CN112279981A - Polymer binder containing soft phase region and hard phase region and preparation method and application thereof - Google Patents

Polymer binder containing soft phase region and hard phase region and preparation method and application thereof Download PDF

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CN112279981A
CN112279981A CN202011128325.XA CN202011128325A CN112279981A CN 112279981 A CN112279981 A CN 112279981A CN 202011128325 A CN202011128325 A CN 202011128325A CN 112279981 A CN112279981 A CN 112279981A
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monomer
binder
hard phase
phase region
soft
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CN112279981B (en
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郭盼龙
李素丽
陈伟平
储霖
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Zhuhai Cosmx Battery Co Ltd
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Zhuhai Cosmx Battery Co Ltd
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    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
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    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
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Abstract

The invention relates to a polymer binder containing a soft phase region and a hard phase region, a preparation method thereof and application thereof in a lithium ion battery. The hard phase region repeating unit provides the binder with high mechanical strength; the soft phase region repeating unit group has excellent chain segment moving capability and a certain amount of repairing groups, thereby endowing the adhesive with good flexibility and self-repairing capability. The adhesive disclosed by the invention has the advantages of high mechanical strength, excellent adhesion, good flexibility and self-repairing capability. Therefore, the adhesive can be widely applied to silicon cathodes or silicon/graphite blended cathodes, and particularly can remarkably reduce the expansion of a cathode pole piece and repair the damage of a bonding network caused by the expansion of the silicon cathode when used in the silicon cathodes, so that the cycle performance of the silicon cathode is remarkably improved.

Description

Polymer binder containing soft phase region and hard phase region and preparation method and application thereof
Technical Field
The invention belongs to the field of binders, and particularly relates to a polymer binder containing a soft phase region and a hard phase region, a preparation method thereof and application thereof in a lithium ion battery.
Background
The theoretical capacity of the silicon-based negative electrode is far greater than that of the graphite negative electrode, and the silicon-based negative electrode has extremely high theoretical capacity, so that the silicon-based negative electrode is the simplest and most effective method for replacing the graphite negative electrode to improve the energy density of the battery. However, the large-scale use of silicon cathodes still faces huge challenges, for example, the silicon cathodes can intercalate and deintercalate more lithium ions during charging and discharging processes, and cause huge volume expansion-contraction effects. Particularly, huge volume expansion can be generated in the lithium embedding process, so that the silicon negative electrode is damaged, the rebound of the silicon negative electrode piece is sharply increased, and even the risk that the silicon negative electrode active layer falls off from the surface of the current collector is caused. Therefore, how to effectively inhibit the volume expansion of the silicon negative electrode and reduce the damage of the SEI film becomes a technical problem which needs to be overcome urgently in the application development of the silicon-based negative electrode.
The silicon negative electrode binder has important effects on improving the peeling strength of the negative electrode plate, inhibiting the silicon negative electrode from expanding and reducing half-electricity/full-electricity rebound of the silicon-based negative electrode plate. At present, the traditional binders such as CMC, SBR, PVDF and the like cannot meet the use requirements of silicon cathodes, while the novel binders such as polyacrylic acid, polyacrylamide, polyimide and the like have larger rigidity and insufficient flexibility, and the risk of bonding failure due to the volume change of the silicon cathodes still exists in the circulating process. Therefore, development of a novel binder having good adhesion, high strength, high flexibility, and capability of repairing damage due to volume expansion of a silicon negative electrode has been required.
Disclosure of Invention
The invention aims to provide a soft-hard phase region combined self-repairing polymer binder material, which has high mechanical strength, flexibility and good cohesiveness and repairs the damage of volume expansion of a silicon negative electrode to the binder. Wherein the hard phase is used for improving the mechanical strength of the binder and inhibiting the silicon negative electrode from expanding, and the soft phase is used for improving the flexibility and the cohesiveness of the binder and endowing the self-repairing performance of the binder.
The purpose of the invention is realized by the following technical scheme:
a polymeric binder comprising a soft phase domain and a hard phase domain, the hard phase domain being polymerized from a rigid monomer a and the soft phase domain being polymerized from a flexible monomer B and a monomer C comprising a dynamic interacting group.
According to an embodiment of the invention, the binder is polymerized by living radical polymerization, such as reversible addition-fragmentation chain transfer polymerization (RAFT) or Atom Transfer Radical Polymerization (ATRP).
According to the embodiment of the invention, the polymerization method of the binder comprises the following specific steps:
firstly, polymerizing a rigid monomer A (forming a hard phase region), after the rigid monomer A is polymerized, adding a flexible monomer B and a monomer C containing a dynamic interaction group into the mixture to be polymerized continuously (forming a soft phase region), and finally obtaining the adhesive simultaneously containing the hard phase region (the rigid monomer A is a structural unit) and the soft phase region (the rigid monomer B and the monomer C containing the dynamic interaction group are structural units). The monomer polymerization mode can be copolymerization in a form of forming a hard phase-soft phase, namely, rigid monomer A is polymerized first, then flexible monomer B and monomer C containing dynamic interaction groups are polymerized, and can also be polymerization in a form of forming a hard phase-soft phase-hard phase or a soft phase-hard phase-soft phase, and can exist in a form of combining more phase regions according to requirements.
In the present invention, rigid monomer means that the Tg of the pure polymer of the monomer is above room temperature; for example, in a glassy state at room temperature.
In the present invention, a flexible monomer means that the Tg of the pure polymer of the monomer is below room temperature; for example, in the elastomeric state at room temperature, the side chains are generally relatively long.
Specifically, the room temperature in the present invention means a temperature of 25 ℃. The monomer-pure polymer refers to a polymer obtained by polymerizing only the monomer.
In the present invention, the dynamic interaction group means a group containing a hydrogen bond, a host-guest interaction, a dynamic covalent bond, a weak coordinate bond, and the like, which can form a dynamic interaction and can be recombined at a certain temperature.
