CN111029522B - Fiber bundle-shaped three-dimensional current collector and preparation method thereof - Google Patents
Fiber bundle-shaped three-dimensional current collector and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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Abstract
The invention discloses a fiber bundle-shaped three-dimensional current collector and a preparation method thereof, wherein the method comprises the steps of 1) adding an initiator into maleic anhydride, then adding methylbenzene, stirring and heating, dropwise adding a mixed solution of acrylic acid and methylbenzene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction, stopping reaction, and carrying out reduced pressure distillation to remove the solvent to obtain a binder; 2) preparing a binder into a binder solution; 3) mixing graphite and conductive particles, fully grinding and uniformly mixing to obtain mixed powder; 4) adding the binder solution into the mixed powder, fully grinding and uniformly mixing again to obtain viscous slurry; 5) and pouring the viscous slurry into a mold, transferring to a cold trap, carrying out constant temperature treatment, transferring to freeze drying, and completely drying to obtain the fiber bundle-shaped three-dimensional current collector. Long-chain alkyl is introduced to stabilize graphite in a three-dimensional network structure, and the graphite is organically combined by hydrophobicity. Both effects are very helpful to improve the cycling stability of the graphite electrode material.
Description
Technical Field
The invention belongs to the field of electrode material preparation, and particularly relates to a fiber bundle-shaped three-dimensional current collector and a preparation method thereof.
Background
The demand of people on green energy in the current society is increasing day by day, the lithium ion battery industry is also rising temperature rapidly, and scientists have carried out a large amount of researches on lithium ion batteries, and with the deepening of the research on lithium ion battery materials, the performance of the lithium ion battery is not only relevant to the active material of the electrode material, but also closely related to the binding capacity of the binding agent. At present, the binding mechanism of the electrode material binder is mainly to utilize hydrogen bonds generated by functional groups in the binder to adsorb active substances, but the problem that the active substances in the electrode material drop off greatly along with the increase of the cycle times of the lithium ion battery is solved.
Disclosure of Invention
Compared with the conventional electrode, the method introduces a large amount of carboxyl, so that the hydrogen bond between the graphite and the binder is stronger, the adsorption is firmer, and Li in the electrode material is absorbed by the graphite and the binder+The capacity of the moving is also improved. Long-chain alkyl is introduced to stabilize graphite in a three-dimensional network structure, and the graphite is organically combined by hydrophobicity. Two of themThe function is very helpful for improving the cycling stability of the graphite electrode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a fiber bundle-shaped three-dimensional current collector comprises the following steps:
1) adding an initiator into maleic anhydride, adding toluene, stirring and heating to 70-80 ℃, starting to slowly dropwise add a mixed solution of acrylic acid and toluene, carrying out heat preservation reaction for 1.5-2 h, cooling to 70 ℃, dropwise adding a mixed solution of higher alcohol and toluene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction for 1.5-2 h, stopping reaction, and carrying out reduced pressure distillation to remove a solvent to obtain a binder;
2) preparing a binder into a binder solution;
3) mixing graphite and conductive particles, fully grinding and uniformly mixing to obtain mixed powder;
4) adding the binder solution into the mixed powder, fully grinding and uniformly mixing again to obtain viscous slurry;
5) and pouring the viscous slurry into a mold, transferring to a cold trap, carrying out constant temperature treatment, transferring to freeze drying, and completely drying to obtain the fiber bundle-shaped three-dimensional current collector.
As a further improvement of the invention, the initiator in the step 1) is benzoyl peroxide, and the addition amount of the benzoyl peroxide is 2-4 wt% of the total mass of the mixed solution.
As a further improvement of the invention, the long-chain alcohol in the step 1) is 12-18 alcohol.
As a further improvement of the invention, the binder concentration in step 2) is 1 to 2 wt.%.
As a further improvement of the invention, in the step 3), the mass ratio of the graphite to the conductive particles is 100 to (10-40).
As a further improvement of the invention, the temperature of the step 5) in the cold trap is-40 to-30 ℃, and the temperature is kept for 2 to 4 hours.
As a further improvement of the invention, the freeze drying pressure in the step 5) is 4-6 Pa, and the duration is 10-15 h.
