CN111961219A - Photo-crosslinking silk fibroin aqueous binder and preparation method and application thereof - Google Patents
Photo-crosslinking silk fibroin aqueous binder and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a photo-crosslinking silk fibroin aqueous binder, wherein the photo-crosslinking silk fibroin aqueous binder is mainly prepared by carrying out covalent crosslinking on methacrylated silk fibroin through a photo-initiator-initiated polymerization reaction. The photo-crosslinking silk fibroin aqueous binder provided by the invention has strong binding power and obviously improved electrochemical performance, is applied to preparing an electrode of a lithium ion battery, improves the integrity of the electrode and enhances the stability of the electrode, thereby improving the electrochemical performance such as the cycle performance, the rate performance and the like of the electrode.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a photo-crosslinking silk fibroin aqueous binder, a preparation method thereof and application thereof in preparation of a lithium ion battery electrode.
Background
Although the lithium-sulfur battery has the advantages of high theoretical specific capacity, high energy density, low price, no pollution and the like, the shuttle effect of lithium polysulfide in the charging and discharging processes of the lithium-sulfur battery and the complex solid-liquid-solid phase change in the charging and discharging processes of a sulfur positive electrode active material seriously hinder the practical application and the industrialized development of the lithium-sulfur battery.
In general, a typical sulfur positive electrode of a lithium sulfur battery is composed of a current collector, a sulfur positive electrode active material with electrochemical activity, a conductive carbon additive and a polymer binder, and although the sulfur positive electrode itself has no electrochemical reaction activity, is not conductive and occupies a small mass proportion (generally less than 10%) in an electrode material, the binder is a very important component in the sulfur positive electrode of the lithium sulfur battery and has a great influence on the electrochemical performance of the battery. Currently, the functions that can be realized by the binders for lithium-sulfur batteries disclosed in the prior art are mainly classified into the following: (1) ensuring intimate contact between the active substance sulphur particles and the conductive carbon additive; (2) providing strong and effective adhesive force to enable the S/C active material to be tightly attached to the current collector; (3) buffering the huge volume change of elemental sulfur in the charging and discharging process and maintaining the structural integrity of the electrode, for a sulfur anode with higher active material load, the function of maintaining the structural integrity of the anode of the polymer adhesive is particularly important; (4) promoting the transmission of lithium ions in the sulfur anode and the transfer of electrons in the sulfur anode; (5) some physicochemical interaction with polysulfides occurs to capture soluble lithium polysulfides; (6) promoting the kinetics of the oxidation-reduction reaction of polysulfides.
The binders currently used are mainly PVDF (polyvinylidene fluoride) and PEO (polyethylene oxide). PEO is a crystalline, thermoplastic, water-soluble ether resin produced by ring-opening polymerization of ethylene oxide, and has the advantages of good ion-conducting property and poor adhesiveness. Although PVDF has a certain adhesive strength and high electrochemical stability, the shuttling phenomenon of lithium polysulfide cannot be reduced, and the poor mechanical properties of PVDF also make the positive electrode structure unstable, and a toxic organic solvent N-methyl pyrrolidone (NMP) is needed in the process of preparing electrode slurry by using PVDF as a binder.
Disclosure of Invention
The present invention is directed to a photo-crosslinking aqueous silk fibroin binder to solve at least one of the above problems.
According to one aspect of the present invention, there is provided a photo-crosslinking aqueous silk fibroin binder, which is prepared by a method comprising the steps of:
(1) dissolving sodium carbonate in deionized water to obtain a sodium carbonate solution;
(2) adding silkworm cocoon into sodium carbonate solution, heating to 80-100 deg.C, maintaining for 1-2 hr, filtering, and drying the residue to obtain fibroin;
(3) adding fibroin into a lithium bromide solution, and adding glycidyl methacrylate for reaction;
(4) filtering the solution reacted in the step (3), and dialyzing the filtrate to obtain a methacrylated silk fibroin solution;
(5) separately packaging a photoinitiator and a methacrylated silk fibroin solution to obtain a photo-crosslinking silk fibroin aqueous binder; when in use, the photoinitiator is added into the methacrylated silk fibroin solution, and the solution is irradiated by a UV lamp after being dissolved.
