CN111909374A - Preparation method and application of lithium battery binder with self-repairing performance - Google Patents
Preparation method and application of lithium battery binder with self-repairing performance Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a lithium battery binder with self-repairing performance. The method comprises the following steps: adding a component A containing dithiolactone functional groups and a component B containing amino functional groups into a solvent, and reacting at 50-100 ℃ for 12 hours to obtain the polymer binder for the lithium battery with self-repairing performance; the component A containing the thiolactone function is N, N '-oxalylthiolactone, N' -malonylthiolactone, N '-succinylthiolactone, N' -glutarylthiolactone, N '-adipoylthiolactone or N, N' -sebacylthiolactone; the component B containing amino functional groups is polyethyleneimine, chitosan, amino cellulose or polylysine. The polymer binder can enable the positive electrode of the lithium battery to have the self-repairing characteristic, thereby greatly improving the problem of electrode material pulverization and being beneficial to improving the discharge specific capacity and the cycling stability of the lithium battery.
Description
The technical field is as follows:
the invention belongs to the field of lithium battery binders. In particular to preparation and application of a lithium battery binder with self-repairing performance.
Background art:
in recent years, the demand and consumption of human energy are increasing day by day, and a novel green environment-friendly high-performance secondary battery as a clean and efficient energy storage and conversion device becomes one of the fields of competitive development of countries in the world, wherein the development of lithium batteries is concerned. Lithium batteries have the advantages of high voltage, high energy density, long cycle life, low internal resistance, etc. (Nature,2001,414, 359-367). Lithium batteries include lithium ion batteries and lithium sulfur batteries, among which lithium ion batteries have been developed as one of the most widely used commercial batteries; in addition, the lithium-sulfur battery is a new lithium battery, which has a theoretical specific capacity and specific energy greater than those of the existing commercial lithium batteries, and thus is a potential new applicable high-performance lithium battery (Advanced Materials,2015,27, 1980-.
The binder is also called adhesive, binder, etc., and is generally a high molecular polymer. The binder is an important component of the positive electrode and the negative electrode of the lithium battery, and basically has the functions of providing adhesive force among the active substance, the conductive agent and the current collector and ensuring the structural stability and integrity of the electrode in the circulating process. The binder has great influence on the performance of the whole battery, such as specific charge-discharge capacity, cycle life, internal resistance, internal pressure during rapid charging and the like. Polyvinylidene fluoride (PVDF) is the most important lithium battery positive binder, 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 lithium battery binders are the current problems to be solved.
Disclosure of Invention
The invention aims to provide a preparation method and application of a lithium battery binder with self-repairing performance aiming at the defects in the prior art. The method firstly reacts a component A containing a multi-amino functional group with a component B containing a dithiolactone functional group 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 lithium battery anode material binder. The sulfydryl can react with each other to generate disulfide bonds with self-repairing performance. The disulfide bond can repair the anode structure damaged by active substance pulverization or volume change in the charging and discharging processes of the lithium battery, so that the discharging specific capacity and the electrochemical cycle performance of the lithium battery can be effectively improved.
The technical scheme of the invention is as follows:
a preparation method of a lithium battery binder with self-repairing performance comprises the following steps:
adding the component A containing the dithiolactone functional group and the component B containing the amino functional group into a solvent, reacting for 12 hours at 50-100 ℃, and concentrating, dialyzing and drying to obtain the binder for the lithium battery with self-repairing performance;
wherein, the mass ratio is that the component A: the component B is (1-10): (1-10); adding 40-60 mg of the component A into each ml of the solvent;
the solvent is N-methylpyrrolidone (NMP), N' -Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or water (H)2O)；
The component A containing the thiolactone function is N, N '-oxalylthiolactone, N' -malonylthiolactone, N '-succinylthiolactone, N' -glutarylthiolactone, N '-adipoylthiolactone or N, N' -sebacylthiolactone;
the component B containing amino functional groups is polyethyleneimine, chitosan, amino cellulose or polylysine (molecular weight range: 800-100000).
The adhesive is a cross-linked network polymer containing a large number of sulfydryl functional groups, and has self-repairing performance.
