CN111129499A - Water-based conductive adhesive for lithium battery and preparation method thereof - Google Patents
Water-based conductive adhesive for lithium battery and preparation method thereof Download PDFInfo
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Abstract
The invention provides a water-based conductive binder for a lithium battery, which comprises 0.01-0.8 part of single-walled carbon nanotube, 1-10 parts of multi-walled carbon nanotube and 10-50 parts of water-based binder, wherein the outer diameter of the single-walled carbon nanotube is 0.4-40 nm, and the thickness of the tube wall is 0.4-40 nm
The length is more than or equal to 1 mu m; the outer diameter of the multi-wall carbon nanotube is 2-20 nm, and the thickness of the tube wall is
The length is 500 nm-10 cm; the length-diameter ratio of the single-walled carbon nanotube to the multi-walled carbon nanotube is more than or equal to 1000 nm. The invention adopts the simple process of one-step synthesis and one-step dispersion to prepare the water-based conductive adhesive for the lithium battery, and has the function of conductivityElectricity, bonding and dispersion performance, less consumption, reduced internal resistance of the battery, improved pole piece bonding force and improved battery cycle performance; in addition, the water-based conductive adhesive has low manufacturing cost, takes water as a solvent in the whole process, and accords with the trend of environmental protection.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a water-based conductive adhesive for a lithium battery and a preparation method thereof.
Background
Currently, there are three main categories of binders widely used in lithium ion batteries: polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR) and sodium carboxymethylcellulose (CMC), wherein the PVDF is mainly used for the oil anode of the lithium ion battery, and N-methyl pyrrolidone (NMP) is used as a solvent, so that the environment is not protected, and the cost is high; SBR and CMC are mainly used for the aqueous negative pole of the lithium ion battery, the consumption is large, and the adhesive force is poor, and the battery made of the SBR and CMC has great internal resistance and has a certain problem for the dispersion performance of the nano material; in addition, the binders do not have conductivity, and a battery manufacturer needs to add a conductive agent into positive or negative electrode pole piece slurry in the process of manufacturing a lithium battery, so that the manufacturing process of the battery is complicated, uneven dispersion among main materials of the positive and negative electrodes, the conductive agent and the binders is easily caused, the advantage of the conductive agent on the conductivity of the main materials of the positive or negative electrodes cannot be fully exerted, or the binding power of the pole pieces is not high enough, powder is easily dropped, the capacity exertion performance of the main materials of the positive or negative electrodes is damaged, and the cycle performance of the battery is not good. Therefore, in order to simplify the pulping process, adapt to the current environmental protection trend and solve the dispersion problem of materials, reduce the using amount of the binder, reduce the internal resistance of the battery, improve the binding force between the active material and the current collector, improve the capacity exertion and the cycle performance of the lithium ion battery, and simultaneously have the indispensable three-in-one product of 'binding + conduction + dispersion'.
Disclosure of Invention
The invention aims to solve the technical problem of providing the aqueous conductive adhesive for the lithium battery and the preparation method thereof, wherein the aqueous conductive adhesive is prepared by a simple process of one-step synthesis and one-step dispersion, has conductive, bonding and dispersing performances, is low in consumption, and can reduce the internal resistance of the battery, improve the bonding force of a pole piece and improve the cycle performance of the battery; in addition, the water-based conductive adhesive has low manufacturing cost, takes water as a solvent in the whole process, and accords with the trend of environmental protection.
In order to solve the technical problems, the invention provides a water-based conductive binder for a lithium battery, which comprises 0.01-0.8 part by weight of single-walled carbon nanotubes, 1-10 parts by weight of multi-walled carbon nanotubes and 10-50 parts by weight of water-based binder; the outer diameter of the single-walled carbon nanotube is 0.4-40 nm, and the thickness of the tube wall is
The length is more than or equal to 1 mu m; the outer diameter of the multi-wall carbon nano tube is 2-20 nm, and the thickness of the tube wall is
The length is 500 nm-10 cm; the length-diameter ratio of the single-walled carbon nanotube to the multi-walled carbon nanotube is more than or equal to 1000 nm.
Preferably, the aqueous conductive adhesive further comprises a dispersant with the mass being 0.2-100 times of the total amount of the carbon nanotubes, and the dispersant is a nonionic polymer compound, an ionic cellulose gum or an ionic polyacrylic acid.
Preferably, the nonionic polymer compound is polyvinylpyrrolidone, the ionic cellulose gum is sodium carboxymethylcellulose, and the ionic polyacrylic acid is a PAA mixture.
Preferably, the aqueous conductive adhesive further comprises 0.5-10 parts by mass of an auxiliary conductive material, wherein the auxiliary conductive material is at least one of graphene, vapor-phase-grown carbon fiber, ultra-dense conductive carbon black and conductive carbon black.
Preferably, the aqueous conductive adhesive further comprises 0.2-25 parts by weight of a conductive polymer, and the conductivity of the conductive polymer is 100-250S/cm; the conductive polymer is one or two of univalent pair anion and univalent pair cation.