According to an embodiment of the invention, the monomer C containing a dynamic interacting group is a monomer containing a group capable of forming a hydrogen bond.
The monomers C containing dynamic interacting groups are selected, for example, from
Figure BDA0002734284660000031
At least one of; preferably, it is
Figure BDA0002734284660000032
Wherein m is 1-8; x is 0-7; y is 1 to 8.
According to an embodiment of the invention, said rigid monomer A is selected from
Figure BDA0002734284660000033
Figure BDA0002734284660000034
At least one of; wherein R1 is Cl, Br, I or F; preferably, it is
Figure BDA0002734284660000035
According to an embodiment of the invention, the flexible monomer B is selected from
Figure BDA0002734284660000036
At least one of; preferably, it is
Figure BDA0002734284660000037
Wherein n is 1 to 8.
According to an embodiment of the present invention, the structure of the binder may be hard phase-soft phase, hard phase-soft phase-hard phase, soft phase-hard phase-soft phase, or may be present in a combination of more phase regions as desired.
According to an embodiment of the invention, the polymer molecular weight Mw of the hard phase region is: 1000-200 ten thousand, the polymer molecular weight Mw of the soft phase region is: 1000-.
According to an embodiment of the present invention, the soft phase region is a random copolymer unit formed by polymerization of monomers B and C.
According to an embodiment of the invention, the molar ratio of hard phase region repeat units to total repeat units is 5-90 mol%, such as 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%.
According to an embodiment of the present invention, the molar ratio of the soft phase region repeating units (sum of repeating units formed by polymerizing the monomers B and C) to the total repeating units is 10 to 95 mol%, such as 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%.
According to an embodiment of the invention, the molar ratio of monomer B and monomer C is between 1 and 20; exemplary are 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 10:1, 15:1, 20: 1; preferably 7: 1.
According to an embodiment of the invention, the binder has a stress of 0.1-20MPa and an elongation at break of 10-200%.
The hard phase area in the binder enables the binder to have high mechanical strength, the soft phase area enables the binder to have good flexibility, and the soft phase area has excellent chain segment movement capability and a certain amount of repairing groups, so that the binder has good self-repairing capability. The structure of the adhesive of the present invention is schematically shown in fig. 13.
The invention also provides a preparation method of the adhesive, which comprises the step of polymerizing the monomer A, the monomer B and the monomer C to form the self-repairing adhesive combining the soft phase region and the hard phase region.
According to the embodiment of the invention, the monomer A is polymerized (forming a hard phase), after the monomer A is polymerized, the monomers B and C are added to continue the polymerization (forming a soft phase), and finally the adhesive containing the hard phase (the monomer A is a structural unit) and the soft phase (the monomers B and C are the structural units) is obtained.
According to an embodiment of the invention, the polymerization mode is living radical polymerization; for example reversible addition-fragmentation chain transfer polymerization (RAFT) or Atom Transfer Radical Polymerization (ATRP).
According to an embodiment of the invention, the temperature of the polymerization reaction is 45-100 ℃; preferably 60-90 ℃; exemplary are 45 deg.C, 60 deg.C, 75 deg.C, 100 deg.C.
According to an embodiment of the present invention, the time of the polymerization reaction is 1 to 24 hours; preferably 4-16 h; exemplary are 1h, 2h, 4h, 6h, 8h, 10h, 12h, 16h, 20h, 24 h.
According to an embodiment of the present invention, a reversible addition-fragmentation chain transfer reagent (RAFT reagent) is added during the reversible addition-fragmentation chain transfer polymerization (RAFT).
Preferably, the RAFT agent is selected from at least one of dibenzyltrithiocarbonate, 4-cyano-4- [ [ (dodecylthio) thiocarbonyl ] thio ] pentanoic acid, 2- (dodecylthio-thiocarbonylthio) -2-methylpropionic acid, cyanomethyl methyl (phenyl) aminodithioate.
Preferably, the RAFT agent is used in a molar ratio of 0.01% to 5% of the total repeat units.
According to the embodiment of the invention, an initiator is added in the polymerization process of the monomer A, the monomer B and the monomer C.
Preferably, the initiator is an oil soluble initiator; for example, at least one of Azobisisobutyronitrile (AIBN), benzoyl peroxide, azobisisoheptonitrile, or azobisisocyano valeric acid; preferably Azobisisobutyronitrile (AIBN).
According to an embodiment of the invention, the initiator is used in a molar ratio of 0.01% to 5% with respect to the total repeating units.
According to an embodiment of the present invention, the method for preparing the binder further comprises the steps of precipitating, washing, and vacuum drying the polymer solution after the polymerization is completed.
The invention also provides application of the adhesive in an electrode plate of a lithium ion battery.
The invention also provides a lithium ion battery electrode plate, which contains the adhesive; for example, the lithium ion battery electrode plate can be a positive plate and/or a negative plate; preferably, the lithium ion battery electrode plate is a negative electrode plate.
According to the embodiment of the invention, the mass percentage of the binder in the electrode plate is 0.1-20 wt%.
According to an embodiment of the present invention, the lithium ion battery electrode sheet further includes an electrode active material and/or a conductive agent.
According to an embodiment of the present invention, the conductive agent is at least one of acetylene black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene, and reduced graphene oxide.
According to an embodiment of the present invention, the negative electrode sheet is selected from at least one of elemental silicon, silicon oxide, natural graphite, artificial graphite, mesophase carbon fiber, mesophase carbon microsphere, soft carbon, and hard carbon.
The invention also provides a preparation method of the lithium ion battery electrode plate, which comprises the steps of preparing the binder, the electrode active substance and/or the conductive agent into slurry, coating and drying; wherein the binder accounts for 0.1-20 wt% of the total mass of the slurry.
According to an embodiment of the present invention, the negative electrode sheet containing the above binder has an average peel strength of 0.1 to 40N/m.
The invention also provides a lithium ion battery, which contains the adhesive and/or the lithium ion battery electrode plate.