The preparation method for synthesizing the component A containing the thiolactone function comprises the following two methods:
the method comprises the following steps: dissolving DL-homocysteine thiolactone hydrochloride in anhydrous dichloromethane, adding triethylamine, cooling to 0 ℃, and then dropwise adding oxalyl chloride into the solution; stirring the reaction system at room temperature for 2 hours, and then removing the redundant solvent by rotary evaporation; drying in vacuum after washing to obtain the N, N' -oxalyl thiolactone;
wherein, 40mmol DL-homocysteine thiolactone hydrochloride, 11.1mL triethylamine and 20mmol oxalyl chloride are added into every 50mL anhydrous dichloromethane;
alternatively, method two, the synthesis steps of the remaining thiol-functional group-containing component A: adding DL-homocysteine thiolactone hydrochloride into a solution containing NaHCO3Stirring for 30 minutes; then, within 30min, dropwise adding 20mmol of diacyl chloride derivative into the mixture, stirring at room temperature overnight, carrying out suction filtration on the obtained solid, washing, filtering and drying to obtain a corresponding component A; the diacid chloride derivative is as follows: malonyl chloride, succinyl chloride, glutaryl chloride, adipoyl chloride or sebacoyl chloride;
wherein each 120ml of the extract contains NaHCO340mmol of DL-homocysteine thiolactone hydrochloride and 20mmol of diacid chloride derivatives are added into the suspending emulsion; each 120mL of the suspoemulsion contained 13.44g of NaHCO3(ii) a The solvent of the suspending emulsion is dioxane and water, and the volume ratio of the dioxane to the water is 2: 1;
the lithium battery binder with self-repairing performance is applied to a lithium battery positive electrode material; the lithium battery is a lithium ion battery or a lithium sulfur battery.
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 at 60-100 ℃ for 12 hours, and drying to obtain the lithium battery anode material for later use.
Wherein, the mass ratio is that: conductive agent: positive electrode active material: dispersant 1: 1: (5-9): (30 to 60)
Positive electrode active material for lithium battery: when the lithium ion battery is used, the positive active material is one of lithium iron phosphate, lithium cobaltate, lithium manganate and lithium nickel cobalt manganate; when the lithium-sulfur battery is used, the positive active material is acetylene black or a sulfur/carbon composite material prepared by Super P and sulfur powder through a sulfur filling method.
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 ball milling rotating speed is 300-600 r.min-1Mixing for 4-8 hours under the condition; the loading capacity of the active substance is 1.2-2 mg-cm-2。
The invention has the substantive characteristics that:
aiming at the technical problem to be solved by the lithium battery, the invention firstly reacts the component A containing the polyamino functional group and the component B containing the dithio lactone functional group to generate a novel crosslinking network polymer containing a large number of sulfydryl functional group side chains. The polymer is used as a binder of the lithium battery positive electrode material, so that the positive electrode material has self-repairing performance, the problem of pulverization of the lithium battery positive electrode material is solved, and the discharge specific capacity and the cycling stability of the lithium battery are greatly improved.
The beneficial effects of the invention are as follows:
the invention firstly reacts a component A containing a polyamino functional group with a component B containing a dithiolactone functional group 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 battery positive electrode 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 due to volume change of an electrode active material in the charging and discharging processes, so that the lithium battery obtains high discharging specific capacity and cycling stability. The traditional lithium battery binder PVDF does not have disulfide bonds with self-repairing performance, and an electrode structure damaged due to volume change cannot be repaired, so that the performance of the battery is poor.
Compared with the lithium ion battery prepared by the traditional lithium battery binder PVDF, the initial discharge specific capacity of the lithium ion battery prepared by the binder is improved by about 11.0%, and the capacity retention rate is about 97.0% (the capacity retention rate of the lithium ion battery prepared by the PVDF is 89.6%); 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 44.0%, and the capacity retention rate is about 91.0% (the capacity retention rate of the lithium-ion battery prepared by the PVDF is 25.3%), so that the binder containing the mercapto functional group and having the self-repairing performance is remarkably improved for the specific capacity and the cycling stability of the lithium battery.
Drawings
FIG. 1 shows the NMR spectra of oxalylthiolactone obtained in examples 1 and 3.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of N, N' -sebacylthiolactone obtained in examples 2 and 4.
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.