Preferably, the aqueous binder is one of polyacrylic acids, polyacrylonitriles, styrene butadiene rubbers, and methylcelluloses.
The invention also provides a preparation method of the water-based conductive adhesive for the lithium battery, which comprises the following steps:
step one, taking 0.01-0.8 part of single-walled carbon nanotube and 1-10 parts of multi-walled carbon nanotube by mass, or taking 0.01-0.8 part of single-walled carbon nanotube, 1-10 parts of multi-walled carbon nanotube by mass, and at least one of 0.5-10 parts of auxiliary conductive material and 0.2-25 parts of conductive polymer by mass, adding into 10-50 parts of aqueous binder solution, introducing inert gas at the temperature of 10-60 ℃, and performing mechanical dispersion to achieve the purpose of dispersing the solution to prepare mixed solution;
and step two, removing residual aggregates and residual monomers of the aqueous binder in the mixed solution obtained in the step one under reduced pressure, vacuumizing for 2-3 hours under the vacuum degree of less than or equal to-0.1 MPa, and thus obtaining the aqueous conductive binder.
The invention also provides a preparation method of the water-based conductive adhesive for the lithium battery, which comprises the following steps:
step one, taking 0.01-0.8 part by mass of a single-walled carbon nanotube and 1-10 parts by mass of a multi-walled carbon nanotube, or taking 0.01-0.8 part by mass of a single-walled carbon nanotube, 1-10 parts by mass of a multi-walled carbon nanotube, and at least one of 0.5-10 parts by mass of an auxiliary conductive material and 0.2-25 parts by mass of a conductive polymer, adding the single-walled carbon nanotube and the multi-walled carbon nanotube into a dispersing agent with the mass being 0.2-10 times of the total mass of the single-walled carbon nanotube and the multi-walled carbon nanotube, and introducing inert gas at the temperature of 10-60 ℃; performing mechanical dispersion to achieve the purpose of dispersing the solution;
removing residual aggregates in the obtained solution under reduced pressure, vacuumizing for 2-3 h under the vacuum degree of less than or equal to-0.1 MPa to obtain a mixed solution with lithium ion conductivity;
and step two, adding the mixed solution obtained in the step one into 10-50 parts of the aqueous binder, and mechanically dispersing to uniformly mix and disperse the mixture to obtain the aqueous conductive binder.
Preferably, in the mixed solution obtained in the first step, the solid content of the single-walled carbon nanotube is 0.1-1.0%, and the solid content of the multi-walled carbon nanotube is 1-10%.
Preferably, the mechanical dispersion is carried out by subjecting the solution to ultrasound under 500W-2000W power, or crushing the solution by using zirconium beads with the diameter of 0.01-0.08 mm under the rotation speed of 200 rpm-1000 rpm through a shearing force, or carrying out single-side impact on the solution under the low pressure of 200 bar-1000 bar, and the treatment time of the mechanical dispersion is 0.5-3 h.
The invention relates to a water-based conductive adhesive for lithium ions and a preparation method thereof, and compared with the existing design, the water-based conductive adhesive has the advantages that: according to the invention, the single-walled carbon nanotube and the multi-walled carbon nanotube, the auxiliary conductive material and the conductive polymer are added into the conventional synthetic water-based binder with good dispersion capacity, so that the water-based conductive binder with multiple functions of 'bonding + conduction + dispersion' is prepared in one step.
By using the aqueous conductive adhesive for the lithium ion battery, only active materials need to be added in the pulping process of the anode or cathode electrode plate slurry, so that the complex and complicated working procedures of the traditional pulping process are avoided, the pulping process is simplified, and the pulping time is saved; meanwhile, the aqueous conductive adhesive has better dispersibility, and solves the problem of difficult dispersion among active materials, adhesives and conductive agents in the traditional pulping process; the carbon nano tube, the auxiliary conductive material or the conductive polymer form a conductive network in the conductive adhesive or the pole piece, so that the conductivity of the aqueous conductive adhesive can be improved, and the internal resistance of the battery can be reduced; in addition, the carbon nano tube, the auxiliary conductive material and the conductive polymer are used as the material reinforcement to improve the binding power of the conductive adhesive on the positive electrode or the negative electrode plate of the battery, so that the problem that the electrode plate is easy to fall off in the traditional process is solved; through the comprehensive action, the capacity characteristic of the positive electrode or negative electrode active material in the lithium ion battery prepared by using the aqueous conductive adhesive is fully exerted, and the cycle performance of the lithium ion battery is improved; in addition, the conductive adhesive disclosed by the invention takes water as a solution medium in the whole process, is non-toxic and pollution-free, is beneficial to environmental protection and adapts to the environmental protection trend; compared with the traditional binder, the aqueous conductive binder has the advantages of less consumption and low manufacturing cost, and is beneficial to large-scale production.