According to an embodiment of the invention, the negative plate of the lithium ion battery contains the binder.
According to an embodiment of the present invention, the lithium ion battery further comprises a positive electrode sheet.
The invention has the beneficial effects that:
the hard phase area in the binder provided by the invention enables the binder to have high mechanical strength and inhibits the silicon negative electrode from expanding, and the soft phase area enables the binder to have good flexibility and cohesiveness; and the soft phase region has excellent chain segment motion capability and a certain amount of repair groups, so that the adhesive has good self-repair capability, the damage of a bonding network caused by the expansion of the silicon negative electrode can be repaired in time, the expansion of the pole piece is reduced, and the cycle life is prolonged. The self-repairing adhesive material based on the soft-hard phase combination has high mechanical strength, excellent adhesion, good flexibility and self-repairing damage performance. Therefore, the adhesive can be widely applied to silicon cathodes or silicon/graphite blended cathodes to remarkably reduce the expansion of a cathode pole piece and repair the damage of an adhesive network caused by the expansion of the silicon cathodes, thereby remarkably improving the cycle performance of the silicon cathodes.
Drawings
FIG. 1 shows the nuclear magnetic spectrum (500MHz, DMSO-d) of Binder 1 obtained in preparation example 16)；
FIG. 2 is a stress-strain curve before and after repair of Binder 1;
FIG. 3 is an infrared spectrum of Binder 2 obtained in preparation example 2;
FIG. 4 is a stress-strain curve before and after repair of Binder 2;
FIG. 5 shows a nuclear magnetic spectrum (500MHz, CDCl) of the binder 3 obtained in preparation example 33)；
FIG. 6 is a stress-strain curve before and after repair of the adhesive 3;
FIG. 7 shows a nuclear magnetic spectrum (500MHz, DMSO-d) of Binder 4 obtained in preparation example 46)；
FIG. 8 is a stress-strain curve before and after repair of the adhesive 4;
FIG. 9 is a plot of cell discharge capacity versus cycle period for example 1, comparative example 1, and comparative example 2;
FIG. 10 is a plot of cell discharge capacity versus cycle period for example 2, comparative example 1, and comparative example 3;
FIG. 11 is a plot of cell discharge capacity versus cycle period for example 3, comparative example 1, and comparative example 4;
FIG. 12 is a plot of cell discharge capacity versus cycle period for example 4, comparative example 1, and comparative example 5;
fig. 13 is a schematic view of the adhesive structure of the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Preparation example 1
Structural formula is
Figure BDA0002734284660000081
The preparation of binder 1 according to (1) comprises the following steps:
(1) hard phase region-containing polymer preparation (styrene building blocks as hard phase): styrene (10.42g, 100mmol), dibenzyl trithiocarbonate (0.160g, 0.55mmol, RAFT reagent), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And after the polymerization reaction is finished, cooling to room temperature, adding the reaction solution into deionized water, separating out a precipitate, filtering, washing with water for multiple times, and performing vacuum drying at room temperature to obtain the polystyrene with the polymer end group containing the RAFT reagent.
(2) Hard-soft domain polymer preparation (ethyl acrylate building block as soft phase, 5-acetamidopentyl acrylate building block providing a repair group): the polymer produced in step (1) (1.04g), amyl 5-acetaminoacrylate (1.99g, 10mmol), ethyl acrylate (7.01g, 70mmol), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. After the polymerization reaction is finished, cooling to room temperature, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at room temperature.
(3) Hard phase-soft phase-hard phase region containing polymer preparation: the polymer produced in step (2) (10.04g), styrene (1.04g, 10mmol), DMF (20mL) and AIBN (2.956mg, 0.018mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And cooling to room temperature after the polymerization reaction is finished, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at 80 ℃ to obtain the polymer binder.
The nuclear magnetic spectrum of the binder obtained in this example is shown in fig. 1.
And (3) repairing performance characterization: the sample of the adhesive obtained in this example was prepared into a standard sample strip (length × width × thickness 80mm × 10mm × 1mm), cut into two halves with a scalpel, and the section was exposed for different times (10min, 20min, 30min, and 40min) at room temperature, and the mechanical properties of the sample after different repair times (different time of section exposure) were respectively tested, and the results are shown in fig. 2. From the results in the figure, the mechanical properties of the initial sample can be basically achieved by repairing the cross section for 40min at normal temperature. Therefore, the adhesive prepared by the embodiment has a quick self-repairing function.
Preparation example 2
Structural formula is
Figure BDA0002734284660000091
The preparation of binder 2 according to (1) comprises the following steps:
(1) hard phase region-containing polymer preparation (acrylamide structural units as hard phases): acrylamide (7.1g, 100mmol), dibenzyl trithiocarbonate (0.160g, 0.55mmol, RAFT reagent), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And cooling to room temperature after the polymerization reaction is finished, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and performing vacuum drying at room temperature to obtain the acrylamide with the polymer end group containing the RAFT reagent.
(2) Hard-soft domain polymer preparation (dimethylaminoethyl acrylate building block as soft phase, 2- (3-ethylureido) ethyl acrylate building block providing a repair group): the polymer prepared in step (1) (2.13g), 2- (3-ethylureido) ethyl acrylate (1g, 5mmol), dimethylaminoethyl acrylate (5.01g, 35mmol), DMF (20mL) and AIBN (18.06mg, 0.11mmol) were weighed into a 100mL Schlenk's bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. After the polymerization reaction is finished, cooling to room temperature, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at room temperature.
(3) Hard phase-soft phase-hard phase region containing polymer preparation: the polymer produced in step (2) (8.14g), acrylamide (2.13g, 30mmol), DMF (20mL) and AIBN (8.87mg, 0.054mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And cooling to room temperature after the polymerization reaction is finished, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at 80 ℃ to obtain the polymer binder.
The nuclear magnetic spectrum of the binder obtained in this example is shown in fig. 3.