As shown in equation 1: firstly, oxalyl chloride and DL-homocysteine thiolactone hydrochloride are catalyzed by triethylamine to react to synthesize the oxalyl chloride and the DL-homocysteine thiolactone hydrochloride to obtain the oxalyl thiolactone N, N' -oxalyl thiolactone, then the oxalyl thiolactone and polyethylene imine with the molecular weight of 800 react at the temperature of 60 ℃ for 12h to obtain a cross-linked network polymer rich in sulfydryl, and the cross-linked network polymer is used as the adhesive with the self-repairing performance in the embodiments 1 and 3.
As shown in equation 2: first by NaHCO3Catalytic oxalyl chloride andDL-homocysteine thiolactone hydrochloride reacts to synthesize N, N' -oxalyl thiolactone, and then reacts with polyethyleneimine with the molecular weight of 800 at the temperature of 60 ℃ for 12 hours to obtain a cross-linked network polymer rich in sulfydryl, which is used as the adhesive with self-repairing performance in examples 2 and 4.
The binder for a lithium battery having self-repairing properties of the present invention is applied to a positive electrode of a lithium battery including a lithium ion battery and a lithium sulfur battery. Examples 1-2 are applied to the preparation of lithium ion batteries; examples 3 to 4 are applied to the preparation of lithium-sulfur batteries.
Example 1
The preparation method and the application of the binder for the lithium battery with the self-repairing performance are characterized by comprising the following steps of:
(1) disulfide lactone functional group-containing component a: synthesis of N, N' -oxalylthiolactone: 6.15g (40mmol) of DL-homocysteine thiolactone hydrochloride are weighed into 50mL of anhydrous dichloromethane, 11.1mL of triethylamine are slowly added thereto, cooling is carried out to 0 ℃ and 1.70mL (20mmol) of oxalyl chloride is added dropwise to the solution. After the reaction was stirred at room temperature for 2 hours, excess solvent was removed by rotary evaporation. The remaining solid was washed successively with 100mL of 0.1mol/L dilute hydrochloric acid, 300mL of deionized water, and the solids were dried in vacuo. Finally obtaining the N, N' -oxalylthiolactone.
(2) Synthesizing a binder for lithium ions having self-repairing properties: 100mg of dithiolactone functional group-containing N, N' -oxalylthiolactone and 200mg of polyamino functional group-containing polyethyleneimine (molecular weight of 800) are heated and reacted in 2mL of DMF at 60 ℃ for 12 hours, and then the mixture is concentrated, dialyzed and dried to obtain the self-repairing adhesive for the lithium battery for later use.
(3) Preparing the positive electrode material of the lithium ion battery by applying the binder for lithium ions with self-repairing performance obtained in the step (2): weighing 0.5000g of commercial lithium iron phosphate, 0.0625g of Super P, 0.0625g of binder and 2.5g of DMF in a ball milling tank. 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 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.
(4) Assembling the lithium ion battery device: in a glove box filled with argon, the pole piece prepared in the step (3) is taken as a positive pole, a lithium piece is taken as a negative pole, and 1M LiPF6And EC/DMC (volume ratio 1: 1) is used as electrolyte, and Celgard-2325 model commercial diaphragm is assembled into a CR2025 model standard button cell.
Example 2
The preparation method and the application of the binder for the lithium battery with the self-repairing performance are characterized by comprising the following steps of:
(1) synthesis of disulfide functional group-containing component AN, N' -sebacoyl thiolactone: 6.15g (40mmol) of DL-homocysteine thiolactone hydrochloride are weighed into a container containing 13.44g of NaHCO3In a suspension of dioxane and water, the volume ratio of dioxane to water is 2: 1 (total 120ml) and the mixture was stirred for 30 minutes. Then, 4.27mL (20mmol) of sebacoyl chloride was added dropwise to the mixture over 30min, stirred at room temperature overnight, and the resulting solid was filtered off with suction, washed with 200mL of deionized water, filtered and dried to give N, N' -sebacoyl thiolactone.
(2) Synthesizing a binder for lithium ions having self-repairing properties: 100mg of N, N' -sebacoyl thiolactone containing dithiolactone functional groups and 200mg of polyethyleneimine (with the molecular weight of 800) containing multi-amino functional groups are heated and reacted in 2mL of DMF at 60 ℃ for 12 hours, and then the binder for the lithium battery with self-repairing performance is obtained through concentration, dialysis and drying.