Drawings
Fig. 1 is an SEM image of the aqueous conductive adhesive of the present invention.
Fig. 2 is a partial SEM image of an electrode sheet made using the aqueous conductive adhesive of the present invention.
Fig. 3 is a graph comparing the cycle performance of a battery fabricated using the aqueous conductive binder of the present invention and a comparative example.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The compositions and weights of examples 1 to 7 and comparative examples 1 to 2 are shown in Table 1, and the performance test data of examples 1 to 7 and comparative examples 1 to 2 are shown in Table 2.
Example 1
The invention provides a water-based conductive binder for lithium ions, which comprises carbon nanotubes and a water-based binder, and specifically comprises 0.01-0.8 part by weight of single-walled carbon nanotubes, 1-10 parts by weight of multi-walled carbon nanotubes and 10-50 parts by weight of water-based binder; the aqueous binder comprises positive and negative electrode aqueous binders with good dispersibility for lithium ion batteries such as PAA polyacrylic acids, PAN polyacrylonitrile, SBR styrene-butadiene rubber, CMC methylcellulose and the like. In this particular embodiment, the aqueous binder is PAA polyacrylic.
The outer diameter of the single-walled carbon nanotube is 0.4-40 nm, and the thickness of the tube wall is
The length is more than or equal to 1 mu m. The outer diameter of the multi-wall carbon nano tube is 2-20 nm, and the thickness of the tube wall is
The length is between 500nm and 10 cm. The length-diameter ratio (the ratio of the length to the diameter) of the single-walled carbon nanotube to the multi-walled carbon nanotube is more than or equal to 1000 nm.
The invention also provides a preparation method of the water-based conductive adhesive for lithium ions, which comprises the following steps:
step one, taking 0.8 part of single-walled carbon nanotube and 10 parts of multi-walled carbon nanotube by mass, adding the single-walled carbon nanotube and the multi-walled carbon nanotube into 50 parts of aqueous polyacrylic acid polymer binder solution, and introducing nitrogen at the temperature of 10-60 ℃ to form a nitrogen atmosphere. And (3) carrying out ultrasonic treatment on the solution by using ultrasonic equipment under the power of 500-2000W, wherein the ultrasonic treatment time is 0.5-3 h, so as to achieve the purpose of dispersing the solution.
And step two, removing residual carbon nanotube aggregates and residual monomers of the aqueous binder in the solution obtained in the step one under reduced pressure, vacuumizing for 2-3 h with the vacuum degree less than or equal to-0.1 MPa, and dispersing the aggregated carbon nanotubes in the binder solution in a single individual manner to obtain the aqueous conductive binder.
Example 2
The difference between this embodiment 2 and embodiment 1 is that: the aqueous conductive binder for lithium ions further comprises a dispersant in an amount of 0.2 to 100 times the total amount of the carbon nanotubes.
The dispersing agent is a non-ionic high molecular compound or an ionic cellulose gum or an ionic polyacrylic acid; the non-ionic high molecular compound adopts polyvinylpyrrolidone (PVP for short), the ionic cellulose glue adopts sodium carboxymethylcellulose (CMC-Na), the ionic polyacrylic acid adopts PAA mixture, and the PAA mixture adopts a commercial product, such as LA133 product of Dyynegele power technology limited company.
The invention also provides a preparation method of the water-based conductive adhesive for lithium ions, which comprises the following steps:
step one, taking 0.4 part of single-walled carbon nanotube and 5 parts of multi-walled carbon nanotube by mass, adding the single-walled carbon nanotube and the multi-walled carbon nanotube into PVP dispersant with the mass being 50 times of the total mass of the carbon nanotubes, and introducing nitrogen at the temperature of 10-60 ℃ to form a nitrogen atmosphere. The zirconium beads with the diameter of 0.01-0.08 mm passing through the sanding equipment smash the solution through shearing force at the rotating speed of 200-1000 rpm, and the processing time is 0.5-3 h, so that the aim of dispersing the solution is achieved.
And (3) removing residual carbon nanotube aggregates in the solution obtained in the first step under reduced pressure, wherein the vacuum degree is less than or equal to-0.1 MPa, and vacuumizing for 2-3 h to obtain a mixed solution with lithium ion conductivity.
In the mixed solution, the solid content of the single-walled carbon nanotube is 0.1-1.0%, and the solid content of the multi-walled carbon nanotube is 1-10%.
And step two, adding the mixed solution obtained in the step one into 30 parts of the aqueous binder at normal temperature (25 ℃), stirring at the rotating speed of 300-1200 rpm for 1-6 h, and dispersing at 10-60 ℃ for 0.5-3 h to uniformly mix and disperse the mixture, thereby obtaining the aqueous conductive binder.
