CN113224309B - Lithium-sulfur battery binder with self-repairing performance and preparation method and application thereof - Google Patents

Lithium-sulfur battery binder with self-repairing performance and preparation method and application thereof Download PDF

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CN113224309B
CN113224309B CN202110514789.2A CN202110514789A CN113224309B CN 113224309 B CN113224309 B CN 113224309B CN 202110514789 A CN202110514789 A CN 202110514789A CN 113224309 B CN113224309 B CN 113224309B
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张效洁
耿士群
姜晓霞
连双
吉海峰
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Hebei University of Technology
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Abstract

The invention relates to a lithium-sulfur battery binder with self-repairing performance and a preparation method and application thereof. The adhesive is a novel cross-linked network polymer containing a large number of sulfydryl functional group side chains, is generated by the reaction of a dithio cyclic carbonate-containing component A and an amino functional group-containing component B, and is used as an adhesive for a positive electrode material of a lithium-sulfur battery; the mutual reaction between sulfydryl is utilized to generate disulfide bonds with self-repairing performance, and then the generation of the disulfide bonds can repair the structural damage of the anode caused by the volume change of active substances in the charging and discharging processes, effectively inhibit the shuttle effect which is one of the main problems of the lithium-sulfur battery, and finally effectively improve the specific discharge capacity and the electrochemical cycle performance of the lithium-sulfur battery.

Description

Lithium-sulfur battery binder with self-repairing performance and preparation method and application thereof
The technical field is as follows:
the invention belongs to the field of lithium-sulfur battery binders. In particular to preparation and application of a lithium-sulfur battery binder with self-repairing performance.
Background art:
with the development of human society and world economy, the continuous consumption of traditional fossil fuels, accompanied by serious environmental pollution and ecological destruction, has been difficult to meet the increasing energy demand. There is a strong desire to alleviate the energy crisis through clean and renewable energy sources and practical application of high performance energy storage systems. Lithium ion batteries, as a typical rechargeable energy storage device, have been leading to global explosion. However, as the requirements of advanced portable electronic products and electric vehicles for energy density are continuously increased, the specific capacity of the lithium ion battery is closer to the theoretical limit. High energy density electrochemical energy storage technologies and systems have become a focus of research in batteries, where the development of lithium sulfur batteries is of great interest. (Advanced Energy Materials,2018,8,1802107) lithium sulfur batteries are a potential novel applicable high-performance lithium sulfur battery (Advanced Materials,2015,27, 1980-.
The binder is also called adhesive, binder, etc., and is generally a high molecular polymer. The binder is generally inert, non-conductive, and is typically added to the electrode in small doses. However, the binder plays an indispensable role in the sulfur positive electrode, and the essential role is to provide adhesion between the active material, the conductive agent, and the current collector, ensuring structural stability and integrity of the electrode during cycling. (Advanced Energy Materials,2018,8,1802107) the binder has a great influence on the performance of the entire battery, such as the specific charge-discharge capacity, the cycle life, the internal resistance, the internal pressure during rapid charging, and the like. Polyvinylidene fluoride (PVDF) is a traditional positive binder of a lithium-sulfur battery, but PVDF has the defects of limited mechanical strength, poor high-temperature resistance, easy swelling in electrolyte and the like, so that the PVDF cannot effectively inhibit the volume change of an electrode material in the charging and discharging processes, the structure of the electrode material is damaged, and the charging and discharging specific capacity and the cycling stability of the battery are reduced (Journal of Energy Chemistry,2020,43, 165-172). Therefore, research and development of high-performance binders for lithium-sulfur batteries are currently problems to be solved.
