CN115395110A - Self-repairing microcapsule, capsule combination and preparation method - Google Patents
Self-repairing microcapsule, capsule combination and preparation method Download PDFInfo
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- CN115395110A CN115395110A CN202210744006.4A CN202210744006A CN115395110A CN 115395110 A CN115395110 A CN 115395110A CN 202210744006 A CN202210744006 A CN 202210744006A CN 115395110 A CN115395110 A CN 115395110A
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- 239000011162 core material Substances 0.000 claims abstract description 60
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- 239000010410 layer Substances 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 30
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 30
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Classifications
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The embodiment of the invention discloses a self-repairing microcapsule integrating movement and communication, a capsule combination and a preparation method. The energy-signal integrated self-repairing microcapsule comprises a core material and a shell material. The core material is Gao Ji Booth free energy substance; the shell material is wrapped on the periphery of the core material. The self-repairing microcapsule and the self-repairing microcapsule combination provided by the embodiment of the invention have high adhesion, high core material ratio, high spontaneity and the like, so that the combination can act as a dynamic and dynamic integrated self-repairing microcapsule and self-repairing microcapsule combination, the crack can be driven to close through stress action-core material flowing-free energy under the condition of a small addition amount, the quick closing repair of micro-damage inside a lithium ion battery and the crack interface adhesion are realized, and the capacity of the lithium ion battery is finally recovered.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a self-repairing microcapsule, a capsule combination and a preparation method.
Background
Lithium ion batteries are the most commonly used energy storage devices, but the service life and safety of the batteries are seriously affected by micro-damage generated inside the batteries during the use process, such as electrode cracks, interface peeling and the like. In particular, the problem of micro-damage of the flexible lithium ion battery is particularly prominent. The light high-strength lithium ion battery can also generate micro-damage inside when bearing external force. Therefore, how to effectively solve the micro-damage inside the lithium ion battery becomes a research hotspot.
The generation and propagation of electrode cracks can cause damages such as the falling of active substances, and the like, and seriously affect the electrochemical performance of the battery. At present, the research on the enhancement of the mechanical property and the adhesion property of the binder is mostly carried out to achieve the purpose of preventing the generation of the electrode cracks. For example, the self-repairing adhesive can perform self-repairing when cracks are generated so as to maintain the complete electrode structure. However, the above binder has a poor research effect, and it is difficult to actually solve the problem of electrode cracking. In a flexible lithium ion battery, due to the special use scene, the problem of electrode cracks is more serious. The electrode flexibility and the design of a novel flexible battery structure can better solve the problem of electrode cracks, but the energy density is sacrificed, and the manufacturing difficulty and the cost of the battery are increased. In addition, the problem of interfacial peeling inside batteries has not been an effective solution.
Disclosure of Invention
In order to effectively solve the problem of internal micro-damage of the lithium ion battery, the invention discloses a self-repairing material which is simple and efficient and can influence the structure and the energy density of the battery to a smaller extent and a preparation method thereof.
One aspect of the invention discloses a self-repairing microcapsule capable of realizing integration of activities and letters.
The self-repairing microcapsule integrated with the dynamic and dynamic functions comprises a core material and a shell material. The core material is Gao Ji buss free energy substance; the shell material is wrapped around the core material.
According to a preferred embodiment of the present invention, the self-repairing microcapsules with integrated motility function comprise a surface modification shell layer; the surface modification shell layer is wrapped on the periphery of the shell material, so that a high-adhesion functional layer is formed on the periphery of the shell material.
According to a preferred embodiment of the present invention, the surface modified shell layer is a polyvinyl alcohol layer.
According to a preferred embodiment of the present invention, the mass fraction of the core material is 60 to 80%.
According to a preferred embodiment of the present invention, the self-repairing microcapsules have a particle size of 20nm to 1um.
According to a preferred embodiment of the invention, the core material is an isocyanate, a polyamine or a polyethylene glycol.
According to a preferred embodiment of the present invention, the shell material is melamine-formaldehyde resin, polyurethane, epoxy resin, polyurea, polyvinyl alcohol, silicone, chitosan or guar gum.
In another aspect of the invention, a self-repairing microcapsule combination with integrated motility function is disclosed.
The self-repairing microcapsule combination integrating the motility and the trust comprises a self-repairing microcapsule A and a self-repairing microcapsule B; wherein the self-repairing microcapsule A and the self-repairing microcapsule B are both formed by the energy-activity integrated self-repairing microcapsule; and the core material of the self-repairing microcapsule A is different from that of the self-repairing microcapsule B.