The preparation method of the photo-crosslinking silk fibroin aqueous binder provided by the invention is characterized in that methacrylic acid groups are introduced into silk fibroin containing amino groups to obtain methacrylated silk fibroin, and when the photo-crosslinking silk fibroin aqueous binder is used, polymerization is initiated by a photoinitiator to obtain the photo-crosslinking silk fibroin binder with binding performance. In the photo-crosslinking silk fibroin binder provided by the invention, abundant amino and hydroxyl groups on silk fibroin molecules have strong adsorption effect on polysulfide, the performance of the polymer binder can be obviously improved, the shuttle effect in the circulation process is relieved, the integrity of an electrode can be improved and the stability of the electrode can be enhanced through a covalent network provided by photo-crosslinking, and thus the electrochemical performance of the lithium ion battery electrode under the long-term circulation condition can be improved.
In some embodiments, in step (1), the pH of the deionized water may be 6.8 to 7.4, and the concentration of the sodium carbonate solution may be 4.5 to 6 g/L.
In some embodiments, in the step (2), the solid-to-liquid ratio of the silkworm cocoon to the sodium carbonate solution may be 10 to 50 g/L.
In some embodiments, in step (3), the solid-to-liquid ratio of the silk fibroin and the lithium bromide solution can be 0.1-0.5 g/mL; the concentration of the lithium bromide solution can be 7-10M (namely 7-10 mol/L); the reaction time may be 2-8 h.
In some embodiments, in step (3), the solid-to-liquid ratio of silk fibroin to glycidyl methacrylate can be 2-10 g/mL; the concentration of glycidyl methacrylate may be 280-450mM (i.e., 280-450 mmol/L).
In some embodiments, in the step (4), the dialysis is deionized water dialysis, the dialysis treatment time is 3-5 days according to the standard that the dialysis bag is not broken by swelling, and the deionized water is replaced during the dialysis; the cut-off molecular weight of the dialysis bag is 3.5-10 kDa.
In some embodiments, the photoinitiator may be selected from one or both of photoinitiator 2959 and lithium phenyl-2, 4, 6-trimethylbenzoylphosphonate.
In some embodiments, the photoinitiator can be used in an amount of 2-10 wt% of methacrylated silk fibroin.
In some embodiments, the irradiation time of the UV lamp may be 20-120 s.
The photo-crosslinking silk fibroin aqueous binder prepared by the preparation method provided by the invention has good binding performance, and can relieve shuttle effect in a circulation process and improve the integrity of an electrode when being applied to a sulfur positive electrode of a lithium-sulfur battery, so that the electrochemical properties such as the circulation performance, the rate performance and the like of the sulfur electrode can be improved.
The application of the photo-crosslinking silk fibroin aqueous binder prepared by the invention is not limited to sulfur electrodes, and can also be applied to the preparation of other lithium ion battery electrodes, including but not limited to: lithium cobaltate positive electrode, lithium iron phosphate positive electrode, lithium cobalt manganese oxide ternary positive electrode, silicon-based negative electrode, graphite negative electrode and the like.
According to another aspect of the invention, a sulfur positive electrode of a lithium sulfur battery is provided, which comprises a current collector and a sulfur positive electrode material coated on the current collector, wherein the sulfur positive electrode material comprises the following components in parts by weight: 5-8 parts of active material, 1-4 parts of conductive agent, 0.5-1.5 parts of methacrylic acidified silk fibroin solution and 0.01-0.15 part of photoinitiator.
In some embodiments, the active material may be selected from sublimed sulfur, Li2S2、Li2S4、Li2S6、Li2S8At least one of (1).
In some embodiments, the conductive agent may be selected from at least one of acetylene black, conductive graphite, Super P, ketjen black, and carbon nanotubes.
In some embodiments, the current collector may be one of a copper foil, an aluminum foil, a copper foam, a copper plated non-woven fabric, a nickel foam, a nickel plated non-woven fabric.
Correspondingly, the invention also provides a preparation method of the sulfur anode, which comprises the following steps:
mixing and ball-milling an active material, a conductive agent, a methacrylic acid-acidified silk fibroin solution and a photoinitiator, coating the mixture on a current collector, irradiating the current collector by using a UV lamp, drying the current collector, and finally cutting a pole piece by using a cutting machine to obtain the sulfur anode.
Detailed Description
The present invention will be described in further detail with reference to embodiments. The examples are for illustration only and do not limit the invention in any way. Unless otherwise specified, the starting materials and reagents used in the examples are conventional products commercially available; the experimental methods of specific conditions not noted in the examples are conventional methods and conventional conditions well known in the art.