(3) Preparing the positive electrode material of the lithium ion battery by applying the binder for lithium ions with self-repairing performance obtained in the step (2): weighing 0.5000g of commercial lithium iron phosphate, 0.0625g of Super P, 0.0625g of binder and 2.5g of DMF in a ball milling tank. 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 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.
(4) Assembling the lithium ion battery device: in thatIn the glove box filled with argon, the pole piece prepared in the step (3) is taken as a positive electrode, the lithium piece is taken as a negative electrode, and 1M LiPF6And EC/DMC (volume ratio 1: 1) is used as electrolyte, and Celgard-2325 model commercial diaphragm is assembled into a CR2025 model standard button cell.
Example 3
The preparation method and the application of the binder for the lithium battery with the self-repairing performance are characterized by comprising the following steps of:
(1) synthesis of dithiolactone functional group-containing component AN, N' -oxalylthiolactone: 6.15g (40mmol) of DL-homocysteine thiolactone hydrochloride are weighed into 50mL of anhydrous dichloromethane, 11.1mL of triethylamine are added slowly thereto, and cooled to 0 ℃ and 1.70mL (20mmol) of oxalyl chloride are gradually added dropwise to the solution. After the reaction was stirred at room temperature for 2 hours, excess solvent was removed by rotary evaporation. The remaining solid was washed successively with 100mL of 0.1mol/L dilute hydrochloric acid, 300mL of deionized water, and the solids were dried in vacuo. Finally obtaining the N, N' -oxalylthiolactone.
(2) Synthesizing a binder for lithium ions having self-repairing properties: 100mg of dithiolactone functional group-containing N, N' -oxalylthiolactone and 200mg of polyamino functional group-containing polyethyleneimine (molecular weight of 800) are heated and reacted in 2mL of DMF at 60 ℃ for 12 hours, and then the mixture is concentrated, dialyzed and dried to obtain the self-repairing adhesive for the lithium battery for later use.
(3) Preparing the positive electrode material of the lithium ion battery by applying the binder for lithium ions 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 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.
(4) Group ofLithium-sulfur secondary battery device containing composite material: in a glove box filled with argon, the pole piece prepared in the step (3) is taken as a positive electrode, a lithium piece is taken as a negative electrode material, and 1.0M LiTFSI, DOL/DME (volume ratio 1: 1)1.0 percent LiNO is added3The mixed electrolyte and a commercial diaphragm of Celgard-2325 model are assembled into a standard button cell of CR2025 model.
Example 4
The preparation method and the application of the binder for the lithium battery with the self-repairing performance are characterized by comprising the following steps of:
(1) synthesis of disulfide functional group-containing component AN, N' -sebacoyl thiolactone: 6.15g (40mmol) of DL-homocysteine thiolactone hydrochloride are weighed into a container containing 13.44g of NaHCO3In a suspension of dioxane and water, the volume ratio of dioxane to water is 2: 1 (total 120ml) and the mixture was stirred for 30 minutes. Then, 4.27mL (20mmol) of sebacoyl chloride was added dropwise to the mixture over 30min, stirred at room temperature overnight, and the resulting solid was filtered off with suction, washed with 200mL of deionized water, filtered and dried to give N, N' -sebacoyl thiolactone.
(2) Synthesizing a binder for lithium ions having self-repairing properties: 100mg of N, N' -sebacoyl thiolactone containing dithiolactone functional groups and 200mg of polyethyleneimine (with the molecular weight of 800) containing multi-amino functional groups are heated and reacted in 2mL of DMF at 60 ℃ for 12 hours, and then the binder for the lithium battery with self-repairing performance is obtained through concentration, dialysis and drying.
(3) Preparing the positive electrode material of the lithium ion battery by applying the binder for lithium ions 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. Heating at 155 ℃ for 12 hours in an argon atmosphere at constant temperature, 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 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.
(4) Lithium sulfur secondary battery device of assembled composite material: in a glove box filled with argon, the pole piece prepared in the step (3) 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.
Comparative example 1
A preparation method of a lithium battery comprises the following steps
(1) Commercial lithium iron phosphate, PVDF and Super P are mixed 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 pole, a lithium piece is taken as a negative pole, and 1M LiPF6And EC/DMC (volume ratio 1: 1) is used as electrolyte, and Celgard-2325 model commercial diaphragm is assembled into a CR2025 model standard button cell.