And (3) repairing performance characterization: the adhesive sample obtained in this example was prepared into a standard sample strip (length × width × thickness 80mm × 10mm × 1mm), cut into two halves with a scalpel, and the section was exposed for different times (10min, 30min) at room temperature, and the mechanical properties of the sample after repair were measured, and the results are shown in fig. 4. From the results in the figure, when the fracture surface is repaired at normal temperature for 30min, the stress can be repaired to 85% of the initial sample, and the strain can be repaired to 82% of the initial sample.
Preparation example 3
Structural formula is
Figure BDA0002734284660000101
Preparation of Binder 3 (2):
(1) preparation of a polymer containing hard phase regions (methyl methacrylate building blocks as hard phase): methyl methacrylate (10g, 100mmol), dibenzyl trithiocarbonate (0.160g, 0.55mmol, RAFT reagent), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And cooling to room temperature after the polymerization reaction is finished, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and performing vacuum drying at room temperature to obtain the methyl methacrylate with the polymer end group containing the RAFT reagent.
(2) Hard phase-soft phase region polymer preparation (butyl acrylate building block as soft phase, 4-amido butyl acrylate building block providing a repair group): the polymer prepared in step (1) (2.0g), butyl 4-acylamidoacrylate (1.85g, 10mmol), butyl acrylate (6.41g, 50mmol), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. After the polymerization reaction is finished, cooling to room temperature, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at room temperature.
(3) Hard phase-soft phase-hard phase region containing polymer preparation: the polymer produced in step (2) (10.25g), methyl methacrylate (2.0g, 20mmol), DMF (20mL) and AIBN (2.956mg, 0.018mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And cooling to room temperature after the polymerization reaction is finished, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at 80 ℃ to obtain the polymer binder.
The nuclear magnetic spectrum of the binder obtained in this example is shown in fig. 5.
And (3) repairing performance characterization: the adhesive sample obtained in this example was prepared into a standard sample strip (length. times. width. times. thickness: 80 mm. times.10 mm. times.1 mm), cut into two halves with a scalpel, and the cross section was contacted for 1 hour at normal temperature, and the mechanical properties of the sample after repair were measured, and the results are shown in FIG. 6. From the results in the figure, when the fracture surface is repaired at normal temperature for 1h, the stress can be repaired to 93% of the initial sample, and the strain can be repaired to 92% of the strain of the initial sample. Therefore, the adhesive prepared by the embodiment has a high self-repairing function.
Preparation example 4
Structural formula is
Figure BDA0002734284660000111
Preparation of Binder 4 of (2):
(1) hard phase region-containing Polymer preparation (4-vinylpyridine units as hard phase): 4-vinylpyridine (10.5g, 100mmol), dibenzyltrithiocarbonate (0.160g, 0.55mmol, RAFT reagent), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And after the polymerization reaction is finished, cooling to room temperature, adding the reaction solution into deionized water, separating out a precipitate, filtering, washing with water for multiple times, and performing vacuum drying at room temperature to obtain the polystyrene with the polymer end group containing the RAFT reagent.
(2) Hard-soft domain polymer preparation (hydroxyethyl acrylate building block as soft phase, 4-acetamidobutyl acrylate building block providing a repair group): the polymer prepared in step (1) (2.1g), butyl 4-acetamidoacrylate (1.86g, 10mmol), hydroxyethyl acrylate (5.81g, 50mmol), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. After the polymerization reaction is finished, cooling to room temperature, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at room temperature.
(3) Hard phase-soft phase-hard phase region containing polymer preparation: the polymer produced in step (2) (9.75g), 4-vinylpyridine (2.1g, 20mmol), DMF (20mL) and AIBN (2.956mg, 0.018mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And cooling to room temperature after the polymerization reaction is finished, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at 80 ℃ to obtain the polymer binder.
The nuclear magnetic spectrum of the binder obtained in this example is characterized by the repair performance shown in fig. 7: the sample was prepared into a standard sample strip (length. times. width. times. thickness: 80 mm. times.10 mm. times.1 mm), cut into two halves with a scalpel, and the section was exposed to different times (10min, 20min, 40min) at room temperature, and the mechanical properties of the sample after the repair were measured, and the results are shown in FIG. 8. From the results in the figure, when the fracture surface is repaired at normal temperature for 40min, the stress can be repaired to 83% of the initial sample, and the strain can be repaired to 87% of the initial sample.
Preparation example 5
Structural formula is
Figure BDA0002734284660000121
The adhesive 5 (compared with the adhesive 1, the adhesive does not contain a repair monomer 5-acetamido amyl acrylate and has no repair function), and the preparation method comprises the following steps:
(1) hard phase region-containing polymer preparation (styrene building blocks as hard phase): styrene (10.42g, 100mmol), dibenzyl trithiocarbonate (0.160g, 0.55mmol, RAFT reagent), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And after the polymerization reaction is finished, cooling to room temperature, adding the reaction solution into deionized water, separating out a precipitate, filtering, washing with water for multiple times, and performing vacuum drying at room temperature to obtain the polystyrene with the polymer end group containing the RAFT reagent.
(2) Hard phase-soft phase region polymer preparation (ethyl acrylate building blocks as soft phase): the polymer produced in step (1) (1.04g), ethyl acrylate (8.01g, 80mmol), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. After the polymerization reaction is finished, cooling to room temperature, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at room temperature.
(3) Hard phase-soft phase-hard phase region containing polymer preparation: the polymer produced in step (2) (10.04g), styrene (1.04g, 10mmol), DMF (20mL) and AIBN (2.956mg, 0.018mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And cooling to room temperature after the polymerization reaction is finished, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at 80 ℃ to obtain the polymer binder.
Preparation example 6
Structural formula is
Figure BDA0002734284660000131
Binder 6 (which does not contain the repair monomer 2- (3-ethylureido) ethyl acrylate, no repair function, as compared to binder 2) is prepared as follows:
(1) hard phase region-containing polymer preparation (acrylamide structural units as hard phases): acrylamide (7.1g, 100mmol), dibenzyl trithiocarbonate (0.160g, 0.55mmol, RAFT reagent), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And cooling to room temperature after the polymerization reaction is finished, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and performing vacuum drying at room temperature to obtain the acrylamide with the polymer end group containing the RAFT reagent.