As a further improvement of the invention, in the step 4), the mass ratio of the graphite to the binder is 100: 10-40.
As a further improvement of the invention, the conductive particles are acetylene black or super-p.
As a further improvement of the invention, in the step 3), the first grinding time is 30-50 min.
As a further improvement of the invention, in the step 4), the second grinding time is 10-30 min.
A fiber bundle-shaped three-dimensional current collector is composed of an active substance, a laminated structure and conductive particles; wherein the active substance is derived from graphite, the mass ratio of the active substance to the binder is 100: 10-40, and the mass ratio of the active substance to the conductive particles is 100: 10-40; the laminated structure is composed of a binding agent synthesized by maleic anhydride, acrylamide and long-chain alcohol.
Compared with the prior art, the invention has the following advantages:
the preparation method of the invention introduces maleic anhydride for esterification, and has the advantages that the esterification can be carried out at 90 ℃, and the simple polyacrylic acid esterification temperature needs to reach 150 ℃. The invention uses anhydride to carry out esterification reaction, the required temperature is low, and the production cost is reduced. Compared with the conventional electrode, the method introduces a large amount of carboxyl, so that the hydrogen bond between the graphite and the binder is stronger, the adsorption is firmer, and Li in the electrode material+The capacity of the moving is also improved. Long-chain alkyl is introduced to stabilize graphite in a three-dimensional network structure, and the graphite is organically combined by hydrophobicity. Both effects are very helpful to improve the cycling stability of the graphite electrode material.
Drawings
FIG. 1 is a diagram of the reaction mechanism for synthesizing the binder of the present invention;
FIG. 2 is a microscopic morphology of the fiber bundle-like three-dimensional current collector of example 1;
fig. 3 is a cycle performance test chart of the fibrous bundle-shaped three-dimensional current collector in example 2.
Detailed Description
The invention is based on the preparation of a fiber bundle-shaped three-dimensional current collector, and the three-dimensional network electrode consists of an active substance, a layered structure and conductive particles; wherein the active substance is derived from graphite, the mass ratio of the active substance to the layered structure is 100: 10-40, and the mass ratio of the active substance to the conductive particles is 100: 10-40. Wherein the conductive particles are selected from acetylene black, super-p.
The principle of the invention is as follows: the invention utilizes the hydrophobic pair of long-chain alkyl in the binder to be organically combined with graphite. Compared with the conventional electrode, the method introduces a large amount of carboxyl, so that the hydrogen bond between the graphite and the binder is stronger, the adsorption is firmer, and Li in the electrode material+The capacity of the moving is also improved. Both effects are very helpful to improve the cycling stability of the graphite electrode material.
As shown in fig. 1, the preparation method of the present invention specifically operates as follows:
first, acrylic acid and maleic anhydride were used for the polymerization: adding a certain amount of maleic anhydride, 2-4 wt% of initiator benzoyl peroxide and a small amount of toluene into a flask, continuously stirring and heating to 70-80 ℃, starting to slowly dropwise add a mixed solution of acrylic acid and toluene, after the mixed solution reacts for 10min, dropwise adding the mixed solution of acrylic acid and toluene again, controlling the reaction temperature to be about 75 ℃, carrying out heat preservation reaction for 1.5-2 h, cooling to 70 ℃, dropwise adding a mixed solution of higher alcohol and toluene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction for 1.5-2 h, stopping the reaction, and carrying out reduced pressure distillation to remove the solvent to obtain the required binder;
after synthesizing the needed binder, preparing the binder into solution with the concentration of 1.0-2.0 wt%, standing for standby, mixing graphite and super-p to ensure that the mass ratio of the graphite to the conductive particles is 100: 10-40, and ball-milling for 30-50 min.
Mixing the binder solution with graphite and super-p to ensure that the mass ratio of the graphite to the carboxymethyl cellulose is 100: 10-40, then carrying out ball milling again for 10-30min to obtain viscous slurry;
pouring the slurry into a mold, adjusting the temperature to-40 to-30 ℃ in a cold trap, keeping the temperature for 2 to 4 hours, transferring the slurry into a freeze dryer, adjusting the pressure to 4 to 6Pa, and keeping the pressure for 10 to 15 hours to ensure complete drying, thereby obtaining the fiber bundle-shaped three-dimensional current collector.