Disclosure of Invention
The invention aims to provide a lithium-sulfur battery positive electrode binder with self-repairing performance, and a preparation method and application thereof, aiming at the defects in the prior art. According to the method, a dithio cyclic carbonate-containing component A and an amino functional group-containing component B react for the first time to generate a novel cross-linked network polymer containing a large number of mercapto functional group side chains, and the novel cross-linked network polymer is used as a binder of a lithium-sulfur battery positive electrode material; the mutual reaction between sulfydryl is utilized to generate disulfide bonds with self-repairing performance, and then the generation of the disulfide bonds can repair the structural damage of the anode caused by the volume change of active substances in the charging and discharging processes, effectively inhibit the shuttle effect which is one of the main problems of the lithium-sulfur battery, and finally effectively improve the specific discharge capacity and the electrochemical cycle performance of the lithium-sulfur battery.
The technical scheme of the invention is as follows:
a lithium-sulfur battery binder with self-repairing performance is a cross-linked network polymer containing a large number of sulfydryl functional group side chains, and the structural formula of the binder is as follows:
Figure BDA0003061554130000021
wherein, the wave pattern in the structural formula represents a diffused polymer segment, and the molecular weight of the polymer is 10000-1000000 g/mol.
The preparation method of the lithium-sulfur battery binder with self-repairing performance comprises the following steps:
adding a component A containing dithio cyclic carbonate and a component B containing amino functional groups into a solvent to obtain a mixed solution, stirring and reacting for 1.5-5 h, and removing the solvent through rotary evaporation to obtain the lithium-sulfur battery binder with self-repairing performance;
wherein, the mass ratio is that the component A: component B ═ (10): (1-10); adding 8-12 mg of component A containing dithio cyclic carbonate into each gram of solvent;
the purity of the solvent is 80 percent;
the solvent is N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or water.
The component A containing dithio cyclic carbonate is ethylene glycol dithio cyclic carbonate, neopentyl glycol dithio cyclic carbonate or polyethylene glycol dithio cyclic carbonate;
the component B containing amino functional groups is polyethyleneimine, chitosan, amino cellulose or polylysine (molecular weight range: 800-100000).
The preparation method of the component A containing the dithio cyclic carbonate comprises the following steps:
adding LiBr into dichloromethane dissolved with diglycidyl ether structural component, and stirring under reflux1～3After hours, dropwise adding a carbon disulfide solution, and continuously refluxing the reaction mixture for 20-28 hours; after the reaction is finished, cooling to room temperature, diluting, extracting, washing an organic phase, drying, and performing rotary evaporation to obtain a yellow viscous oily product, namely a component A of the dithio cyclic carbonate;
wherein, 6 to 9mmol of components containing diglycidyl ether structure, 0.4 to 0.6mmol of LiBr and 12 to 18mmol of CS are added into every 20ml of anhydrous dichloromethane solvent2。
The component containing the diglycidyl ether structure and CS2The molar ratio of (a) to (b) is 1: 2.
The diglycidyl ether structure-containing component comprises: ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, or polyethylene glycol diglycidyl ether.
The adhesive is a cross-linked network polymer containing a large number of mercapto functional groups, and has self-repairing performance.
The lithium-sulfur battery binder with self-repairing performance is applied to serving as a cathode material binder of a lithium-sulfur battery.
The method specifically comprises the following steps: ball-milling and mixing the binder, a conductive agent, a positive active substance and a dispersing agent into slurry, and coating the slurry on a carbon-aluminum foil current collector with the coating thickness of 15-20 microns; and heating and drying at 60-100 ℃ to obtain the positive electrode material of the lithium-sulfur battery.
Wherein, the mass ratio is that: conductive agent: positive electrode active material: dispersant 1: 0.5-2: (6-10): (30-60);
the positive active substance of the lithium-sulfur battery is a sulfur/carbon composite material prepared by a substance D and sulfur powder through a sulfur filling method; the substance D is a carbon nano tube, acetylene black or Super P;
the conductive agent is acetylene black, Super P, a carbon nano tube or graphene;
the dispersant is N-methylpyrrolidone (NMP), N' -Dimethylformamide (DMF) or water (H)2O)；
The current collector is specifically a carbon aluminum foil.