(2) Hard phase-soft phase region polymer preparation (dimethylaminoethyl acrylate building blocks as soft phase): the polymer (2.13g) produced in step (1), dimethylaminoethyl acrylate (5.726g, 40mmol), DMF (20mL) and AIBN (18.06mg, 0.11mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. After the polymerization reaction is finished, cooling to room temperature, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at room temperature.
(3) Hard phase-soft phase-hard phase region containing polymer preparation: the polymer produced in step (2) (8.14g), acrylamide (2.13g, 30mmol), DMF (20mL) and AIBN (8.87mg, 0.054mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And cooling to room temperature after the polymerization reaction is finished, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at 80 ℃ to obtain the polymer binder.
Preparation example 7
Structural formula is
Figure BDA0002734284660000141
The adhesive 7 (compared with the adhesive 3, the adhesive does not contain a repairing monomer, namely 4-amido butyl acrylate, and has no repairing function) is prepared by the following steps:
(1) preparation of a polymer containing hard phase regions (methyl methacrylate building blocks as hard phase): methyl methacrylate (10g, 100mmol), dibenzyl trithiocarbonate (0.160g, 0.55mmol, RAFT reagent), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And cooling to room temperature after the polymerization reaction is finished, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and performing vacuum drying at room temperature to obtain the methyl methacrylate with the polymer end group containing the RAFT reagent.
(2) Hard phase-soft phase region polymer preparation (butyl acrylate building block as soft phase): the polymer (2.0g) produced in step (1), butyl acrylate (7.68g, 60mmol), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. After the polymerization reaction is finished, cooling to room temperature, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at room temperature.
(3) Hard phase-soft phase-hard phase region containing polymer preparation: the polymer produced in (2) (10.25g), methyl methacrylate (2.0g, 20mmol), DMF (20mL) and AIBN (2.956mg, 0.018mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And cooling to room temperature after the polymerization reaction is finished, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at 80 ℃ to obtain the polymer binder.
Preparation example 8
Structural formula is
Figure BDA0002734284660000151
The adhesive 8 (compared with the adhesive 4, the adhesive does not contain a repairing monomer 4-acetamido butyl acrylate and has no repairing function) is prepared by the following steps:
(1) hard phase region-containing Polymer preparation (4-vinylpyridine units as hard phase): 4-vinylpyridine (10.5g, 100mmol), dibenzyltrithiocarbonate (0.160g, 0.55mmol, RAFT reagent), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And after the polymerization reaction is finished, cooling to room temperature, adding the reaction solution into deionized water, separating out a precipitate, filtering, washing with water for multiple times, and performing vacuum drying at room temperature to obtain the polystyrene with the polymer end group containing the RAFT reagent.
(2) Hard phase-soft phase region polymer preparation (hydroxyethyl acrylate building blocks as soft phase): the polymer produced in (1) (2.1g), hydroxyethyl acrylate (6.96g, 60mmol), DMF (20mL) and AIBN (29.56mg, 0.18mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. After the polymerization reaction is finished, cooling to room temperature, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at room temperature.
(3) Hard phase-soft phase-hard phase region containing polymer preparation: the polymer produced in (2) (9.75g), 4-vinylpyridine (2.1g, 20mmol), DMF (20mL) and AIBN (2.956mg, 0.018mmol) were weighed into a 100mL Schlenk bottle. Oxygen was removed 3 times by freeze-thaw and then reacted at 75 ℃ for 12 h. And cooling to room temperature after the polymerization reaction is finished, adding the reaction solution into deionized water to separate out a precipitate, filtering, washing with water for multiple times, and drying in vacuum at 80 ℃ to obtain the polymer binder.
Example 1
A lithium ion battery is prepared by the following steps:
the nano silicon active substance, the conductive agent carbon black (Super-P) and the binder 1 obtained in preparation example 1 are dispersed in an N-methylpyrrolidone (NMP) solvent in a mass ratio of 8:1:1, and are ground and stirred to form uniform slurry, and the uniform slurry is coated on a copper foil. Then the pole piece is placed in a drying oven, dried for 36h at 80 ℃, cut into a circular pole piece with the diameter of 1cm, and stored in a glove box (the surface density is 1 mg/cm)2)。
And assembling 2032 button cells by using lithium sheets as counter electrodes. Wherein the electrolyte adopts (EC/DMC/DEC ═ 1:1:1, 1M LiPF6) The solution, containing fluoroethylene carbonate (FEC) additive (10 vol%) in the electrolyte, was left to stand for 12 h.
And (3) testing the constant-current charge and discharge performance of the battery which is well placed on a blue-ray test system, wherein the charge and discharge current is 500mA/g, the voltage range is 0.01-1V, and the test result is shown in figure 9. From the results of the graph, it can be seen that the first cycle discharge capacity of the battery was 3510mAh/g, the discharge capacity after cycle 310 (T) was 2120mAh/g, and the capacity retention rate was 60.40%. The initial thickness of the pole piece is 41.3 μm, the thickness of the pole piece disassembled in air-electricity mode after the cycle of 310T is 80.3 μm, and the rebound rate of the pole piece is 94.43% (Table 1). The capacity retention rate and the pole piece rebound rate are better than those of comparative example 1 and comparative example 2.
Example 2
A lithium ion battery is prepared by the following steps:
dispersing nano silicon active substances, conductive agent carbon black (Super-P) and the binder 2 obtained in the preparation example 2 in an NMP solvent in a mass ratio of 8:1:1, grinding and stirring to form uniform slurry, and coating the uniform slurry on a copper foil. Then the pole piece is placed in a drying oven, dried for 36h at 80 ℃, cut into a circular pole piece with the diameter of 1cm, and stored in a glove box (the surface density is 1 mg/cm)2)。
And assembling 2032 button cells by using lithium sheets as counter electrodes. It is composed ofIn the electrolyte, the electrolyte adopts (EC/DMC/DEC ═ 1:1:1, 1M LiPF6) The solution, containing the FEC additive in the electrolyte (10 vol%), was left to stand for 12 h.