Example 3
The difference between this embodiment 3 and embodiment 1 is that: the aqueous conductive binder for lithium ions further comprises 0.5-10 parts by mass of an auxiliary conductive material, wherein the auxiliary conductive material is at least one of graphene, Vapor Grown Carbon Fiber (VGCF), ultra-dense conductive carbon black (SP) and conductive carbon black. In this embodiment, the auxiliary conductive material is graphene.
The invention also provides a preparation method of the water-based conductive adhesive for lithium ions, which comprises the following steps:
step one, 0.01 part of single-walled carbon nanotube, 1 part of multi-walled carbon nanotube and 10 parts of graphene are taken according to the parts by mass and added into 50 parts of aqueous binder, and nitrogen is introduced at the temperature of 10-60 ℃ to form a nitrogen atmosphere. And (3) performing single-side impact on the solution at a low pressure of 200-1000 bar by using a low-pressure homogenizer for 0.5-3 h to achieve the aim of dispersing the solution.
And step two, removing residual carbon nano tubes, graphene aggregates and residual monomers of the aqueous binder in the solution obtained in the step one under reduced pressure, vacuumizing for 2-3 h with the vacuum degree less than or equal to-0.1 MPa, and dispersing the aggregated carbon nano tubes and graphene in the binder solution in a single individual manner to obtain the aqueous conductive binder.
Example 4
The difference between this embodiment 4 and embodiment 2 is that: the aqueous conductive binder for lithium ions further comprises 0.5-10 parts by mass of an auxiliary conductive material, wherein the auxiliary conductive material is at least one of graphene, Vapor Grown Carbon Fiber (VGCF), ultra-dense conductive carbon black (SP) and conductive carbon black. In this embodiment, the auxiliary conductive material is vapor-grown carbon fiber.
The invention also provides a preparation method of the water-based conductive adhesive for lithium ions, which comprises the following steps:
step one, taking 0.01 part of single-walled carbon nanotube, 1 part of multi-walled carbon nanotube and 5 parts of vapor-grown carbon fiber by mass, adding the single-walled carbon nanotube, the multi-walled carbon nanotube and the vapor-grown carbon fiber into PVP dispersant which is 0.2 time of the total amount of the carbon nanotubes, and introducing nitrogen at the temperature of 10-60 ℃ to form a nitrogen atmosphere. The zirconium beads with the diameter of 0.01-0.08 mm passing through the sanding equipment smash the solution through shearing force at the rotating speed of 200-1000 rpm, and the processing time is 0.5-3 h, so that the aim of dispersing the solution is achieved.
And (3) removing residual carbon nano tubes and vapor-grown carbon fiber aggregates in the obtained solution under reduced pressure, wherein the vacuum degree is less than or equal to-0.1 MPa, and vacuumizing for 2-3 h to obtain a mixed solution with lithium ion conductivity.
In the mixed solution, the solid content of the single-walled carbon nanotube is 0.1-1.0%, and the solid content of the multi-walled carbon nanotube is 1-10%.
And step two, adding the mixed solution obtained in the step one into 10 parts of the aqueous binder at normal temperature (25 ℃), stirring at the rotating speed of 300-1200 rpm for 1-6 h, and dispersing at 10-60 ℃ for 0.5-3 h to uniformly mix and disperse the mixture, thereby obtaining the aqueous conductive binder.
Example 5
The difference between this embodiment 5 and embodiment 1 is that: the aqueous conductive adhesive for lithium ions further comprises 0.2-25 parts by weight of a conductive polymer, wherein the conductivity of the conductive polymer is 100-250S/cm; the conductive polymer is one or two of univalent pair anion and univalent pair cation. In this embodiment, monovalent counter anions are used for the conductive polymer.
Specifically, 0.2-10 parts by mass of polyacrylonitrile (PAN for short) and 0.4-10 parts by mass of polypyrrole (PPy for short) are added into a binder of 10-40 parts by mass of polyacrylic acid, and the mixture is dispersed by an in-situ polymerization method at the temperature of 60-80 ℃ to obtain the monovalent anion-pair conductive polymer.
The invention also provides a preparation method of the water-based conductive adhesive for lithium ions, which comprises the following steps:
step one, 0.01 part of single-walled carbon nanotube, 1 part of multi-walled carbon nanotube and 25 parts of univalent pair anion conducting polymer are taken according to the mass parts and added into 50 parts of aqueous binder, and nitrogen is introduced at the temperature of 10-60 ℃ to form a nitrogen atmosphere. And (3) performing single-side impact on the solution at a low pressure of 200-1000 bar by using a low-pressure homogenizer for 0.5-3 h to achieve the aim of dispersing the solution.
And step two, removing residual carbon nanotube aggregates and residual binder monomers under reduced pressure, vacuumizing for 2-3 h under the vacuum degree of less than or equal to-0.1 MPa, and dispersing the aggregated carbon nanotubes in a binder solution by using single individuals to obtain the aqueous conductive binder.
Example 6
The present embodiment 6 differs from embodiment 1 in that: the aqueous conductive binder for lithium ions further comprises 0.5-10 parts by mass of an auxiliary conductive material and 0.2-25 parts by weight of a conductive polymer.