Example 1 preparation of photo-crosslinking type aqueous Silk fibroin Binder
The method comprises the following steps:
(1) under the action of magnetic stirring, 5.3g of sodium carbonate is added into deionized water with the amount of 1LpH being between 6.8 and 7.4 to be dissolved, so as to obtain sodium carbonate solution;
(2) adding 20g of silkworm cocoon into sodium carbonate solution, heating to 100 deg.C, maintaining for 1-2 hr, and stirring occasionally; filtering, drying the filter residue to obtain fibroin;
(3) dissolving 4g of silk fibroin in 16mL of a lithium bromide solution (containing 12.95g of lithium bromide) with the concentration of 9.3M, and adding 1.2mL of glycidyl methacrylate with the concentration of 424mM for reaction for 3 h;
(4) filtering the solution reacted in the step (3) through filter cloth, and dialyzing the solution by using a dialysis membrane with the molecular weight cutoff of 3.5-10kDa and deionized water to obtain a methacrylated silk fibroin solution (the concentration is 2.5 wt%);
(5) respectively and independently packaging a photoinitiator 2959 and the methacrylated silk fibroin solution prepared in the step (4) to obtain a photo-crosslinking silk fibroin aqueous binder; when in use, the photoinitiator 2959 is added into the methacrylated silk fibroin solution, and the solution is irradiated by a UV lamp for 20-120s after being dissolved.
EXAMPLE 2 preparation of photo-crosslinked fibroin aqueous Binder
The method comprises the following steps:
(1) under the action of magnetic stirring, 5.3g of sodium carbonate is added into deionized water with the amount of 1LpH being between 6.8 and 7.4 to be dissolved, so as to obtain sodium carbonate solution;
(2) adding 40g of silkworm cocoon into sodium carbonate solution, heating to 100 deg.C, maintaining for 1-2 hr, and stirring occasionally; filtering, drying the filter residue to obtain fibroin;
(3) dissolving 20g of silk fibroin in 100mL of 8M lithium bromide solution (containing 69.48g of lithium bromide), and adding 6mL of 424mM glycidyl methacrylate for reaction for 4 h;
(4) filtering the solution reacted in the step (3) through filter cloth, and dialyzing the solution by using a dialysis membrane with the molecular weight cutoff of 3.5-10kDa and deionized water to obtain a methacrylated silk fibroin solution (the concentration is 2.5 wt%);
(5) respectively and separately packaging a photoinitiator, namely phenyl-2, 4, 6-trimethyl benzoyl lithium phosphonate and the methacrylated silk fibroin solution prepared in the step (4), so as to obtain a photo-crosslinking silk fibroin aqueous binder; when in use, the photoinitiator lithium phenyl-2, 4, 6-trimethylbenzoylphosphonate is added into the methacrylated silk fibroin solution, and the solution is irradiated for 20-120s by a UV lamp after being dissolved.
Example 3 preparation of photo-crosslinked silk fibroin aqueous binder
The method comprises the following steps:
(1) under the action of magnetic stirring, 10.6g of sodium carbonate is added into deionized water with the amount of 2LpH between 6.8 and 7.4 to be dissolved, so that sodium carbonate solution is obtained;
(2) adding 30g of silkworm cocoon into sodium carbonate solution, heating to 80 deg.C, maintaining for 1-2 hr, and stirring occasionally; filtering, drying the filter residue to obtain fibroin;
(3) dissolving 4g of silk fibroin in 20mL of 9M lithium bromide solution (containing 15.63g of lithium bromide), adding 1.2mL of 424mM glycidyl methacrylate, and reacting for 8 h;
(4) filtering the solution reacted in the step (3) through filter cloth, and dialyzing the solution by using a dialysis membrane with the molecular weight cutoff of 3.5-10kDa and deionized water to obtain a methacrylated silk fibroin solution (the concentration is 2.5 wt%);
(5) respectively and separately packaging a photoinitiator, namely phenyl-2, 4, 6-trimethyl benzoyl lithium phosphonate and the methacrylated silk fibroin solution prepared in the step (4), so as to obtain a photo-crosslinking silk fibroin aqueous binder; when in use, the photoinitiator lithium phenyl-2, 4, 6-trimethylbenzoylphosphonate is added into the methacrylated silk fibroin solution, and the solution is irradiated for 20-120s by a UV lamp after being dissolved.
