Ah | 4.6Ah |
Comparative example 1 sample cell | 7.8Ah | 3.8Ah |
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (5)
1. The low-temperature lead-carbon battery electrolyte is characterized in that: comprises the following raw materials in percentage by mass:
30-35% of sulfuric acid, 60-66% of deionized water, 0.05-0.2% of hydrogen bond inhibitor, 0.01-0.05% of modified sodium lignosulfonate and 0.5-1% of anhydrous sodium sulfate.
2. The low-temperature lead-carbon battery electrolyte according to claim 1, wherein: the mass concentration of sulfuric acid is 34%.
3. The low-temperature lead-carbon battery electrolyte according to claim 1, wherein: the hydrogen bond inhibitor is urea, dimethyl sulfoxide, SCN-Salt or I-A mixture of two or more of the salts.
4. The low-temperature lead-carbon battery electrolyte according to claim 1, wherein: the preparation steps of the modified sodium lignosulphonate are as follows:
(1) dissolving sodium lignosulfonate powder in deionized water, wherein the mass fraction of the sodium lignosulfonate powder is more than 10%;
(2) adding carbon particle loaded Pd catalyst powder, and magnetically stirring;
(3) introducing hydrogen, and reacting at 10-40 ℃ for 2-6 h;
(4) filtering catalyst particles, and taking supernatant;
(5) adding 30-50% of sulfuric acid solution, and standing for 1-2 h;
(6) separating to obtain the precipitate of sodium lignosulphonate;
(7) and (3) washing the precipitate by using absolute ethyl alcohol, drying under vacuum, and grinding to obtain the modified sodium lignosulfonate.
5. The low-temperature lead-carbon battery electrolyte according to claim 4, wherein: in step (7), drying is carried out for 1h at 80 ℃ under vacuum.
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CN112366367A (en) * | 2020-11-09 | 2021-02-12 | 江苏理工学院 | Aqueous lithium ion electrolyte and battery |
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