And (3) testing the constant-current charge and discharge performance of the battery which is well placed on a blue-ray test system, wherein the charge and discharge current is 500mA/g, the voltage range is 0.01-1V, and the test result is shown in figure 10. As can be seen from the results in the figure, the first cycle discharge capacity of the battery is 3515mAh/g, the discharge capacity after 310 cycles is 1986mAh/g, and the capacity retention rate is 50.50%. The initial thickness of the pole piece is 41.1 μm, the thickness of the pole piece disassembled in air-electricity mode after 310T circulation is 80.3 μm, and the rebound rate of the pole piece is 95.38% (Table 1). The capacity retention rate and the pole piece rebound rate are better than those of comparative example 1 and comparative example 3.
Example 3
A lithium ion battery is prepared by the following steps:
the nano silicon active material, the conductive agent carbon black (Super-P) and the binder 3 obtained in preparation example 3 were dispersed in NMP solvent in a mass ratio of 8:1:1, and a uniform slurry was formed by grinding and stirring and coated on a copper foil. Then the pole piece is placed in a drying oven, dried for 36h at 80 ℃, cut into a circular pole piece with the diameter of 1cm, and stored in a glove box (the surface density is 1 mg/cm)2)。
And assembling 2032 button cells by using lithium sheets as counter electrodes. Wherein the electrolyte adopts (EC/DMC/DEC ═ 1:1:1, 1M LiPF6) The solution, containing the FEC additive in the electrolyte (10 vol%), was left to stand for 12 h.
And (3) testing the constant-current charge and discharge performance of the battery which is well placed on a blue-ray test system, wherein the charge and discharge current is 500mA/g, the voltage range is 0.01-1V, and the test result is shown in figure 11. From the results in the figure, it can be seen that the first cycle discharge capacity of the battery was 3520mAh/g, the discharge capacity after cycle 310 was 1964mAh/g, and the capacity retention rate was 55.80%. The initial thickness of the pole piece is 41.2 μm, the thickness of the pole piece disassembled in air-electricity mode after 310T circulation is 81.3 μm, and the rebound rate of the pole piece is 97.33% (Table 1). The capacity retention rate and the pole piece rebound rate are better than those of comparative example 1 and comparative example 4.
Example 4
A lithium ion battery is prepared by the following steps:
the nano silicon active material, the conductive agent carbon black (Super-P) and the binder 4 obtained in preparation example 4 were dispersed in NMP solvent at a mass ratio of 8:1:1, and a uniform slurry was formed by grinding and stirring and coated on a copper foil. Then the pole piece is placed in a drying oven, dried for 36h at 80 ℃, cut into a circular pole piece with the diameter of 1cm, and stored in a glove box (the surface density is 1 mg/cm)2)。
And assembling 2032 button cells by using lithium sheets as counter electrodes. Wherein the electrolyte adopts (EC/DMC/DEC ═ 1:1:1, 1M LiPF6) The solution, containing the FEC additive in the electrolyte (10 vol%), was left to stand for 12 h.
And (3) testing the constant-current charge and discharge performance of the battery which is well placed on a blue-ray test system, wherein the charge and discharge current is 500mA/g, the voltage range is 0.01-1V, and the test result is shown in figure 12. From the results in the figure, it can be seen that the first cycle discharge capacity of the battery was 3518mAh/g, the discharge capacity after cycle 310 was 1886mAh/g, and the capacity retention rate was 53.60%. The initial thickness of the pole piece is 41.5 μm, the thickness of the pole piece disassembled in air-electricity mode after 310T circulation is 82.3 μm, and the rebound rate of the pole piece is 98.31% (table 1). The capacity retention rate and the pole piece rebound rate are better than those of comparative example 1 and comparative example 4.
Comparative example 1
A lithium ion battery is prepared by the following steps:
nano silicon active material, conductive agent carbon black (Super-P) and commercial PAA (Mw:25w) were dispersed in NMP solvent at a mass ratio of 8:1:1, formed into uniform slurry by grinding and stirring, and coated on a copper foil. Then the pole piece is placed in a drying oven, dried for 36h at 80 ℃, cut into a circular pole piece with the diameter of 1cm, and stored in a glove box (the surface density is 1 mg/cm)2). And assembling 2032 button cells by using lithium sheets as counter electrodes. Wherein, the electrolyte adopts (EC/DMC/DEC ═ 1:1:1, 1M LiPF6) solution, the electrolyte contains FEC additive (10 vol%), and the assembled battery is kept still for 12 h.
And (3) testing the constant-current charge and discharge performance of the battery which is well placed on a blue-ray test system, wherein the charge and discharge current is 500mA/g, the voltage range is 0.01-1V, and the test result is shown in figure 9. From the results in the figure, it can be seen that the first cycle discharge capacity of the battery was 3521mAh/g, the discharge capacity after 310 cycles of the cycle was 1080mAh/g, and the capacity retention rate was 30.67%. The initial thickness of the pole piece is 41.3 μm, the thickness of the pole piece disassembled in air-electricity mode after 310T circulation is 92.3 μm, and the rebound rate of the pole piece is 123.49% (Table 1).
Comparative example 2
A lithium ion battery is prepared by the following steps:
the nano silicon active substance, the conductive agent carbon black (Super-P) and the binder 5 obtained in preparation example 5 were dispersed in NMP solvent in a mass ratio of 8:1:1, and a uniform slurry was formed by grinding and stirring and coated on a copper foil. Then the pole piece is placed in a drying oven, dried for 36h at 80 ℃, cut into a circular pole piece with the diameter of 1cm, and stored in a glove box (the surface density is 1 mg/cm)2). And assembling 2032 button cells by using lithium sheets as counter electrodes. Wherein, the electrolyte adopts (EC/DMC/DEC ═ 1:1:1, 1M LiPF6) solution, the electrolyte contains FEC additive (10 vol%), and the assembled battery is kept still for 12 h.