Example 4 preparation of photo-crosslinked silk fibroin aqueous binder
The method comprises the following steps:
(1) under the action of magnetic stirring, 5.3g of sodium carbonate is added into deionized water with the amount of 1LpH being between 6.8 and 7.4 to be dissolved, so as to obtain sodium carbonate solution;
(2) adding 15g of silkworm cocoon into sodium carbonate solution, heating to 90 deg.C, maintaining for 1-2 hr, and stirring occasionally; filtering, drying the filter residue to obtain fibroin;
(3) dissolving 10g of silk fibroin in 50mL of 10M lithium bromide solution (containing 43.43g of lithium bromide), and adding 3mL of 424mM glycidyl methacrylate for reaction for 6 h;
(4) filtering the solution reacted in the step (3) through filter cloth, and dialyzing the solution by using a dialysis membrane with the molecular weight cutoff of 3.5-10kDa and deionized water to obtain a methacrylated silk fibroin solution (the concentration is 2.5 wt%);
(5) respectively and independently packaging a photoinitiator 2959 and the methacrylated silk fibroin solution prepared in the step (4) to obtain a photo-crosslinking silk fibroin aqueous binder; when in use, the photoinitiator 2959 is added into the methacrylated silk fibroin solution, and the solution is irradiated by a UV lamp for 20-120s after being dissolved.
EXAMPLE 5 preparation of lithium-Sulfur Battery
The method comprises the following steps:
(1) mixing 0.8g of 2.5 wt% methacrylated silk fibroin solution prepared in example 1 (the content of methacrylated silk fibroin is 0.02g), 0.002g of photoinitiator 2959, 0.12g of sulfur powder and 0.06g of conductive agent Super P, performing ball milling in 0.2g of deionized water to prepare electrode slurry, uniformly coating the electrode slurry on a current collector aluminum foil by adopting a blade coating method, irradiating for 90s by using a UV lamp, then placing in a 60 ℃ oven for drying for 48 hours, and finally cutting out a pole piece with a corresponding size by using a cutting machine to obtain a sulfur positive pole;
(2) transferring the sulfur positive pole piece prepared in the step (1) into a glove box filled with argon and having water content less than 10ppm, weighing piece by piece, recording, and assembling the sulfur positive pole piece, a polypropylene diaphragm, electrolyte and a lithium negative pole into a battery in the glove box to obtain a lithium-sulfur battery; wherein, 1.0mol/L of lithium bistrifluoromethylsulfonyl imide and 1.0% of lithium nitrate are dissolved in 1, 2-dimethoxyethane and 1, 3-dioxolane 1: 1 the mixed solution is used as an electrolyte.
EXAMPLE 6 preparation of lithium Sulfur Battery
The method comprises the following steps:
(1) mixing 1.6g of 2.5 wt% methacrylated silk fibroin solution prepared in example 1 (the content of methacrylated silk fibroin is 0.04g), 0.002g of photoinitiator 2959, 0.24g of sulfur powder and 0.12g of conductive agent Super P, performing ball milling in 0.4g of deionized water to prepare electrode slurry, uniformly coating the electrode slurry on a current collector aluminum foil by adopting a blade coating method, irradiating for 60s by using a UV lamp, then placing in a 60 ℃ oven for drying for 48 hours, and finally cutting out a pole piece with a corresponding size by using a cutting machine to obtain a sulfur positive pole;
(2) transferring the sulfur positive pole piece prepared in the step (1) into a glove box filled with argon and having water content less than 10ppm, weighing piece by piece, recording, and assembling the sulfur positive pole piece, a polypropylene diaphragm, electrolyte and a lithium negative pole into a battery in the glove box to obtain a lithium-sulfur battery; wherein, 1.0mol/L of lithium bistrifluoromethylsulfonyl imide and 1.0% of lithium nitrate are dissolved in 1, 2-dimethoxyethane and 1, 3-dioxolane 1: 1 the mixed solution is used as an electrolyte.