The auxiliary conductive material is at least one of graphene, Vapor Grown Carbon Fiber (VGCF), ultra-dense conductive carbon black (SP) and conductive carbon black. In this embodiment, the auxiliary conductive material is conductive carbon black.
The conductivity of the conductive polymer is 100-250S/cm; the conductive polymer is at least one of monovalent pair anion and monovalent pair cation. In this embodiment, monovalent counter anions are used for the conductive polymer. Adding 0.2-10 parts of polyacrylonitrile (PAN for short) and 0.4-10 parts of polypyrrole (PPy for short) into 10-40 parts of polyacrylic acid binder in parts by mass, and dispersing at 60-80 ℃ by an in-situ polymerization method to obtain the monovalent anion-pair conducting polymer.
The invention also provides a preparation method of the water-based conductive adhesive for lithium ions, which comprises the following steps:
step one, 0.4 part of single-walled carbon nanotube, 5 parts of multi-walled carbon nanotube, 0.5 part of conductive carbon black and 13 parts of monovalent anion conductive polymer are taken according to the mass parts and added into 30 parts of aqueous binder, and nitrogen is introduced at the temperature of 10-60 ℃ to form a nitrogen atmosphere. And (3) carrying out ultrasonic treatment on the solution by using ultrasonic equipment under the power of 500-2000W for 0.5-3 h so as to achieve the purpose of dispersing the solution.
And step two, removing residual carbon nano tubes, aggregate of the conductive carbon black and residual binder monomers in the solution obtained in the step one under reduced pressure, vacuumizing for 2-3 h under the vacuum degree of less than or equal to-0.1 MPa, and dispersing the aggregated carbon nano tubes and the conductive carbon black in the binder solution in a single individual manner to obtain the aqueous conductive binder.
Example 7
The difference between this embodiment 7 and embodiment 2 is that: the aqueous conductive binder for lithium ions further comprises 0.5-10 parts by mass of an auxiliary conductive material and 0.2-25 parts by weight of a conductive polymer.
The auxiliary conductive material is at least one of graphene, Vapor Grown Carbon Fiber (VGCF), ultra-dense conductive carbon black (SP) and conductive carbon black. In this embodiment, the auxiliary conductive material is conductive carbon black.
The conductivity of the conductive polymer is 100-250S/cm; the conductive polymer is at least one of monovalent pair anion and monovalent pair cation. In this embodiment, monovalent counter anions are used for the conductive polymer. Adding 0.2-10 parts of polyacrylonitrile (PAN for short) and 0.4-10 parts of polypyrrole (PPy for short) into 10-40 parts of polyacrylic acid binder in parts by mass, and dispersing at 60-80 ℃ by an in-situ polymerization method to obtain the monovalent anion-pair conducting polymer.
The invention also provides a preparation method of the water-based conductive adhesive for lithium ions, which comprises the following steps:
step one, 0.8 part of single-walled carbon nanotube, 10 parts of multi-walled carbon nanotube, 10 parts of ultra-dense conductive carbon black and 0.2 part of monovalent anionic conductive polymer are taken according to the mass parts and added into PAA dispersant which is 100 times of the total amount of the carbon nanotube, and nitrogen is introduced at the temperature of 10-60 ℃ to form a nitrogen atmosphere. The zirconium beads with the diameter of 0.01-0.08 mm passing through the sanding equipment smash the solution through shearing force at the rotating speed of 200-1000 rpm, and the processing time is 0.5-3 h, so that the aim of dispersing the solution is achieved.
And (3) removing the residual carbon nano tubes, the extremely dense conductive carbon black and the conductive polymer aggregate in the obtained solution under reduced pressure, vacuumizing for 2-3 h under the vacuum degree of less than or equal to-0.1 MPa, and obtaining the mixed solution with the lithium ion conductivity.
In the mixed solution, the solid content of the single-walled carbon nanotube is 0.1-1.0%, and the solid content of the multi-walled carbon nanotube is 1-10%.
And step two, adding the mixed solution obtained in the step one into 50 parts of the aqueous binder at normal temperature (25 ℃), stirring at the rotating speed of 300-1200 rpm for 1-6 h, and dispersing at 10-60 ℃ for 0.5-3 h to uniformly mix and disperse the mixture, thereby obtaining the aqueous conductive binder.
Comparative example 1
Comparative example 1 the existing conventional SBR + CMC + SP system was chosen.
Comparative example 2
Comparative example 2 an existing commonly used PAA + CMC + SP system was selected.
TABLE 1
The aqueous binder can also be positive and negative aqueous binders used by various lithium ion batteries such as PAN polyacrylonitrile, SBR (styrene butadiene rubber), CMC (carboxy methyl cellulose) and the like, and has the same effect; the dispersant can also use CMC-Na and PAA mixture, and the effect is equivalent; the auxiliary conductive material can also use any combination of the materials used in examples 3, 4, 6 and 7, the effects are basically equal, and the conductivity is different based on different proportions; the conductive polymer may also be a monovalent cation conductive polymer, and the effect is equivalent.