Comparative example 2
The preparation method of the lithium-sulfur battery comprises the following steps
(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 thatIn the 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 of 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.
Examples 1-2 are preparations in which the binder having self-repairing property of the present invention is applied to a lithium ion battery, and comparative example 1 is a lithium ion battery manufactured using a conventional PVDF binder. The lithium ion batteries manufactured in examples 1 to 2 and comparative example 1 were prepared using the same materials and processes except for the type of the binder.
Examples 3 to 4 are preparations in which the binder having self-repairing property of the present invention is applied to a lithium sulfur battery, and comparative example 2 is a lithium sulfur battery fabricated using a conventional PVDF binder. Examples 3 to 4 and comparative example 2 were fabricated using the same materials and process, except that the binder was used.
To verify the properties of the materials obtained in examples 1 to 4 and comparative examples 1 to 2, the following alignment was performed for the relevant characterization and performance tests.
Nuclear magnetic hydrogen spectrum
Performing nuclear magnetic hydrogen spectrum test on the components AN, N '-oxalylthiolactone and N, N' -sebacylthiolactone containing the dithiolactone functional groups prepared in the examples 1-4, and 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. FIGS. 1 and 2 are NMR spectra of oxalylthiolactone and sebacylthiolactone, respectively, showing that both were successfully synthesized.
(II) Battery cycle Performance test
The lithium ion batteries prepared in examples 1 to 4 and comparative example 1 and the lithium sulfur batteries prepared in examples 5 to 8 and comparative example 2 were subjected to cycle performance tests under the condition of 0.2C, respectively, and the loading amount of the positive electrode active material was 1.2mg cm-2. From tables 1 and 2, it can be seen that the lithium ion battery and the lithium sulfur battery have self-repairing function by using the composite material of the present invention, compared with the battery prepared by using PVDF as a binderThe lithium battery prepared by the binder with the performance has more excellent specific discharge capacity and cycling stability.
Table 1 binder with self-healing properties according to the invention or PVDF corresponding lithium ion battery electrochemical cycling test
Table 2 binder with self-healing properties according to the invention or PVDF corresponding lithium-sulfur battery electrochemical cycling test
Compared with the lithium ion battery prepared by the traditional lithium battery binder PVDF, the initial discharge specific capacity of the lithium ion battery prepared by the binder is improved by about 11.0 percent, and the capacity retention rate is improved by about 8.3 percent; 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 44.0%, and the capacity retention rate is improved by about 259.7%.
The above description is only a few preferred embodiments of the present invention, but the present invention is not limited to the above-mentioned 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 preparation method of a lithium battery binder with self-repairing performance is characterized by comprising the following steps:
adding a component A containing dithiolactone functional groups and a component B containing amino functional groups into a solvent, reacting for 12 hours at 50-100 ℃, and concentrating, dialyzing and drying to obtain the polymer binder for the lithium battery with self-repairing performance;
wherein, the mass ratio is that the component A: the component B is (1-10): (1-10); adding 40-60 mg of the component A into each ml of the solvent;
the component A containing the thiolactone function is N, N '-oxalylthiolactone, N' -malonylthiolactone, N '-succinylthiolactone, N' -glutarylthiolactone, N '-adipoylthiolactone or N, N' -sebacylthiolactone;
the component B containing amino functional groups is polyethyleneimine, chitosan, amino cellulose or polylysine (molecular weight range: 800-100000).
2. The method for preparing a lithium battery binder having self-repairing properties according to claim 1, wherein the solvent is N-methylpyrrolidone (NMP), N' -Dimethylformamide (DMF), Dimethylsulfoxide (DMSO), or water (H)2O)。
3. The method for preparing a lithium battery binder with self-repairing property as claimed in claim 1, wherein the binder is a cross-linked network polymer containing mercapto functional groups and has self-repairing property.