EXAMPLE 7 preparation of lithium-Sulfur Battery
The method comprises the following steps:
(1) mixing 0.92g of 2.5 wt% methacrylated silk fibroin prepared in example 4 (the content of the methacrylated silk fibroin is 0.023g), 0.002g of photoinitiator 2959, 0.14g of sulfur powder and 0.07g of conductive agent Super P, performing ball milling in 0.3g of deionized water to prepare electrode slurry, uniformly coating the electrode slurry on a current collector aluminum foil by adopting a blade coating method, irradiating for 40s by using a UV lamp, then placing in a 60 ℃ oven for drying for 48 hours, and finally cutting out a pole piece with a corresponding size by using a cutting machine to obtain a sulfur positive pole;
(2) transferring the sulfur positive pole piece prepared in the step (1) into a glove box filled with argon and having water content less than 10ppm, weighing piece by piece, recording, and assembling the sulfur positive pole piece, a polypropylene diaphragm, electrolyte and a lithium negative pole into a battery in the glove box to obtain a lithium-sulfur battery; wherein, 1.0mol/L of lithium bistrifluoromethylsulfonyl imide and 1.0% of lithium nitrate are dissolved in 1, 2-dimethoxyethane and 1, 3-dioxolane 1: 1 the mixed solution is used as an electrolyte.
EXAMPLE 8 preparation of lithium Sulfur Battery
The method comprises the following steps:
(1) mixing 2.4g of 2.5 wt% methacrylated silk fibroin solution prepared in example 2 (the content of methacrylated silk fibroin is 0.06g), 0.002g of photoinitiator, namely phenyl-2, 4, 6-trimethyl benzoyl lithium phosphonate, 0.36g of sulfur powder and 0.18g of conductive agent Super P, performing ball milling in 0.6g of deionized water to prepare electrode slurry, uniformly coating the electrode slurry on a current collector aluminum foil by adopting a blade coating method, irradiating for 50s by using a UV lamp, then placing in a 60 ℃ drying oven for drying for 48 hours, and finally cutting out a pole piece with a corresponding size by using a cutting machine to obtain a sulfur positive pole;
(2) transferring the sulfur positive pole piece prepared in the step (1) into a glove box filled with argon and having water content less than 10ppm, weighing piece by piece, recording, and assembling the sulfur positive pole piece, a polypropylene diaphragm, electrolyte and a lithium negative pole into a battery in the glove box to obtain a lithium-sulfur battery; wherein, 1.0mol/L of lithium bistrifluoromethylsulfonyl imide and 1.0% of lithium nitrate are dissolved in 1, 2-dimethoxyethane and 1, 3-dioxolane 1: 1 the mixed solution is used as an electrolyte.
EXAMPLE 9 preparation of lithium Sulfur Battery
The method comprises the following steps:
(1) taking 1.08g of 2.5 wt% methacrylated silk fibroin solution prepared in example 3 (the content of methacrylated silk fibroin is 0.027g), 0.002g of photoinitiator lithium phenyl-2, 4, 6-trimethylbenzoylphosphonate, 0.16g of sulfur powder and 0.08g of conductive agent Super P, mixing, carrying out ball milling in 0.4g of deionized water to prepare electrode slurry, uniformly coating the electrode slurry on a current collector aluminum foil by adopting a blade coating method, irradiating for 20s by using a UV lamp, then placing in a 60 ℃ oven for drying for 48 hours, and finally cutting out a pole piece with a corresponding size by using a cutting machine to obtain a sulfur positive pole;
(2) transferring the sulfur positive pole piece prepared in the step (1) into a glove box filled with argon and having water content less than 10ppm, weighing piece by piece, recording, and assembling the sulfur positive pole piece, a polypropylene diaphragm, electrolyte and a lithium negative pole into a battery in the glove box to obtain a lithium-sulfur battery; wherein, 1.0mol/L of lithium bistrifluoromethylsulfonyl imide and 1.0% of lithium nitrate are dissolved in 1, 2-dimethoxyethane and 1, 3-dioxolane 1: 1 the mixed solution is used as an electrolyte.