The invention is further illustrated by the following specific examples and figures:
example 1
First, acrylic acid and maleic anhydride were used for the polymerization: adding a certain amount of maleic anhydride, 3 wt% of initiator benzoyl peroxide and a small amount of toluene into a flask, continuously stirring and heating to 70-80 ℃, starting to slowly dropwise add a mixed solution of acrylic acid and toluene, after the mixture reacts for 10min, dropwise adding a mixed solution of acrylic acid and toluene again, controlling the reaction temperature to be about 75 ℃, carrying out heat preservation reaction for 2h, cooling to 70 ℃, dropwise adding a mixed solution of octadecanol and toluene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction for 2h, stopping the reaction, and carrying out reduced pressure distillation to remove the solvent to obtain the required binder; after synthesizing the needed binder, preparing a binder solution with the concentration of 1.0 wt%, standing, mixing graphite and super-p to ensure that the mass ratio of the graphite to the conductive particles super-p is 100: 10, and ball-milling for 30 min. Mixing the solution with graphite and super-p to ensure that the mass ratio of the graphite to the carboxymethyl cellulose is 100: 10, then ball-milling again for 10min to obtain viscous slurry, pouring the slurry into a mould, adjusting the temperature to-40 ℃ in a cold trap, keeping the temperature for 3h, then transferring the slurry into a freeze dryer, adjusting the pressure to 5Pa, keeping the pressure for 12h, and ensuring complete drying to obtain the fiber bundle-shaped three-dimensional current collector.
Fig. 2 shows the micro-morphology of the fiber bundle-like three-dimensional current collector in example 1, and it is seen from the figure that the prepared binder has uniformly dispersed graphite in the layered structure, and graphite particles are tightly adsorbed on the layered network, so that the binder has a stable net-like three-dimensional structure, and can greatly improve the cycle stability of the electrode material.
Example 2
First, acrylic acid and maleic anhydride were used for the polymerization: adding a certain amount of maleic anhydride, 3 wt% of initiator benzoyl peroxide and a small amount of toluene into a flask, continuously stirring and heating to 70-80 ℃, starting to slowly dropwise add a mixed solution of acrylic acid and toluene, after the mixed solution reacts for 10min, dropwise adding the mixed solution of acrylic acid and toluene again, controlling the reaction temperature to be about 75 ℃, carrying out heat preservation reaction for 2h, cooling to 70 ℃, dropwise adding a mixed solution of hexadecanol and toluene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction for 2h, stopping the reaction, and carrying out reduced pressure distillation to remove the solvent to obtain the required binder; after synthesizing the needed binder, preparing a binder solution with the concentration of 1.0 wt%, standing, mixing graphite and super-p to ensure that the mass ratio of the graphite to the conductive particles super-p is 100: 20, and ball-milling for 30 min. Mixing the solution with graphite and super-p to ensure that the mass ratio of the graphite to the carboxymethyl cellulose is 100: 15, then ball-milling again for 10min to obtain viscous slurry, pouring the slurry into a mould, adjusting the temperature to-40 ℃ in a cold trap, keeping the temperature for 3h, then transferring the slurry into a freeze dryer, adjusting the pressure to 5Pa, keeping the pressure for 12h, and ensuring complete drying to obtain the fiber bundle-shaped three-dimensional current collector.
Fig. 3 is a cycle performance test chart of the fiber bundle-shaped three-dimensional current collector in example 2; according to the circulation condition of the button half cell assembled by the electrode, the prepared binder has obvious effect, and the cell shows good stability.