And (3) testing the constant-current charge and discharge performance of the battery which is well placed on a blue-ray test system, wherein the charge and discharge current is 500mA/g, the voltage range is 0.01-1V, and the test result is shown in figure 9. As can be seen from the results in the figure, the first cycle discharge capacity of the battery was 3510mAh/g, the discharge capacity after 310T cycle was 1490mAh/g, and the capacity retention rate was 42.45%. The initial thickness of the pole piece is 41.4 μm, the thickness of the pole piece disassembled in air-electricity mode after 310T circulation is 93.4 μm, and the rebound rate of the pole piece is 125.6% (table 1).
Comparative example 3
A lithium ion battery is prepared by the following steps:
the nano silicon active substance, the conductive agent carbon black (Super-P) and the binder 6 obtained in preparation example 6 were dispersed in NMP solvent in a mass ratio of 8:1:1, and a uniform slurry was formed by grinding and stirring and coated on a copper foil. Then the pole piece is placed in a drying oven, dried for 36h at 80 ℃, cut into a circular electrode piece with the diameter of 1cm, and placed in a glove box for storage (surface)The density is 1mg/cm2). And assembling 2032 button cells by using lithium sheets as counter electrodes. Wherein, the electrolyte adopts (EC/DMC/DEC ═ 1:1:1, 1M LiPF6) solution, the electrolyte contains FEC additive (10 vol%), and the assembled battery is kept still for 12 h.
And (3) testing the constant-current charge and discharge performance of the battery which is well placed on a blue-ray test system, wherein the charge and discharge current is 500mA/g, the voltage range is 0.01-1V, and the test result is shown in figure 10. From the results in the figure, it can be seen that the first cycle discharge capacity of the battery is 3508mAh/g, the discharge capacity after 310T cycling is 1010mAh/g, and the capacity retention rate is 28.79%. The initial thickness of the pole piece is 41.6 μm, the thickness of the pole piece disassembled in air-electricity mode after 310T circulation is 91.6 μm, and the rebound rate of the pole piece is 120.19% (Table 1).
Comparative example 4
A lithium ion battery is prepared by the following steps:
the nano silicon active material, the conductive agent carbon black (Super-P) and the binder 7 obtained in preparation example 7 were dispersed in NMP solvent at a mass ratio of 8:1:1, and a uniform slurry was formed by grinding and stirring and coated on a copper foil. Then the pole piece is placed in a drying oven, dried for 36h at 80 ℃, cut into a circular pole piece with the diameter of 1cm, and stored in a glove box (the surface density is 1 mg/cm)2). And assembling 2032 button cells by using lithium sheets as counter electrodes. Wherein, the electrolyte adopts (EC/DMC/DEC ═ 1:1:1, 1M LiPF6) solution, the electrolyte contains FEC additive (10 vol%), and the assembled battery is kept still for 12 h.
And (3) testing the constant-current charge and discharge performance of the battery which is well placed on a blue-ray test system, wherein the charge and discharge current is 500mA/g, the voltage range is 0.01-1V, and the test result is shown in figure 11. As can be seen from the results in the figure, the first cycle discharge capacity of the battery is 3514mAh/g, the discharge capacity after 310T circulation is 820mAh/g, and the capacity retention rate is 23.34%. The initial thickness of the pole piece is 41.1 μm, the thickness of the pole piece disassembled in air-electricity after 310T circulation is 91.2 μm, and the rebound rate of the pole piece is 121.90% (Table 1).
Comparative example 5
A lithium ion battery is prepared by the following steps:
mixing the nanometerA silicon active material, a conductive agent carbon black (Super-P) and the binder 8 obtained in preparation example 8 were dispersed in NMP solvent at a mass ratio of 8:1:1, formed into a uniform slurry by grinding and stirring, and coated on a copper foil. Then the pole piece is placed in a drying oven, dried for 36h at 80 ℃, cut into a circular pole piece with the diameter of 1cm, and stored in a glove box (the surface density is 1 mg/cm)2). And assembling 2032 button cells by using lithium sheets as counter electrodes. Wherein, the electrolyte adopts (EC/DMC/DEC ═ 1:1:1, 1M LiPF6) solution, the electrolyte contains FEC additive (10 vol%), and the assembled battery is kept still for 12 h.
And (3) testing the constant-current charge and discharge performance of the battery which is well placed on a blue-ray test system, wherein the charge and discharge current is 500mA/g, the voltage range is 0.01-1V, and the test result is shown in figure 12. From the results in the figure, it can be seen that the first cycle discharge capacity of the battery is 3517mAh/g, the discharge capacity after 310T circulation is 1460mAh/g, and the capacity retention rate is 41.51%. The initial thickness of the pole piece is 41.7 μm, the thickness of the pole piece disassembled in air-electricity mode after 310T circulation is 92.6 μm, and the rebound rate of the pole piece is 122.06% (Table 1).
Table 1: examples 1-4, comparative examples 1-5 starting sheet thickness and pole piece thickness and expansion rate after 310 cycles for electrokinetic disassembly.
Experimental protocol Pole piece thickness before cycle Pole piece thickness after 310 cycles Rebound rate of pole piece
Example 1 41.3μm 80.3μm 94.43％
Example 2 41.1μm 80.3μm 95.38％
Example 3 41.2μm 81.3μm 97.33％
Example 4 41.5μm 82.3μm 98.31％
Comparative example 1 41.3μm 92.3μm 123.49％
Comparative example 2 41.4μm 93.4μm 125.60％
Comparative example 3 41.6μm 91.6μm 120.19％
Comparative example 4 41.1μm 91.2μm 121.90％
Comparative example 5 41.7μm 92.6μm 122.06％
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A polymeric binder comprising soft and hard phase domains, wherein the hard phase domains are polymerized from a rigid monomer a and the soft phase domains are polymerized from a flexible monomer B and a monomer C comprising a dynamic interacting group.