Comparative example 1
The method comprises the following steps:
(1) mixing 0.02g of PVDF with 0.12g of sulfur powder and 0.06g of conductive agent Super P, carrying out ball milling in 0.2g of N-methylpyrrolidone to prepare electrode slurry, uniformly coating the electrode slurry on a current collector aluminum foil by adopting a blade coating method, then placing the current collector aluminum foil on a 60 ℃ drying oven for drying for 48 hours, and finally cutting out a pole piece with a corresponding size by using a cutting machine to obtain a sulfur positive pole;
(2) transferring the sulfur positive pole piece prepared in the step (1) into a glove box filled with argon and having water content less than 10ppm, weighing piece by piece, recording, and assembling the sulfur positive pole piece, a polypropylene diaphragm, electrolyte and a lithium negative pole into a battery in the glove box to obtain a lithium-sulfur battery; wherein, 1.0mol/L of lithium bistrifluoromethylsulfonyl imide and 1.0% of lithium nitrate are dissolved in 1, 2-dimethoxyethane and 1, 3-dioxolane 1: 1 the mixed solution is used as an electrolyte.
Test example 1 adhesion Performance test
Test samples:
sample 1: 0.002g of photoinitiator 2959 was added to 0.8g of the 2.5 wt% methacrylated silk fibroin solution prepared in example 1 (methacrylated silk fibroin content: 0.02g), and after stirring and dissolution, the solution was irradiated with a UV lamp for 90 seconds, thus obtaining sample 1.
Sample 2: 0.002g of photoinitiator 2959 was added to 1.6g of the methacrylated silk fibroin solution (methacrylated silk fibroin content 0.04g) having a concentration of 2.5 wt% prepared in example 1, and after stirring and dissolution, the sample 2 was irradiated with a UV lamp for 60 seconds to obtain sample 2.
Sample 3: 0.002g of photoinitiator 2959 was added to 0.92g of the methacrylated silk fibroin solution (methacrylated silk fibroin content: 0.023g) having a concentration of 2.5 wt% prepared in example 4, and after stirring and dissolution, the sample was irradiated with a UV lamp for 40 seconds, thus obtaining sample 3.
Sample 4: 0.002g of photo-initiator lithium phenyl-2, 4, 6-trimethylbenzoylphosphonate was added to 2.4g of the 2.5 wt% methacrylated silk fibroin solution prepared in example 2 (the methacrylated silk fibroin content was 0.06g), and after stirring and dissolution, the sample 4 was obtained by irradiating with a UV lamp for 50 seconds.
Sample 5: 0.002g of lithium phenyl-2, 4, 6-trimethylbenzoylphosphonate as a photoinitiator was added to 1.08g of 2.5 wt% methacrylated silk fibroin solution (methacrylated silk fibroin content: 0.027g) prepared in example 3, and after stirring and dissolution, the mixture was irradiated with a UV lamp for 20 seconds, thereby obtaining sample 5.
PVDF binder: 0.02g of PVDF was dissolved in 0.2g N-methylpyrrolidone to prepare a PVDF binder.
The test method comprises the following steps: the adhesive strength of the adhesive was reacted by testing the peel strength of the aluminum foil sheet with the aid of an universal tensile machine. The test method comprises the following steps: taking out two aluminum foil sheets with the specification of 40mm wide and 100mm long, and cleaning the aluminum foil sheets by alcohol before use; during testing, one end of two pieces of aluminum foil is coated with enough adhesive, the coating area is 5.5cm multiplied by 1.3cm, and the aluminum foil is placed in a 60 ℃ oven for 2 hours for drying after being coated; and finally, fixing one end of the stripped sample on a tension probe, stripping at 180 degrees at a constant speed of 10mm/min, and testing the stripping force in the stripping process to represent the strength of the adhesive force of the adhesive.
And (3) test results: as shown in table 1.
Table 1 adhesive Performance test results of the adhesive
| Sample (I) | Adhesive force (N) |
| Sample 1 | 5.22 |
| Sample 2 | 5.06 |
| Sample 3 | 4.76 |
| Sample No. 4 | 4.94 |
| Sample No. 5 | 4.36 |
| PVDF binder | 0.17 |
As can be seen from the results in table 1, the binding power of the photo-crosslinked silk fibroin aqueous binder prepared in example 1 of the present invention (sample 1) can be 30 times that of PVDF, and the binding power of the photo-crosslinked silk fibroin aqueous binder prepared in other examples is also significantly higher than that of PVDF, which indicates that the photo-crosslinked silk fibroin aqueous binder prepared in the present invention has more excellent binding performance than PVDF. The adhesive has excellent adhesive property, so that the contact impedance among the active substance, the conductive agent and the adhesive can be reduced, and the utilization rate of the active substance is improved; and the structural stability of the electrode in the circulating process is favorably kept, so that the circulating stability of the battery can be improved.