Example 3
First, acrylic acid and maleic anhydride were used for the polymerization: adding a certain amount of maleic anhydride, 3 wt% of initiator benzoyl peroxide and a small amount of toluene into a flask, continuously stirring and heating to 70-80 ℃, starting to slowly dropwise add a mixed solution of acrylic acid and toluene, after the mixture reacts for 10min, dropwise adding a mixed solution of acrylic acid and toluene again, controlling the reaction temperature to be about 75 ℃, carrying out heat preservation reaction for 2h, cooling to 70 ℃, dropwise adding a mixed solution of dodecanol and toluene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction for 2h, stopping the reaction, and carrying out reduced pressure distillation to remove the solvent to obtain the required binder; after synthesizing the needed binder, preparing a binder solution with the concentration of 1.5 wt%, standing, mixing graphite and super-p to ensure that the mass ratio of the graphite to the conductive particles super-p is 100: 15, and carrying out ball milling for 35 min. Mixing the solution with graphite and super-p to ensure that the mass ratio of the graphite to the carboxymethyl cellulose is 100: 20, then ball-milling again for 10min to obtain viscous slurry, pouring the slurry into a mould, adjusting the temperature to-40 ℃ in a cold trap, keeping the temperature for 3h, then transferring the slurry into a freeze dryer, adjusting the pressure to 5Pa, keeping the pressure for 12h, and ensuring complete drying to obtain the fiber bundle-shaped three-dimensional current collector.
Example 4
First, acrylic acid and maleic anhydride were used for the polymerization: adding a certain amount of maleic anhydride, 3 wt% of initiator benzoyl peroxide and a small amount of toluene into a flask, continuously stirring and heating to 70-80 ℃, starting to slowly dropwise add a mixed solution of acrylic acid and toluene, after the mixture reacts for 10min, dropwise adding the mixed solution of acrylic acid and toluene again, controlling the reaction temperature to be about 75 ℃, carrying out heat preservation reaction for 2h, cooling to 70 ℃, dropwise adding a mixed solution of tetradecanol and toluene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction for 2h, stopping the reaction, and carrying out reduced pressure distillation to remove the solvent to obtain the required binder; after synthesizing the needed binder, preparing a binder solution with the concentration of 2.0 wt%, standing, mixing graphite and super-p to ensure that the mass ratio of the graphite to the conductive particles super-p is 100: 10, and ball-milling for 30 min. Mixing the solution with graphite and super-p to ensure that the mass ratio of the graphite to the carboxymethyl cellulose is 100: 30, then ball-milling again for 20min to obtain viscous slurry, pouring the slurry into a mould, adjusting the temperature to-40 ℃ in a cold trap, keeping the temperature for 3h, then transferring the slurry into a freeze dryer, adjusting the pressure to 5Pa, keeping the pressure for 12h, and ensuring complete drying to obtain the fiber bundle-shaped three-dimensional current collector.
Example 5
First, acrylic acid and maleic anhydride were used for the polymerization: adding a certain amount of maleic anhydride, 3 wt% of initiator benzoyl peroxide and a small amount of toluene into a flask, continuously stirring and heating to 70-80 ℃, starting to slowly dropwise add a mixed solution of acrylic acid and toluene, after the mixture reacts for 10min, dropwise adding a mixed solution of acrylic acid and toluene again, controlling the reaction temperature to be about 75 ℃, carrying out heat preservation reaction for 2h, cooling to 70 ℃, dropwise adding a mixed solution of octadecanol and toluene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction for 2h, stopping the reaction, and carrying out reduced pressure distillation to remove the solvent to obtain the required binder; after synthesizing the needed binder, preparing a binder solution with the concentration of 1.0 wt%, standing, mixing graphite and super-p to ensure that the mass ratio of the graphite to the conductive particle acetylene black is 100: 20, and ball-milling for 350 min. Mixing the solution with graphite and super-p to ensure that the mass ratio of the graphite to the carboxymethyl cellulose is 100: 20, then ball-milling again for 15min to obtain viscous slurry, pouring the slurry into a mould, adjusting the temperature to-40 ℃ in a cold trap, keeping the temperature for 3h, then transferring the slurry into a freeze dryer, adjusting the pressure to 5Pa, keeping the pressure for 12h, and ensuring complete drying to obtain the fiber bundle-shaped three-dimensional current collector.