In another aspect, the invention discloses a preparation method of the self-repairing microcapsule with integrated functions. The preparation method of the self-repairing microcapsule with the integrated function and trust comprises the following steps:
step one, preparing a microcapsule shell prepolymer:
dissolving the shell material raw material of the energy-activity-signal-integrated self-repairing microcapsule in water, and stirring the mixture uniformly at the rotating speed of 400 to 800r/min under the conditions of room temperature to 55 ℃ and pH value of 3 to 7 to obtain a prepolymer solution or a homogeneous polymer solution; wherein the mass fraction of the prepolymer solution or the homogeneous polymer solution is 5-20%;
step two, microcapsule emulsification:
stirring the core material of the energy-activity-trust integrated self-repairing microcapsule and an emulsifier at the temperature of 55-80 ℃ and the pH value of 3-7 at the rotating speed of 800-1500 r/min for 10-45 min, then adding water, stirring and emulsifying at the rotating speed of more than 1500r/min for 15-60 min to obtain stable oil-in-water emulsion; wherein, the concentration of the core material raw material is 3-20 wt%, and the concentration of the emulsifier is 0.5-2 wt%;
step three, crosslinking the shell layer of the microcapsule:
slowly adding the prepolymer solution or the homogeneous polymer solution prepared in the step one into the oil-in-water emulsion prepared in the step two; then, adjusting the stirring speed to be 100-500 r/min, and continuing to react for 0.5-4 h; after the reaction is finished, repeatedly cleaning the microcapsule for 2 to 5 times by using deionized water and alcohol, and performing suction filtration and vacuum drying to obtain the microcapsule; wherein the mass ratio of the prepolymer solution or homogeneous polymer solution prepared in the first step to the oil-in-water emulsion prepared in the second step is 1: 0.0375-0.15.
According to a preferred embodiment of the present invention, the method for preparing the mobile and trusted self-repairing microcapsule further comprises:
step four, microcapsule surface modification:
adding the microcapsule in the third step into 2-18 wt% of the surface modification shell layer material solution of the energy and communication integrated self-repairing microcapsule under the stirring conditions of 50-90 ℃ and 300-1000 r/min, stirring for 1-3 h, washing with deionized water and ethanol, and vacuum drying to obtain the self-repairing microcapsule.
Compared with the prior art, the self-repairing microcapsule, the capsule combination and the preparation method of the invention have the following beneficial effects:
the combination of the energy-communication integrated self-repairing microcapsule and the energy-communication integrated self-repairing microcapsule provided by the embodiment of the invention can receive a stress signal generated by micro-damage, timely break and respond and complete spontaneous repair. The specific process is as follows: under the stress condition, with the micro damage of the lithium ion battery, the shell layer of the microcapsule is broken and the core material with high Gibbs free energy is released, the core material spontaneously flows to the damaged part and is mixed, and the core material is driven by the free energy to carry out spontaneous reaction under the action of supermolecule action or polycondensation reaction such as hydrogen bond, coordination bond, electrostatic interaction and the like to form a high-conductivity and high-adhesion repairing layer, so that the repairing of microcracks is realized, and the battery capacity is recovered. Furthermore, a layer of high-adhesion functional layer can be modified outside the microcapsule to serve as an active adhesion site to improve the structural integrity of the electrode, and the cycle stability of the battery is improved under the condition that the energy density of the battery is not influenced.
Therefore, the combination of the energy-signal integrated self-repairing microcapsule and the energy-signal integrated self-repairing microcapsule provided by the embodiment of the invention has high adhesion, high core material ratio, high spontaneity and the like, so that the combination of the energy-signal integrated self-repairing microcapsule and the self-repairing microcapsule can act as an energy-signal integrated self-repairing microcapsule combination, cracks can be driven to close through stress action, quick closing repair of micro damage inside a lithium ion battery and crack interface adhesion are realized, and the capacity of the lithium ion battery is finally recovered.