2. The polymeric binder of claim 1 wherein the rigid monomer means that the Tg of the monomer alone is above room temperature; for example, in a glassy state at room temperature;
the flexible monomer means that the Tg of the pure polymer of the monomer is below room temperature; for example, in a highly elastic state at room temperature;
the monomer containing the dynamic interaction group refers to a monomer containing hydrogen bonds, subject-guest interactions, dynamic covalent bonds, weak coordinate bonds and other groups.
Preferably, the binder is polymerized by living radical polymerization, such as reversible addition-fragmentation chain transfer polymerization (RAFT) or Atom Transfer Radical Polymerization (ATRP);
preferably, the polymerization method of the binder comprises the following specific steps:
firstly, polymerizing a rigid monomer A (forming a hard phase region), after the rigid monomer A is polymerized, adding a flexible monomer B and a monomer C containing a dynamic interaction group into the mixture to continue polymerizing the mixture (forming a soft phase region), and finally obtaining a binder simultaneously containing the hard phase region and the soft phase region; the monomer polymerization mode can be copolymerization in a form of forming a hard phase-soft phase, namely, rigid monomer A is polymerized first, then flexible monomer B and monomer C containing dynamic interaction groups are polymerized, and can also be polymerization in a form of forming a hard phase-soft phase-hard phase or a soft phase-hard phase-soft phase, and can exist in a form of combining more phase regions according to requirements.
The monomer C containing the dynamic interaction group is a monomer containing a group capable of forming a hydrogen bond;
preferably, the monomer C containing a dynamic interaction group is, for example, selected from
Figure FDA0002734284650000011
At least one of; preferably, it is
Figure FDA0002734284650000021
Wherein m is 1-8; x is 0-7; y is 1-8;
preferably, said rigid monomer A is selected from
Figure FDA0002734284650000022
Figure FDA0002734284650000023
At least one of; wherein R1 is Cl, Br, I or F; preferably, it is
Figure FDA0002734284650000024
Preferably, the flexible monomer B is selected from
Figure FDA0002734284650000025
At least one of; preferably, it is
Figure FDA0002734284650000026
Wherein n is 1 to 8.
3. The polymeric binder of claim 1 wherein the binder has a structure of hard phase-soft phase, hard phase-soft phase-hard phase, soft phase-hard phase-soft phase, or a combination of more phase domains as desired;
preferably, the polymer molecular weight Mw of the hard phase region is: 1000-200 ten thousand, the polymer molecular weight Mw of the soft phase region is: 1000-;
preferably, the soft phase region is a random copolymer unit formed by polymerization of monomers B and C;
preferably, the hard phase region repeat units are present in a molar ratio of 5 to 90 mol% of the total repeat units,
preferably, the molar ratio of the soft-phase region repeating unit (the sum of the repeating units formed by polymerizing the monomer B and the monomer C) to the total repeating unit is 10 to 95 mol%;
preferably, the molar ratio of the monomer B to the monomer C is 1-20;
preferably, the adhesive has a stress of 0.1 to 20MPa and an elongation at break of 10 to 200%.
4. A method of preparing a polymeric binder as claimed in any one of claims 1 to 3, comprising: polymerizing a rigid monomer A, a flexible monomer B and a monomer C containing a dynamic interaction group to form a self-repairing adhesive combining a soft-hard phase region;
preferably, the rigid monomer A is polymerized, and then the flexible monomer B and the monomer C containing the dynamic interaction group are added to continue polymerization, so as to finally obtain the binder containing the hard phase region and the soft phase region;
preferably, the polymerization mode is living radical polymerization; for example, reversible addition-fragmentation chain transfer polymerization (RAFT) or Atom Transfer Radical Polymerization (ATRP);
preferably, the temperature of the polymerization reaction is 45-100 ℃;
preferably, the time of the polymerization reaction is 1 to 24 hours; preferably, during the reversible addition-fragmentation chain transfer polymerization (RAFT), a reversible addition-fragmentation chain transfer reagent (RAFT reagent) is added;
preferably, the RAFT agent is selected from at least one of dibenzyltrithiocarbonate, 4-cyano-4- [ [ (dodecylthio) thiocarbonyl ] thio ] pentanoic acid, 2- (dodecylthio thiocarbonylthio) -2-methylpropionic acid, cyanomethyl methyl (phenyl) aminodithioate;
preferably, the RAFT agent is used in a molar ratio of 0.01% to 5% of the total repeat units.
5. Use of the polymer binder of any one of claims 1-3 in an electrode sheet of a lithium ion battery.
6. An electrode sheet for lithium ion batteries, characterized by containing the polymer binder according to any one of claims 1 to 3;
for example, the lithium ion battery electrode plate can be a positive plate and/or a negative plate; preferably, the lithium ion battery electrode plate is a negative electrode plate.
7. The electrode sheet of the lithium ion battery according to claim 6, wherein the binder is contained in the electrode sheet in an amount of 0.1 to 20 wt%.
8. The lithium ion battery electrode sheet according to claim 6 or 7, further comprising an electrode active material and/or a conductive agent;
preferably, the conductive agent is at least one of acetylene black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide;
preferably, the negative electrode sheet is selected from at least one of elemental silicon, silicon monoxide, natural graphite, artificial graphite, mesophase carbon fiber, mesophase carbon microsphere, soft carbon and hard carbon.
9. The method for producing an electrode sheet for a lithium ion battery according to any one of claims 6 to 8, which comprises preparing the polymer binder according to any one of claims 1 to 3 and an electrode active material and/or a conductive agent into a slurry, coating and drying; wherein the binder accounts for 0.1-20 wt% of the total mass of the slurry.
10. A lithium ion battery comprising the lithium ion battery electrode sheet according to any one of claims 6 to 8.
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