The ball milling rotating speed is 300-600 r.min-1Mixing for 4-8 hours under the condition;
the active substance loading amount is 1.2-2 mg-cm-2。
The invention has the substantive characteristics that:
aiming at the problem of pulverization and falling off of the material caused by huge volume expansion and contraction of the lithium-sulfur battery anode, the invention firstly reacts the component A containing dithio cyclic carbonate and the component B containing polyamino functional groups to prepare a novel cross-linked network polymer containing a large number of mercapto functional group side chains. The polymer is used as a binder of the lithium-sulfur battery anode material, so that the anode material has self-repairing performance, the problem of electrode structure damage caused by volume change of the lithium-sulfur battery anode is solved, and the structure and the cycling stability of the lithium-sulfur battery anode are greatly improved.
The invention has the beneficial effects that:
the invention firstly reacts the component A containing dithio cyclic carbonate with the component B containing multi-amino functional groups to obtain a novel cross-linked network polymer containing a large number of mercapto functional group side chains, and the novel cross-linked network polymer is used as a binder of a lithium-sulfur battery anode material. The mercapto functional groups in the adhesive can react with each other to generate disulfide bonds with self-repairing performance. The disulfide bond can repair an electrode structure damaged by volume change of an electrode active material in the charging and discharging processes, so that the positive electrode of the lithium-sulfur battery has better structural stability and cycling stability. And the traditional PVDF binder for the lithium-sulfur battery has no disulfide bond with self-repairing performance, and cannot repair an electrode structure damaged due to volume change, so that the performance of the battery is poor.
As shown in the table, sample 1 is a lithium sulfur battery prepared with the novel binder, and sample 2 is a lithium sulfur battery prepared with PVDF. Compared with the prior art, under 1C, the initial specific discharge capacity of the lithium-sulfur battery prepared by the novel binder is 1253.7mAh g-1After 100 cycles, the capacity retention rate is 79.5%; while the initial specific discharge capacity of the lithium-sulfur battery prepared by the traditional PVDF is 1021.6mAh g-1And after 100 cycles, the capacity retention rate is 52.7%.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of component A obtained in example 1.
FIG. 2 is an infrared spectrum of component A obtained in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Figure BDA0003061554130000041
As shown in the reaction formula: firstly, the component containing the diglycidyl ether structure and CS are catalyzed by LiBr2The component A containing dithio cyclic carbonate is synthesized and then reacts with the component B containing polyamino functional groups with the molecular weight of 25000 at the temperature of 100 ℃ for 24 hours to obtain a cross-linked network polymer rich in sulfhydryl groups, and the cross-linked network polymer is taken as the binder of the embodiment:
Figure BDA0003061554130000042
in the above formula, the wavy patterns represent diffused polymer segments, and the molecular weight of the polymer is 10000-1000000 g/mol.
Example 1
The preparation method and the application of the binder for the positive electrode of the lithium-sulfur battery with self-repairing performance are characterized by comprising the following steps:
(1) synthesis of component A containing a dithiocyclic carbonate: ethylene glycol dithiocyclic carbonate: this was dissolved in 20mL of dry methylene chloride as a solvent for 1.32g (7.6mmol) of ethylene glycol diglycidyl ether, and 0.52g (0.6mmol) of LiBr was added thereto. After stirring at reflux for 2 hours, 1.73g (22.8mmol) of carbon disulphide are added dropwise and the reaction mixture is refluxed for 24 hours. After the reaction was complete and cooled to room temperature, the mixture was diluted with 40mL of deionized water, extracted three times with 50mL of dichloromethane and the organic phase was collected. The organic phase was again washed with 200mL of deionized water and anhydrous MgSO was added4And (5) drying. Finally, the dichloromethane was removed by rotary evaporation to give 2.18g of a yellow viscous oily product in 88% yield.
(2) Synthesizing a binder with self-repairing performance: 100mg of ethylene glycol dithiocyclic carbonate obtained in (1) and 300mg of polyethyleneimine (molecular weight: 10) were weighed3-106) And 2g of DMF (dimethyl formamide) is put in a single-mouth bottle, stirred and reacted for 2 hours, and then the DMF is removed by rotary evaporation to obtain the lithium-sulfur battery binder with self-repairing performance for later use.