TABLE 2
The method for detecting each property in table 2 is as follows.
Detection of the conductivity:
the aqueous conductive adhesive for the lithium ion battery obtained in the embodiment is coated on a PE film with a thickness of 100 μm, and the coatings of the aqueous conductive adhesive in the embodiments 1 to 7 and the adhesives in the comparative examples 1 to 2 are dried at 70 ℃ for 5 hours, then cooled to room temperature of 25 ℃, and a four-probe tester is used for testing the corresponding conductivity.
Preparing cathode electrode plate slurry:
(1) in examples 1 to 7, negative electrode plate slurry was prepared using a water-based conductive binder;
mixing the aqueous conductive adhesive and the silicon-based composite negative electrode active material (based on solid content) in the examples 1-7 according to the mass fraction of 2.5 w% and 97.5 wt%, adding deionized water according to the proportion that the total solid content is 45 wt%, dispersing the negative electrode plate slurry of the examples 1-7 by using a double planetary kneader, regularly using a granularity testing scraper to observe whether particles exist or not by naked eyes during the dispersion process, stopping the dispersion if no particles exist, and recording the dispersion time of each example, as shown in table 2, so as to obtain the uniformly dispersed negative electrode plate slurry prepared by using the aqueous conductive adhesive.
(2) According to the materials used in comparative examples 1 and 2, SBR (SN307) and PAA (LA133) binders in a proportion of 2 wt% in mass fraction (in terms of solid content) were mixed and dispersed with 0.5 wt% of CMC binders, respectively, using a double planetary kneader, and the presence of particles was observed by naked eyes using a particle size test blade at regular time during the dispersion, and if no particles were observed by naked eyes, the dispersion was stopped, and the second step was performed; adding 1.0 wt% of SP into the mixed solution, performing mixing and dispersing by using a double planetary kneader, regularly using a particle size testing scraper to observe whether particles exist or not by naked eyes during the dispersing process, and stopping dispersing if no particles exist after the particles are dispersed until the particles are observed by naked eyes, and performing a third step; adding 96.5 wt% of silicon-based composite active material, adding deionized water according to the proportion that the total solid component is 45 wt%, dispersing by using a double planetary kneader, regularly using a particle size testing scraper in the dispersing process, observing whether particles exist or not by naked eyes, stopping dispersing if no particles exist, and recording the total dispersing time as shown in table 2.
Detecting the particle size D90 of the slurry of the negative electrode pole piece:
1g of the uniformly dispersed negative electrode sheet slurry prepared by using the aqueous conductive binders of examples 1 to 7 and the binders of comparative examples 1 to 2 was diluted in 100g of water, and the particle size D90 was measured by using a malvern 2000 particle size tester, as shown in table 2, the larger the particle size D90, the larger the particle size.
And (3) detecting the binding power of the rolled negative pole piece:
firstly, manufacturing a lithium ion battery negative pole piece; according to the prior art, the uniformly dispersed negative electrode pole piece slurry prepared by using the water-based conductive adhesives of the examples 1-7 and the adhesives of the comparative examples 1-2 is coated on a 10 mu m thick copper foil serving as a current collector after passing through a 100-mesh screen, dried for 5min at the temperature of 120 ℃, naturally cooled to room temperature in a furnace, and then cooled to 10 multiplied by 104And (3) calendering the load of N/m unit length to obtain an electrode piece as a lithium ion battery cathode, wherein the lithium ion battery cathode SEM is shown in figure 2, the lines are carbon nano tubes, the particles are Si-O, and the carbon nano tubes are free of aggregates and uniformly coated on the active material.
The negative electrode sheet obtained above was rolled to prepare a strip of 20cm × 2.5cm in size, a double-sided adhesive tape was attached to a steel plate of 1mm in thickness on the current collector, a transparent adhesive tape was attached to the coating layer, and the coating layer was peeled off in a direction of 180 ° at a speed of 100mm/min by a tensile tester, and the average value was measured to obtain the measured adhesion force after rolling of the negative electrode sheet, as shown in table 2. The stronger the adhesion, the tighter the adhesion of the pole piece.
The performance evaluation of the simulated lithium battery (battery internal resistance, positive electrode gram capacity exertion and 100-week cycle maintenance) comprises the following steps:
firstly, manufacturing a lithium battery according to the prior art; preparing a silicon-based and graphite composite negative electrode material; the silicon-based and graphite composite negative electrode material is preferably SiOx (1< x <2) or a Si-C composite material containing C or Si and C, natural graphite or artificial graphite, and a silicon-based and graphite composite negative electrode material with the gram volume of 600 mAh/g. The simulated lithium ion battery is prepared by adopting the negative electrode and the positive electrode (commercial LFP pole piece) prepared by the negative electrode pole piece slurry prepared by the aqueous conductive adhesive of the embodiment 1-7 and the adhesive of the comparative example 1-2.