Additional features of the invention will be set forth in part in the description which follows. Additional features of some aspects of the invention will become apparent to those of ordinary skill in the art upon examination of the following description and accompanying drawings or may be learned by the manufacture or operation of the embodiments. The features of the present disclosure may be realized and attained by practice or use of various methods, instrumentalities and combinations of the specific embodiments described below.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not limit the invention. Like reference symbols in the various drawings indicate like elements. Wherein,
FIG. 1 is a schematic representation of the operation of a mobile and integrated self-healing microcapsule composition according to some embodiments of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
It should be noted that if the terms "first", "second", etc. are used in the description and claims of the present invention and in the accompanying drawings, they are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged under appropriate circumstances in order to facilitate the description of the embodiments of the invention herein. Furthermore, if the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
In the present invention, if the terms "upper", "lower", "left", "right", "front", "rear", "top", "bottom", "inner", "outer", "middle", "vertical", "horizontal", "lateral", "longitudinal", etc. are referred to, the orientation or positional relationship indicated is based on the orientation or positional relationship shown in the drawings. These terms are used primarily to better describe the invention and its embodiments and are not intended to limit the indicated devices, elements or components to a particular orientation or to be constructed and operated in a particular orientation.
Moreover, some of the above terms may be used to indicate other meanings besides the orientation or positional relationship, for example, the term "on" may also be used to indicate some kind of attachment or connection relationship in some cases. The specific meanings of these terms in the present invention can be understood by those skilled in the art as appropriate.
In addition, in the present invention, the terms "mounted," "disposed," "provided," "connected," "sleeved," and the like should be construed broadly if they are referred to. For example, it may be a fixed connection, a removable connection, or a unitary construction; can be a mechanical connection, or an electrical connection; may be directly connected, or indirectly connected through intervening media, or may be in internal communication between two devices, elements or components. The specific meanings of the above terms in the present invention can be understood according to specific situations by those of ordinary skill in the art.
In the embodiment of the invention, the dynamic information means that the liquid material flows under the induction of an external stress signal, and the Gao Ji Booth free energy is used as a driving force to trigger the spontaneous reaction of the core material, so that the core material is promoted to be converted from a flowing state to a fixed state, and the self-repairing of damages such as cracks is realized.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Example 1
The embodiment discloses a self-repairing microcapsule with integrated function.
As shown in fig. 1, the self-healing microcapsule with integrated motility function can comprise a core material 1 and a shell material 2. The shell material 2 is wrapped around the core material 1.
The core material 1 may be a high gibbs free energy substance. For example, the core material may be isocyanate, polyamine or polyethylene glycol.
Wherein, the shell material 2 can adopt a material which can be broken and responded in time along with the micro-damage of the lithium ion battery under the stress condition. Illustratively, the shell material may be melamine-formaldehyde resin, polyurethane, epoxy resin, polyurea, polyvinyl alcohol, silicone, chitosan, or guar gum.
By adopting the technical scheme, the self-repairing microcapsule integrating the functions of energy and information can receive stress signals generated by micro-damage, timely break and respond and complete spontaneous repair. The specific process is as follows: under the stress condition, with the micro damage of the lithium ion battery, the shell layer of the microcapsule is broken and the core material with high Gibbs free energy is released, the core material spontaneously flows to the damaged part and is mixed, and the core material is driven by the free energy to carry out spontaneous reaction under the action of supermolecule action or polycondensation reaction such as hydrogen bond, coordination bond, electrostatic interaction and the like to form a high-conductivity and high-adhesion repairing layer, so that the repairing of microcracks is realized, and the battery capacity is recovered.
Example 2
The embodiment discloses a self-repairing microcapsule capable of realizing integration of functions and information.
As shown in fig. 1, the self-repairing microcapsule with integrated motility function disclosed in this embodiment can comprise a core material 1, a shell material 2 and a surface modification shell layer 3. The shell material 2 is wrapped around the core material 1. The surface-modified shell layer 3 is wrapped on the periphery of the shell material 2, so that a high-adhesion functional layer is formed on the periphery of the shell material 2.
The core material 1 may be a high gibbs free energy substance. For example, the core material may be isocyanate, polyamine or polyethylene glycol.
Wherein, the shell material 2 can adopt a material which can be broken and responded in time along with the micro-damage of the lithium ion battery under the stress condition. Illustratively, the shell material may be melamine-formaldehyde resin, polyurethane, epoxy resin, polyurea, polyvinyl alcohol, silicone, chitosan, or guar gum.
The surface modification shell layer 3 can be made of a material capable of forming a layer of high-adhesion functional layer outside the microcapsule shell material 2. For example, the surface modified shell layer may be a polyvinyl alcohol layer.
A surface modification shell layer with a high adhesion function is formed outside the shell material 2, and can be used as an active adhesion site to improve the structural integrity of the electrode and improve the cycle stability of the battery without influencing the energy density of the battery.
Further, in the present example, the mass fraction of the core material 1 was 60 to 80%.