Test example 2 Electrical Property test of lithium-sulfur Battery
Test samples: examples 5 to 9 and comparative example 1.
The test method comprises the following steps: the test is carried out on a Land 2001A battery tester in a constant current charging and discharging mode, the cut-off voltage is 1.7-2.8V, the test current is 0.5C (836mA/g), the test temperature is 30 ℃, and the cycle number is 200.
And (3) test results: as shown in table 2.
Table 2 examples 5-9 electrochemical cycling performance of lithium-sulfur batteries prepared in comparative example 1
The results in table 2 show that, under the same test conditions, the lithium sulfur battery assembled by using the photo-crosslinking silk fibroin aqueous binder prepared by the present invention has higher initial discharge specific capacity and capacity retention rate compared with the lithium sulfur battery assembled by using the conventional PVDF binder, which indicates that the photo-crosslinking silk fibroin aqueous binder provided by the present invention can significantly improve the cycling stability of the lithium sulfur battery.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the photo-crosslinking silk fibroin aqueous binder comprises the following steps:
(1) dissolving sodium carbonate in deionized water to obtain a sodium carbonate solution;
(2) adding silkworm cocoon into sodium carbonate solution, heating to 80-100 deg.C, maintaining for 1-2 hr, filtering, and drying the residue to obtain fibroin;
(3) adding fibroin into a lithium bromide solution, and adding glycidyl methacrylate for reaction;
(4) filtering the solution reacted in the step (3), and dialyzing the filtrate to obtain a methacrylated silk fibroin solution;
(5) separately packaging a photoinitiator and a methacrylated silk fibroin solution to obtain a photo-crosslinking silk fibroin aqueous binder; when in use, the photoinitiator is added into the methacrylated silk fibroin solution, and the solution is irradiated by a UV lamp after being dissolved.
2. The preparation method according to claim 1, wherein in the step (1), the pH value of the deionized water is 6.8-7.4, and the concentration of the sodium carbonate solution is 4.5-6 g/L; in the step (2), the solid-to-liquid ratio of the silkworm cocoon to the sodium carbonate solution is 10-50 g/L.
3. The preparation method according to claim 1 or 2, wherein in the step (3), the solid-to-liquid ratio of the fibroin and the lithium bromide solution is 0.1-0.5 g/mL; the concentration of the lithium bromide solution is 7-10M; the reaction time is 2-8 h.
4. The method according to claim 3, wherein the concentration of the glycidyl methacrylate in the step (3) is 280-450 mM; the solid-liquid ratio of the fibroin to the glycidyl methacrylate is 2-10 g/mL.
5. The method according to claim 4, wherein the photoinitiator is one or two selected from the group consisting of a photoinitiator 2959 and lithium phenyl-2, 4, 6-trimethylbenzoylphosphonate.
6. The photo-crosslinking silk fibroin aqueous binder prepared by the preparation method of any one of claims 1-5.
7. The use of the photo-crosslinked silk fibroin aqueous binder of claim 6 in the preparation of lithium ion battery electrodes.
8. The sulfur positive electrode of the lithium-sulfur battery comprises a current collector and a sulfur positive electrode material coated on the current collector, wherein the sulfur positive electrode material comprises the following components in parts by weight: 5-8 parts of active material, 1-4 parts of conductive agent, 0.5-1.5 parts of methacrylic acidified silk fibroin solution and 0.01-0.15 part of photoinitiator.
9. The sulfur positive electrode of claim 8, wherein the active material is selected from the group consisting of sublimed sulfur, Li2S2、Li2S4、Li2S6、Li2S8At least one of; the conductive agent is at least one of acetylene black, conductive graphite, Super P, Ketjen black and carbon nano tubes; the photoinitiator is selected from one or two of a photoinitiator 2959 and phenyl-2, 4, 6-trimethyl benzoyl lithium phosphonate; the current collector is one of copper foil, aluminum foil, foam copper, non-woven fabric plated with copper, foam nickel and non-woven fabric plated with nickel.
10. The method for producing a sulfur positive electrode according to claim 8 or 9, comprising the steps of:
mixing and ball-milling an active material, a conductive agent, a methacrylic acid-acidified silk fibroin solution and a photoinitiator, coating the mixture on a current collector, irradiating the current collector by using a UV lamp, drying the current collector, and finally cutting a pole piece by using a cutting machine to obtain the sulfur anode.
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