The internal resistance of the battery was measured under the conditions of 50% SOC and 3.3V, and the cathode capacity was measured under the condition of 3.5V, as shown in table 2.
And then testing the first coulombic efficiency of the charge-discharge cycle of the lithium ion battery and the coulombic efficiency and the capacity retention rate after 100 cycles by adopting a constant current method, and recording the obtained cycle retention rate value after 100 cycles of charge-discharge, as shown in table 2. The trend of the cycle retention rate with cycle number is shown in FIG. 3.
As can be seen from table 2, the aqueous conductive binder of the present invention is used in a relatively small amount. Compared with the comparative examples 1-2, the pulping process for preparing the cathode electrode plate slurry by using the aqueous conductive adhesive in the examples 1-7 only needs to add an active material in the pulping process, so that the pulping process is simplified, and the pulping time is saved.
As can be seen from table 2, the particle size D90 of the negative electrode plate slurry prepared by using the aqueous conductive adhesives of examples 1 to 7 of the present invention is smaller than that of comparative examples 1 to 2, which indicates that aggregates of the conductive material in the present invention are all dispersed, i.e., the aqueous conductive adhesives of the present invention have a better dispersion effect than conventional adhesives.
As can be seen from Table 2, the binding power of the rolled negative electrode pole piece manufactured by using the aqueous conductive adhesive of the embodiments 1-7 of the invention is higher than that of the comparative examples 1-2, so that the conductive material in the negative electrode pole piece of the invention plays a role of a mechanical reinforcement in the adhesive and the active material, and the improvement of the self binding power of the aqueous conductive adhesive is facilitated.
As can be seen from table 2 and fig. 3, compared with the binders of comparative examples 1 to 2, the aqueous conductive binders of examples 1 to 7 of the present invention, which use a plurality of conductive materials, are superior to conductive carbon black and conductive graphite commonly used in the current mainstream market, have good conductivity and strong dispersibility, are beneficial to the insertion/extraction of lithium ions, and fully exert the performance of active materials, so that the internal resistance of the battery is smaller, the gram capacity of the positive electrode is better exerted, and in a cycle test, the capacity loss is less, so the cycle retention rate is higher.
In addition, as shown in table 2, the battery performance is different due to the differences in the dispersibility and the internal resistance of the battery between the examples 1 to 7 and the comparative examples 1 to 2 due to the different conductive material ratios and the different types of conductive materials. The embodiment of the invention integrates bonding, conduction and dispersion, which is obviously beneficial to improving the dispersibility of the cathode electrode plate slurry, improving the cohesive force of the aqueous conductive adhesive and improving the conductivity of the aqueous conductive adhesive, thereby reducing the internal resistance of the battery, and the total amount of the aqueous conductive adhesive is less, and the invention has unique advantages in gram capacity of the positive electrode of the battery and the cycle performance of the battery; in example 7, the carbon nanotubes with high conductivity, the auxiliary conductive material, and the conductive polymer are added, so that the conductivity is the strongest, and the active material, the conductive material, and the binder in the slurry of the negative electrode plate are uniformly dispersed, so that the internal resistance of the battery is small, the gram capacity of the positive electrode is best, and the cycle performance of the battery is also best. In the comparative examples 1-2, the conventional binder, the conductive agent and the active material are not uniformly dispersed, the conductivity is poor, the internal resistance of the battery is high, the pole piece is easy to fall off, the capacity of the battery cannot be exerted, and the cycle is easy to attenuate.
Fig. 1 is an SEM image of an aqueous conductive adhesive. 1g of the aqueous conductive adhesive sample prepared in the embodiment 1 of the invention is dropped on a copper foil, and then dried in a forced air drying oven at 70 ℃, and a small piece is cut out and observed under a scanning electron microscope. The black area is a binder adhesive film, the luminescent lines are carbon nanotubes dispersed in the adhesive film, wherein the spider network indicates that the carbon nanotubes are uniformly dispersed in the binder to form a net structure, which is beneficial to the conduction of lithium ions and verifies the consistency of the design structure and the actual structure of the aqueous conductive binder.
Fig. 2 is an SEM image of an electrode sheet made using an aqueous conductive adhesive. The lines are carbon nanotubes, the large particles are active material Si-O, and the carbon nanotubes are uniformly coated on the active material without aggregates, so that the cathode electrode plate slurry is uniformly dispersed, the carbon nanotubes are in a conductive network in the cathode electrode plate slurry, the conduction of lithium ions is facilitated, and the consistency of the structural design and the actual structure of the aqueous conductive adhesive is verified.