Further, in the present example, the particle size of the self-repairing microcapsules having an integrated motility function is 20nm to 1um.
The energy and signal integrated self-repairing microcapsule of the embodiment has high adhesion, high core material ratio, high spontaneity and the like, can drive cracks to close through microcapsule rupture-core material flowing-free energy under the action of stress under the condition of a small adding amount, realizes quick closing repair of micro damage inside a lithium ion battery and crack interface adhesion, and finally recovers the capacity of the lithium ion battery. In addition, the active and active integrated self-repairing microcapsule of the embodiment can receive stress signals generated by micro-damage and timely break and respond and complete spontaneous repair. The specific process is as follows: under the stress condition, with the micro damage of the lithium ion battery, the shell layer of the microcapsule is broken and the core material with high Gibbs free energy is released, the core material spontaneously flows to the damaged part and is mixed, and the core material is driven by the free energy to carry out spontaneous reaction under the action of supermolecule action or polycondensation reaction such as hydrogen bond, coordination bond, electrostatic interaction and the like to form a high-conductivity and high-adhesion repairing layer, so that the repairing of microcracks is realized, and the battery capacity is recovered. And a surface modification shell layer with a high adhesion function is formed outside the shell material 2, and the surface modification shell layer can be used as an active adhesion site to improve the structural integrity of the electrode, and the cycle stability of the battery is improved under the condition that the energy density of the battery is not influenced.
Example 3
The embodiment discloses a self-repairing microcapsule combination with integrated function and reliability.
As shown in fig. 1, the self-repairing microcapsule combination with integrated motility function disclosed in this embodiment includes a self-repairing microcapsule a and a self-repairing microcapsule B.
Wherein the self-repairing microcapsule A and the self-repairing microcapsule B are both formed by the self-repairing microcapsules described in the embodiment 1 or the embodiment 2. The core material of the self-repairing microcapsule A is different from that of the self-repairing microcapsule B.
For example, in some embodiments, the core material of self-healing microcapsule a may be isocyanate (e.g., 4,4' -dicyclohexylmethane diisocyanate) and the core material of self-healing microcapsule B may be polyamine (e.g., diethylenetriamine).
For another example, in some embodiments, the core material of the self-repairing microcapsule a may be isocyanate (e.g., 4,4' -dicyclohexylmethane diisocyanate), and the core material of the self-repairing microcapsule B may be polyol (e.g., polyethylene glycol).
The energy and signal integrated self-repairing microcapsule combination of the embodiment can receive stress signals generated by micro-damage and timely break and respond and complete spontaneous repair. The specific process is as follows: under the stress condition, with the micro damage of the lithium ion battery, the shell layer of the microcapsule is broken and two core materials with high Gibbs free energy are released, the core materials spontaneously flow to the damaged part and are mixed, and spontaneous reaction is carried out under the drive of the free energy through supermolecule action or polycondensation reaction such as hydrogen bond, coordination bond, electrostatic interaction and the like to form a high-conductivity and high-adhesion repairing layer, so that the repairing of microcracks is realized, and the battery capacity is recovered.
Furthermore, the self-repairing microcapsule with integrated dynamic and dynamic functions of the embodiment has high adhesion, high core material ratio, high spontaneity and the like, and can drive cracks to close through stress action, core material flowing and free energy under the condition of a small addition amount, so that quick closing repair and crack interface adhesion of micro-damage in the lithium ion battery are realized, and finally the capacity of the lithium ion battery is recovered. And a surface modification shell layer with a high adhesion function is formed outside the shell material 2, and the surface modification shell layer can be used as an active adhesion site to improve the structural integrity of the electrode, and the cycle stability of the battery is improved under the condition that the energy density of the battery is not influenced.