Example 6
First, acrylic acid and maleic anhydride were used for the polymerization: adding a certain amount of maleic anhydride, 3 wt% of initiator benzoyl peroxide and a small amount of toluene into a flask, continuously stirring and heating to 70-80 ℃, starting to slowly dropwise add a mixed solution of acrylic acid and toluene, after the mixture reacts for 10min, dropwise adding a mixed solution of acrylic acid and toluene again, controlling the reaction temperature to be about 75 ℃, carrying out heat preservation reaction for 2h, cooling to 70 ℃, dropwise adding a mixed solution of dodecanol and toluene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction for 2h, stopping the reaction, and carrying out reduced pressure distillation to remove the solvent to obtain the required binder; after synthesizing the needed binder, preparing a binder solution with the concentration of 1.0 wt%, standing, mixing graphite and super-p to ensure that the mass ratio of the graphite to the conductive particles super-p is 100: 40, and ball-milling for 50 min. Mixing the solution with graphite and super-p to ensure that the mass ratio of the graphite to the carboxymethyl cellulose is 100: 40, then ball-milling again for 30min to obtain viscous slurry, pouring the slurry into a mould, adjusting the temperature to-40 ℃ in a cold trap, keeping the temperature for 3h, then transferring the slurry into a freeze dryer, adjusting the pressure to 5Pa, keeping the pressure for 12h, and ensuring complete drying to obtain the fiber bundle-shaped three-dimensional current collector.
Example 7
First, acrylic acid and maleic anhydride were used for the polymerization: adding a certain amount of maleic anhydride, 3 wt% of initiator benzoyl peroxide and a small amount of toluene into a flask, continuously stirring and heating to 70-80 ℃, starting to slowly dropwise add a mixed solution of acrylic acid and toluene, after the mixture reacts for 10min, dropwise adding a mixed solution of acrylic acid and toluene again, controlling the reaction temperature to be about 75 ℃, carrying out heat preservation reaction for 2h, cooling to 70 ℃, dropwise adding a mixed solution of octadecanol and toluene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction for 2h, stopping the reaction, and carrying out reduced pressure distillation to remove the solvent to obtain the required binder; after synthesizing the needed binder, preparing a binder solution with the concentration of 1.0 wt%, standing, mixing graphite and super-p to ensure that the mass ratio of the graphite to the conductive particle acetylene black is 100: 35, and ball-milling for 40 min. Mixing the solution with graphite and super-p to ensure that the mass ratio of the graphite to the carboxymethyl cellulose is 100: 10, then ball-milling again for 10min to obtain viscous slurry, pouring the slurry into a mould, adjusting the temperature to-40 ℃ in a cold trap, keeping the temperature for 3h, then transferring the slurry into a freeze dryer, adjusting the pressure to 5Pa, keeping the pressure for 12h, and ensuring complete drying to obtain the fiber bundle-shaped three-dimensional current collector.
Example 8
First, acrylic acid and maleic anhydride were used for the polymerization: adding a certain amount of maleic anhydride, 2 wt% of initiator benzoyl peroxide and a small amount of toluene into a flask, continuously stirring and heating to 80 ℃, starting to slowly dropwise add a mixed solution of acrylic acid and toluene, reacting for 8min, then dropwise adding a mixed solution of acrylic acid and toluene again, controlling the reaction temperature to be about 75 ℃, carrying out heat preservation reaction for 1.5h, cooling to 70 ℃, dropwise adding a mixed solution of octadecanol and toluene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction for 1.5h, stopping the reaction, and carrying out reduced pressure distillation to remove the solvent to obtain the required binder; after synthesizing the needed binder, preparing a binder solution with the concentration of 1.0 wt%, standing, mixing graphite and super-p to ensure that the mass ratio of the graphite to the conductive particle acetylene black is 100: 10, and ball-milling for 30 min. Mixing the solution with graphite and super-p to ensure that the mass ratio of the graphite to the carboxymethyl cellulose is 100: 10, then ball-milling again for 10min to obtain viscous slurry, pouring the slurry into a mould, adjusting the temperature to-40 ℃ in a cold trap, keeping the temperature for 2h, then transferring the slurry into a freeze dryer, adjusting the pressure to 4Pa for 10h, and ensuring complete drying to obtain the fiber bundle-shaped three-dimensional current collector.