Claims (10)
1. A water-based conductive adhesive for lithium batteries is characterized in that: the adhesive comprises 0.01-0.8 part by weight of single-walled carbon nanotubes, 1-10 parts by weight of multi-walled carbon nanotubes and 10-50 parts by weight of aqueous binder; the outer diameter of the single-walled carbon nanotube is 0.4-40 nm, and the thickness of the tube wall is
The length is more than or equal to 1 mu m; the outer diameter of the multi-wall carbon nano tube is 2-20 nm, and the thickness of the tube wall is
The length is 500 nm-10 cm; the length-diameter ratio of the single-walled carbon nanotube to the multi-walled carbon nanotube is more than or equal to 1000 nm.
2. The aqueous conductive adhesive for lithium batteries according to claim 1, further comprising a dispersant in an amount of 0.2 to 100 times by mass based on the total amount of the carbon nanotubes, wherein the dispersant is a nonionic polymer compound, an ionic cellulose gum or an ionic polyacrylic acid.
3. The aqueous conductive adhesive for lithium batteries according to claim 2, wherein the nonionic polymer compound is polyvinylpyrrolidone, the ionic cellulose gum is sodium carboxymethylcellulose, and the ionic polyacrylic acid is PAA mixture.
4. The aqueous conductive adhesive for lithium batteries according to claim 1, further comprising 0.5 to 10 parts by mass of an auxiliary conductive material, wherein the auxiliary conductive material is at least one of graphene, vapor-grown carbon fiber, ultra-dense conductive carbon black and conductive carbon black.
5. The aqueous conductive adhesive for lithium batteries according to claim 1, further comprising 0.2 to 25 parts by weight of a conductive polymer having an electrical conductivity of 100 to 250S/cm; the conductive polymer is one or two of univalent pair anion and univalent pair cation.
6. The aqueous conductive adhesive for lithium batteries according to any one of claims 1 to 5, wherein the aqueous adhesive is one of polyacrylic acids, polyacrylonitriles, styrene butadiene rubbers, and methylcelluloses.
7. The preparation method of the water-based conductive adhesive for the lithium battery is characterized by comprising the following steps of:
step one, taking 0.01-0.8 part of single-walled carbon nanotube and 1-10 parts of multi-walled carbon nanotube by mass, or taking 0.01-0.8 part of single-walled carbon nanotube, 1-10 parts of multi-walled carbon nanotube by mass, and at least one of 0.5-10 parts of auxiliary conductive material and 0.2-25 parts of conductive polymer by mass, adding into 10-50 parts of aqueous binder solution, introducing inert gas at the temperature of 10-60 ℃, and performing mechanical dispersion to achieve the purpose of dispersing the solution to prepare mixed solution;
and step two, removing residual aggregates and residual monomers of the aqueous binder in the mixed solution obtained in the step one under reduced pressure, vacuumizing for 2-3 hours under the vacuum degree of less than or equal to-0.1 MPa, and thus obtaining the aqueous conductive binder.
8. The preparation method of the water-based conductive adhesive for the lithium battery is characterized by comprising the following steps of:
step one, taking 0.01-0.8 part by mass of a single-walled carbon nanotube and 1-10 parts by mass of a multi-walled carbon nanotube, or taking 0.01-0.8 part by mass of a single-walled carbon nanotube, 1-10 parts by mass of a multi-walled carbon nanotube, and at least one of 0.5-10 parts by mass of an auxiliary conductive material and 0.2-25 parts by mass of a conductive polymer, adding the single-walled carbon nanotube and the multi-walled carbon nanotube into a dispersing agent with the mass being 0.2-10 times of the total mass of the single-walled carbon nanotube and the multi-walled carbon nanotube, and introducing inert gas at the temperature of 10-60 ℃; performing mechanical dispersion to achieve the purpose of dispersing the solution;
removing residual aggregates in the obtained solution under reduced pressure, vacuumizing for 2-3 h under the vacuum degree of less than or equal to-0.1 MPa to obtain a mixed solution with lithium ion conductivity;
and step two, adding the mixed solution obtained in the step one into 10-50 parts of the aqueous binder, and mechanically dispersing to uniformly mix and disperse the mixture to obtain the aqueous conductive binder.
9. The method as claimed in claim 8, wherein the mixed solution obtained in the first step has a solid content of single-walled carbon nanotubes of 0.1-1.0% and a solid content of multi-walled carbon nanotubes of 1-10%.
10. The method for preparing an aqueous conductive adhesive for a lithium battery according to any one of claims 7 to 9, wherein the mechanical dispersion is performed by subjecting the solution to ultrasound at a power of 500W to 2000W, or by crushing the solution by a shearing force using zirconium beads having a diameter of 0.01 to 0.08mm at a rotation speed of 200rpm to 1000rpm, or by subjecting the solution to single-side impact at a low pressure of 200bar to 1000bar, and the treatment time of the mechanical dispersion is 0.5 to 3 hours.
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| CN114784280A (en) * | 2022-05-11 | 2022-07-22 | 浙江南都电源动力股份有限公司 | Composite primer conductive agent and preparation method and application thereof |
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