The embodiment of the invention also discloses a preparation method of the self-repairing microcapsule with the integration of movement and communication. The preparation method of the self-repairing microcapsule mainly comprises the following steps:
step one, preparing a microcapsule shell prepolymer:
dissolving the shell material raw material of the energy and signal integrated self-repairing microcapsule of the embodiment 1, the embodiment 2 or the embodiment 3 in water, and stirring the mixture at the room temperature to 55 ℃ and the pH value of the mixture of 3 to 7 at the rotating speed of 400 to 800r/min until the mixture is uniform to obtain a prepolymer solution or a homogeneous polymer solution; wherein the mass fraction of the prepolymer solution or the homogeneous polymer solution is 5-20%;
step two, microcapsule emulsification:
stirring the core material of the energy and signal integrated self-repairing microcapsule of the embodiment 1, the embodiment 2 or the embodiment 3 and an emulsifier at the temperature of 55-80 ℃ and the pH value of 3-7 for 10-45 min at the rotating speed of 800-1500 r/min, then adding water and stirring and emulsifying at the rotating speed of more than 1500r/min for 15-60 min to obtain stable oil-in-water type emulsion; wherein, the concentration of the core material raw material is 3-20 wt%, and the concentration of the emulsifier is 0.5-2 wt%;
step three, crosslinking the shell layer of the microcapsule:
slowly adding the prepolymer solution or the homogeneous polymer solution prepared in the step one into the oil-in-water emulsion prepared in the step two; then, adjusting the stirring speed to be 100-500 r/min, and continuing to react for 0.5-4 h; after the reaction is finished, repeatedly cleaning the microcapsule for 2 to 5 times by using deionized water and alcohol, and performing suction filtration and vacuum drying to obtain the microcapsule; wherein the mass ratio of the prepolymer solution or homogeneous polymer solution prepared in the first step to the oil-in-water emulsion prepared in the second step is 1: 0.0375-0.15.
Further, the preparation method of the mobile and trusted integrated self-repairing microcapsule can further comprise the following steps:
step four, microcapsule surface modification:
and (3) adding the microcapsule prepared in the third step into 2-18 wt% of the surface modification shell layer material solution of the self-repairing microcapsule of the embodiment 1, the embodiment 2 or the embodiment 3 under the stirring conditions of 50-90 ℃ and 300-1000 r/min, stirring for 1-3 h, washing with deionized water and ethanol, and drying in vacuum to obtain the self-repairing microcapsule.
The following will describe in detail the method for producing the integrated self-repairing microcapsules of the present invention with reference to examples.
Example 4
The preparation method of the self-repairing microcapsule with integrated function and trust disclosed by the embodiment mainly comprises the following steps:
step one, preparing a microcapsule shell prepolymer:
adding 5g of EMA solution (2.5 wt%), 0.503g of urea, 0.05g of resorcinol and 0.065g of ammonium chloride into 20ml of deionized water, stirring at the rotating speed of 500r/min for 20min, adjusting the pH value of the solution to 3.5, and reacting at 55 ℃ for 1h to obtain a prepolymerization solution of the shell material.
Step two, microcapsule emulsification:
1g of 4,4 '-dicyclohexylmethane diisocyanate was dropped into an aqueous solution (10 ml) containing 2wt% of gum arabic at 55 ℃ and pH3.5 and 900r/min, stirred for 30min, and then emulsified by adding an appropriate amount of water and stirring at a rotation speed of more than 1500r/min for 15 to 60min, so that the concentration of 4,4' -dicyclohexylmethane diisocyanate was 3 to 20wt% and the concentration of gum arabic was 0.5 to 2wt%. Emulsion A coated with 4,4' -dicyclohexylmethane diisocyanate was obtained.
Step three, crosslinking the shell layer of the microcapsule:
slowly dripping the prepolymer solution in the first step into the emulsion A prepared in the second step at the temperature of 65 ℃ at 500r/min, reacting for 50min, washing with deionized water/ethanol, filtering, and drying in vacuum to obtain the PUF microcapsule A wrapping 4,4' -dicyclohexylmethane diisocyanate. Wherein the mass ratio of the prepolymer solution in the first step to the emulsion A prepared in the second step is 1: 0.0375-0.15.
Further, the method can also comprise the following steps:
step four, microcapsule surface modification:
preparing 5wt% polyvinyl alcohol aqueous solution, stirring at the speed of 800r/min for 1h at the temperature of 90 ℃, and cooling to room temperature for later use; slowly adding the microcapsule prepared in the third step into a polyvinyl alcohol solution, stirring and reacting at the speed of 600r/min for 1h at the temperature of 55 ℃, washing with deionized water/alcohol, and drying in vacuum to obtain the polyvinyl alcohol modified self-repairing microcapsule A. The particle size of the polyvinyl alcohol modified self-repairing microcapsule A is 150nm, and the content of the core material is 79%.
Example 5
The preparation method of the self-repairing microcapsule with integrated function and trust disclosed by the embodiment mainly comprises the following steps:
step one, preparing a microcapsule shell prepolymer:
adding 5g of EMA solution (2.5 wt%), 0.503g of urea, 0.05g of resorcinol and 0.065g of ammonium chloride into 20ml of deionized water, stirring at the rotating speed of 500r/min for 20min, adjusting the pH value of the solution to 3.5, and reacting at 55 ℃ for 1h to obtain a prepolymerization solution of the shell material.