Example 9
First, acrylic acid and maleic anhydride were used for the polymerization: adding a certain amount of maleic anhydride, 4 wt% of initiator benzoyl peroxide and a small amount of toluene into a flask, continuously stirring and heating to 70 ℃, starting to slowly dropwise add a mixed solution of acrylic acid and toluene, reacting for 12min, then dropwise adding a mixed solution of acrylic acid and toluene again, controlling the reaction temperature to be about 75 ℃, carrying out heat preservation reaction for 2h, cooling to 70 ℃, dropwise adding a mixed solution of higher alcohol and toluene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction for 2h, stopping the reaction, and carrying out reduced pressure distillation to remove the solvent to obtain the required binder;
after synthesizing the required binder, preparing the binder into a solution with the concentration of 2.0 wt%, standing for later use, mixing graphite and super-p to ensure that the mass ratio of the graphite to the conductive particles super-p is 100: 40, and ball-milling for 50 min.
Mixing the binder solution with graphite and super-p to ensure that the mass ratio of the graphite to the carboxymethyl cellulose is 100: 40, then carrying out ball milling again for 30min to obtain viscous slurry;
pouring the slurry into a mold, adjusting the temperature to-30 ℃ in a cold trap, keeping the temperature constant for 4 hours, transferring the slurry into a freeze dryer, adjusting the pressure to 6Pa, and keeping the pressure for 15 hours to ensure complete drying, thereby obtaining the fiber bundle-shaped three-dimensional current collector.
The foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the fiber bundle-shaped three-dimensional current collector is characterized by comprising the following steps of:
1) adding an initiator into maleic anhydride, adding toluene, stirring and heating to 70-80 ℃, starting to slowly dropwise add a mixed solution of acrylic acid and toluene, carrying out heat preservation reaction for 1.5-2 h, cooling to 70 ℃, dropwise adding a mixed solution of long-chain alcohol and toluene, adding a catalyst, heating to 85 ℃, carrying out heat preservation reaction for 1.5-2 h, stopping reaction, and carrying out reduced pressure distillation to remove a solvent to obtain a binder;
2) preparing a binder into a binder solution;
3) mixing graphite and conductive particles, fully grinding and uniformly mixing to obtain mixed powder;
4) adding the binder solution into the mixed powder, fully grinding and uniformly mixing again to obtain viscous slurry;
5) and pouring the viscous slurry into a mold, transferring to a cold trap, carrying out constant temperature treatment, transferring to freeze drying, and completely drying to obtain the fiber bundle-shaped three-dimensional current collector.
2. The method for preparing the fiber bundle-shaped three-dimensional current collector according to claim 1, wherein the initiator in the step 1) is benzoyl peroxide, and the addition amount of the benzoyl peroxide is 2-4 wt% of the total mass of the mixed solution.
3. The method for preparing the fibrous bundle-shaped three-dimensional current collector according to claim 1, wherein the long-chain alcohol in step 1) is 12-18 alcohol.
4. The method for preparing the fibrous bundle-shaped three-dimensional current collector according to claim 1, wherein the binder concentration in the step 2) is 1-2 wt%.
5. The method for preparing the fiber bundle-shaped three-dimensional current collector as claimed in claim 1, wherein the mass ratio of graphite to the conductive particles in the step 3) is 100: 10-40.
6. The preparation method of the fiber bundle-shaped three-dimensional current collector according to claim 1, wherein the temperature in the cold trap in the step 5) is-40 to-30 ℃, and the temperature is kept constant for 2 to 4 hours.
7. The method for preparing the fiber bundle-shaped three-dimensional current collector according to claim 1, wherein the freeze-drying pressure in the step 5) is 4-6 Pa, and the duration is 10-15 h.
8. The method for preparing the fiber bundle-shaped three-dimensional current collector as claimed in claim 1, wherein in the step 4), the mass ratio of the graphite to the binder is 100: 10-40.
9. The method for preparing the fiber bundle-shaped three-dimensional current collector according to claim 1, wherein the conductive particles are acetylene black or super-p.
10. A fibrous bundle-like three-dimensional current collector, characterized by: the three-dimensional current collector consists of an active substance, a layered structure and conductive particles; wherein the active substance is derived from graphite, the mass ratio of the active substance to the binder is 100: 10-40, and the mass ratio of the active substance to the conductive particles is 100: 10-40; the laminated structure is composed of a binding agent synthesized by maleic anhydride, acrylamide and long-chain alcohol.
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| CN111029522A (en) | 2020-04-17 |
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