Wherein ethylene glycol dithiocyclic carbonate: the mass ratio of polyethyleneimine is 1: 3, the purity of DMF is 80%.
(3) Preparing a positive electrode material of the lithium-sulfur battery by using the binder with self-repairing performance obtained in the step (2): mixing industrial sulfur powder with Super P in a ratio of 2: 1, heating at the constant temperature of 155 ℃ in an argon atmosphere for 12 hours, and cooling to room temperature to obtain the sulfur/carbon composite material for later use.
0.5000g of sulfur/carbon composite material, 0.0625g of Super P, 0.0625g of binder and 2.5g of DMF were weighed into a ball mill jar. Mixing and processing for 6 hours to be slurry under the condition that the ball milling rotating speed is 400 r/min. Coating the slurry on a carbon aluminum foil with the coating thickness of 15 mu m, drying the prepared wet pole piece in a vacuum drying oven at 80 ℃ for 12 hours, and cutting the wet pole piece into an electrode piece with the diameter of 10mm to be used as a positive electrode material of the lithium-sulfur battery for later use.
(4) Lithium sulfur secondary battery device of assembled composite material: under the condition of filling with argonIn the glove box, the pole piece prepared in the step (3) is taken as a positive electrode, the lithium piece is taken as a negative electrode material, and 1.0M LiTFSI, DOL/DME (volume ratio is 1: 1) and 1.0% LiNO are added3The mixed electrolyte and a commercial diaphragm of Celgard-2325 model are assembled into a standard button cell of CR2025 model.
Macroscopic observation experiment: after 50 cycles of charge and discharge tests on the anodes prepared with different binders on the nova battery tester, the anode material was peeled off from the separator at room temperature, and the anodes prepared with the conventional PVDF binder showed considerable active material coming off the current collector and many cracks on the surface. While the adhesive with "self-healing" properties does not have any components adhered to the separator and the surface is still intact. The volume change of the anode material in the charging and discharging process is proved that the binder plays a self-repairing role. This is because the binder contains a large number of disulfide bonds, and a network structure of disulfide bonds is formed. Because the disulfide bond is very close to the disulfide bond, when the disulfide bond is broken, the disulfide bond can be recombined to form a new disulfide bond as long as the disulfide bond is at a proper temperature (the disulfide bond is a weak covalent bond and can be self-repaired at a lower temperature), so that the material can realize self-repairing
Further, after 1g of the binder was put into 10mL of mixed electrolyte and subjected to centrifugal stirring for 5min, significant delamination occurred, indicating that the binder was not dissolved, and thus the binder was known to be a crosslinked network polymer.
Comparative example
A method of making a lithium sulfur battery comprising the steps of:
(1) mixing industrial sulfur powder with Super P in a ratio of 2: 1, heating at the constant temperature of 155 ℃ in an argon atmosphere for 12 hours, and cooling to room temperature to obtain the sulfur/carbon composite material for later use. Mixing a sulfur/carbon composite material, PVDF and Super P according to a mass ratio of 8: 1: 1 weighing 0.5000g, 0.0625g and 0.0625g in a ball milling tank, adding 2.5g DMF, mixing and processing for 6 hours to form slurry under the condition that the ball milling rotating speed is 400 r/min. Coating the slurry on a carbon aluminum foil with the coating thickness of 15 mu m, drying the prepared wet pole piece in a vacuum drying oven at 80 ℃ for 12 hours, and cutting the pole piece into an electrode piece with the diameter of 10mm to be used as a positive electrode material of a lithium battery for later use.
(2) In a glove box filled with argon, the pole piece prepared in the step (1) is taken as a positive electrode, a lithium piece is taken as a negative electrode material, and 1.0M LiTFSI, DOL/DME (volume ratio is 1: 1) and 1.0% LiNO are added3The mixed electrolyte and a commercial diaphragm of Celgard-2325 model are assembled into a standard button cell of CR2025 model.