4. The process for preparing a lithium battery binder having self-healing properties according to claim 1, characterized in that said process for preparing a composition a containing thiolactone functions comprises the following two processes:
the method comprises the following steps: dissolving DL-homocysteine thiolactone hydrochloride in anhydrous dichloromethane, adding triethylamine, cooling to 0 ℃, and then dropwise adding oxalyl chloride into the solution; stirring the reaction system at room temperature for 2 hours, and then removing the redundant solvent by rotary evaporation; drying in vacuum after washing to obtain the N, N' -oxalyl thiolactone;
wherein, 40mmol DL-homocysteine thiolactone hydrochloride, 11.1mL triethylamine and 20mmol oxalyl chloride are added into every 50mL anhydrous dichloromethane;
or, method two, the restSynthesis procedure of the thiolactone-containing component A: adding DL-homocysteine thiolactone hydrochloride into a solution containing NaHCO3Stirring for 30 minutes; then, within 30min, dropwise adding 20mmol of diacyl chloride derivative into the mixture, stirring at room temperature overnight, carrying out suction filtration on the obtained solid, washing, filtering and drying to obtain a corresponding component A; the diacid chloride derivative is as follows: malonyl chloride, succinyl chloride, glutaryl chloride, adipoyl chloride or sebacoyl chloride;
wherein each 120ml of the extract contains NaHCO340mmol of DL-homocysteine thiolactone hydrochloride and 20mmol of diacid chloride derivatives are added into the suspending emulsion; each 120mL of the suspoemulsion contained 13.44g of NaHCO3(ii) a The solvent of the suspending emulsion is dioxane and water, and the volume ratio of the dioxane to the water is 2: 1.
5. the use of a binder for lithium batteries having self-healing properties, prepared by the process according to claim 1, for a positive electrode material in lithium batteries.
6. Use of a lithium battery binder having self-healing properties prepared according to the method of claim 5, wherein the lithium battery is a lithium ion battery or a lithium sulfur battery.
7. Use of a lithium battery binder having self-healing properties prepared according to the method of claim 5, characterized by comprising the steps of:
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 at 60-100 ℃ for 12 hours, drying, and using the dried material as a positive electrode material of a lithium battery for later use;
wherein the mass ratio is that the adhesive: conductive agent: positive electrode active material: dispersant 1: 1: (5-9): (30-60).
8. Use of a binder for lithium batteries with self-healing properties, prepared according to the process of claim 7, characterized in that the positive active material of lithium batteries: when the lithium ion battery is used, the positive active material is one of lithium iron phosphate, lithium cobaltate, lithium manganate and lithium nickel cobalt manganate; when the lithium-sulfur battery is used, the positive active substance is acetylene black or a sulfur/carbon composite material prepared by Super P and sulfur powder through a sulfur filling method;
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)。
9. The use of a lithium battery binder having self-repairing properties prepared by the method of claim 7, wherein the ball milling rotation speed is 300 to 600 r-min-1Mixing for 4-8 hours under the condition; the loading capacity of the active substance is 1.2-2 mg-cm-2。
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| CN112652773A (en) * | 2020-12-24 | 2021-04-13 | 中山大学 | Multifunctional self-repairing binder for lithium-sulfur battery positive electrode and preparation method and application thereof |
| CN113224309A (en) * | 2021-05-12 | 2021-08-06 | 河北工业大学 | Lithium-sulfur battery binder with self-repairing performance and preparation method and application thereof |
| CN113224308A (en) * | 2021-05-12 | 2021-08-06 | 河北工业大学 | Lithium ion battery cathode binder with self-repairing performance and preparation method and application thereof |
| CN113363485A (en) * | 2021-05-28 | 2021-09-07 | 万向一二三股份公司 | Negative electrode slurry of lithium battery and preparation method thereof |
| CN117080449A (en) * | 2023-10-16 | 2023-11-17 | 瑞浦兰钧能源股份有限公司 | Self-repairing binder for battery and preparation method thereof |
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| CN113363485A (en) * | 2021-05-28 | 2021-09-07 | 万向一二三股份公司 | Negative electrode slurry of lithium battery and preparation method thereof |
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| CN117080449A (en) * | 2023-10-16 | 2023-11-17 | 瑞浦兰钧能源股份有限公司 | Self-repairing binder for battery and preparation method thereof |
| CN117080449B (en) * | 2023-10-16 | 2024-02-06 | 瑞浦兰钧能源股份有限公司 | Self-repairing binder for battery and preparation method thereof |
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