The example is to apply the binder having self-repairing property of the present invention to the preparation of a lithium sulfur battery, and the comparative example is to fabricate a lithium sulfur battery using a conventional PVDF binder. The lithium sulfur batteries manufactured in examples and comparative examples were manufactured using the same materials and processes except for the type of binder.
In order to verify the properties of the materials obtained in the above examples and comparative examples, the following characterization and performance tests were carried out.
Nuclear magnetic hydrogen spectrum
Component A containing the dithiocyclic carbonate prepared in the examples: performing nuclear magnetic hydrogen spectrum test on the dithiocyclic carbonate, specifically dissolving the component A in deuterated dimethyl sulfoxide (DMSO-d) respectively6) In (1). The test was performed using an AVANCE400 NMR spectrometer from Brucker. The chart shows the NMR spectra of cyclic dithiocarbonates, both of which were successfully synthesized.
(II) Battery cycle Performance test
The lithium sulfur batteries prepared in examples and comparative examples were subjected to cycle performance test at a current density of 0.2C, and the negative active material loading was 1.2mg cm-2. The following table shows that the lithium-sulfur battery prepared by using the binder with self-repairing performance of the present invention has more excellent specific discharge capacity and cycle stability than the battery prepared by using PVDF as a binder.
Table binder with self-healing properties according to the invention or PVDF-corresponding electrochemical cycling test of lithium-sulfur batteries
Figure BDA0003061554130000061
Compared with the lithium-sulfur battery prepared by the traditional lithium battery binder PVDF, the initial specific discharge capacity of the lithium-sulfur battery prepared by the binder is improved by about 22.7%, and the capacity retention rate is improved by about 50.8%. Sample 1 has a high capacity retention rate and good cycle stability, while sample 2 has a fast capacity fade and poor cycle stability. It can also be seen from the table that the coulombic efficiency during the cycle of sample 1 is higher than that of sample 2, and the average coulombic efficiency for 100 cycles is 97.01%, while that of sample 2 is only 91.89%. The higher the coulombic efficiency is, the less the irreversible capacity loss in the charge-discharge process is, the stronger the polysulfide adsorption effect is, and the shuttle effect is more effectively inhibited. This is because the mercapto functional groups in the binder can react with each other to form disulfide bonds having self-repairing properties. The disulfide bond can repair an electrode structure damaged by volume change of an electrode active material in the charging and discharging processes, so that the positive electrode of the lithium-sulfur battery has better structural stability and cycling stability. Therefore, the adhesive containing the mercapto functional group and having the self-repairing performance has obvious improvement on the specific capacity and the cycling stability of the lithium-sulfur battery.
(III) Infrared Spectroscopy
The lithium-sulfur battery positive electrode binders with self-repairing performance prepared in examples 1, 2 and 3 were subjected to infrared spectroscopy, specifically, a layer of light and thin binder was coated on a pressed KBr blank sheet. The test was performed using a Brucker TENSOR 27 fourier transform infrared spectrometer. Fig. 2 is an infrared spectrum of a lithium sulfur battery positive electrode binder having self-repairing properties, showing that the lithium sulfur battery positive electrode binder having self-repairing properties has been successfully synthesized.
Example 2
The other steps are the same as the example 1, except that ethylene glycol dithiocyclic carbonate is replaced by neopentyl glycol dithiocyclic carbonate, and polyethyleneimine is replaced by amino cellulose;
the properties of the resulting material were close to those of example 1.
Example 3
The other steps are the same as the example 1, except that ethylene glycol dithiocyclic carbonate is replaced by polyethylene glycol dithiocyclic carbonate, and polyethyleneimine is replaced by chitosan;
the properties of the resulting material were close to those of example 1.
The above description is only a preferred embodiment of the present invention, but the present invention is not limited to the above-described embodiments. The foregoing detailed description is to be considered as illustrative and not restrictive, and changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention.
The invention is not the best known technology.

Claims (9)

1. A lithium-sulfur battery binder with self-repairing performance is characterized in that the binder is a cross-linked network polymer containing a sulfydryl functional group side chain, and the structural formula of the binder is as follows:
Figure 398144DEST_PATH_IMAGE001
wherein, the wave pattern in the structural formula represents a diffused polymer segment, and the molecular weight of the polymer is 10000-1000000 g/mol.
2. The method of preparing a binder for lithium-sulfur batteries with self-healing properties according to claim 1, characterized in that it comprises the following steps:
adding a component A containing dithio cyclic carbonate and a component B containing amino functional groups into a solvent to obtain a mixed solution, stirring and reacting for 1.5-5 h, and removing the solvent through rotary evaporation to obtain the lithium-sulfur battery binder with self-repairing performance;
wherein, the mass ratio is that the component A: component B = (10): (1-10); adding 8-12 mg of component A containing dithio cyclic carbonate into each gram of solvent;
the component A containing dithio cyclic carbonate is ethylene glycol dithio cyclic carbonate;
the component B containing amino functional groups is polyethyleneimine, and the molecular weight range is as follows: 800 to 100000.
3. The method of claim 2, wherein the solvent is N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), Dimethylsulfoxide (DMSO), or water.
4. The method of claim 2, wherein the dithiocyclic carbonate-containing component A is prepared by the following steps:
adding LiBr into dichloromethane dissolved with diglycidyl ether structural components, stirring for 1-3 hours under reflux, dropwise adding a carbon disulfide solution, and continuously refluxing the reaction mixture for 20-28 hours; after the reaction is finished, cooling to room temperature, diluting, extracting, washing an organic phase, drying, and performing rotary evaporation to obtain a yellow viscous oily product, namely a component A of the dithio cyclic carbonate;
wherein, 6 to 9mmol of components containing diglycidyl ether structure, 0.4 to 0.6mmol of LiBr and 12 to 18mmol of CS are added into every 20ml of anhydrous dichloromethane solvent2；
The component containing the diglycidyl ether structure and CS2The molar ratio of (a) to (b) is 1: 2;
the diglycidyl ether-containing structural components are as follows: ethylene glycol diglycidyl ether.
5. The use of a binder for lithium-sulfur batteries with self-healing properties according to claim 1, characterized by being used as a binder for the positive electrode material of lithium-sulfur batteries.
6. The use of a binder for lithium-sulfur batteries with self-healing properties according to claim 5, characterized in that it comprises in particular the following steps: ball-milling and mixing the binder, a conductive agent, a positive active substance and a dispersing agent into slurry, and coating the slurry on a carbon-aluminum foil current collector with the coating thickness of 15-20 microns; heating and drying at 60-100 ℃ to obtain the positive electrode material of the lithium-sulfur battery;
wherein, the mass ratio is that: conductive agent: positive electrode active material: dispersant = 1: 0.5-2: (6-10): (30-60).
7. Use of a binder for lithium sulphur batteries with self-healing properties according to claim 6, characterized in that the positive active material of the lithium sulphur battery: the positive active substance of the lithium-sulfur battery is a sulfur/carbon composite material prepared by a substance D and sulfur powder through a sulfur filling method; the substance D is a carbon nano tube, acetylene black or Super P;
the conductive agent is acetylene black, Super P, a carbon nano tube or graphene;
the dispersant is N-methylpyrrolidone (NMP), N' -Dimethylformamide (DMF) or water (H)2O）；
The current collector is specifically a carbon aluminum foil.
8. The use of the binder for lithium-sulfur batteries with self-repairing property according to claim 6, wherein the ball milling speed is 300-600 r-min-1Mixing and processing for 4-8 hours under the condition.
9. The use of the binder for lithium-sulfur batteries with self-repairing properties according to claim 6, wherein the loading of the active material is 1.2 to 2 mg-cm-2。
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