Step two, microcapsule emulsification:
dropping 1g of diethylenetriamine into an aqueous solution (10 ml) containing 2wt% of Arabic gum at the temperature of 55 ℃, pH3.5 and 1500r/min, stirring for 30min, adding proper amount of water, stirring and emulsifying at the rotating speed of more than 1500r/min for 15-60 min, and ensuring that the concentration of the diethylenetriamine is 3-20 wt% and the concentration of the Arabic gum is 0.5-2 wt%. Obtaining emulsion B wrapping the diethylenetriamine.
Step three, crosslinking the shell layer of the microcapsule:
slowly dripping the prepolymer solution in the first step into the emulsion B in the second step at the temperature of 65 ℃ at 500r/min, reacting for 50min, washing with deionized water/ethanol, filtering, and drying in vacuum to obtain the PUF microcapsule B wrapping diethylenetriamine. Wherein the mass ratio of the prepolymer solution in the first step to the emulsion B prepared in the second step is 1: 0.0375-0.15.
Further, the method can also comprise the following steps:
step four, microcapsule surface modification:
preparing 5wt% polyvinyl alcohol aqueous solution, stirring at the speed of 800r/min for 1h at the temperature of 90 ℃, and cooling to room temperature for later use; slowly adding the microcapsule prepared in the third step into a polyvinyl alcohol solution, stirring and reacting at the speed of 600r/min for 1h at the temperature of 55 ℃, washing with deionized water/alcohol, and drying in vacuum to obtain the polyvinyl alcohol modified self-repairing microcapsule B. The particle size of the polyvinyl alcohol modified self-repairing microcapsule B is 170nm, and the content of the core material is 82%.
Example 6
The preparation method of the self-repairing microcapsule with integrated function and trust disclosed by the embodiment mainly comprises the following steps:
step one, preparing a microcapsule shell prepolymer:
adding 5g of EMA solution (2.5 wt%), 0.503g of urea, 0.05g of resorcinol and 0.065g of ammonium chloride into 20ml of deionized water, stirring at the rotating speed of 500r/min for 20min, adjusting the pH value of the solution to 3.5, and reacting at 55 ℃ for 1h to obtain a prepolymerization solution of the shell material.
Step two, microcapsule emulsification:
0.8g of 4,4 '-dicyclohexylmethane diisocyanate was dropped into an aqueous solution (10 ml) containing 1wt% of gum arabic at 55 ℃ and a pH of 3.5 and 900r/min, and stirred for 20min, and then an appropriate amount of water was added thereto and stirred at a rotation speed of more than 1500r/min to emulsify the mixture for 15 to 60min, so that the concentration of 4,4' -dicyclohexylmethane diisocyanate was 3 to 20wt% and the concentration of gum arabic was 0.5 to 2wt%. Emulsion A coated with 4,4' -dicyclohexylmethane diisocyanate was obtained.
Step three, crosslinking the shell layer of the microcapsule:
slowly and dropwise adding the prepolymer solution obtained in the first step into the emulsion A at the temperature of 65 ℃ at 200r/min, reacting for 40min, washing with deionized water/ethanol, performing suction filtration, and performing vacuum drying to obtain the PUF microcapsule A wrapping 4,4' -dicyclohexylmethane diisocyanate. Wherein, the mass ratio of the prepolymer solution in the first step to the emulsion A prepared in the second step is 1: 0.0375-0.15.
Further, the method can also comprise the following steps:
step four, microcapsule surface modification:
preparing 5wt% polyvinyl alcohol aqueous solution, stirring at 90 ℃ at a speed of 800r/min for 1h, and cooling to room temperature for later use; slowly adding the microcapsule prepared in the third step into a polyvinyl alcohol solution, stirring and reacting at the speed of 1000r/min for 1.5h at the temperature of 55 ℃, washing with deionized water/alcohol, and drying in vacuum to obtain the polyvinyl alcohol modified self-repairing microcapsule A. Wherein, the particle diameter of the self-repairing microcapsule A is 70nm, and the content of the core material is 86%.
Example 7
The preparation method of the self-repairing microcapsule with integrated function and trust disclosed by the embodiment mainly comprises the following steps:
step one, preparing a microcapsule shell prepolymer:
adding 5g of EMA solution (2.5 wt%), 0.503g of urea, 0.05g of resorcinol and 0.065g of ammonium chloride into 20ml of deionized water, stirring at the rotating speed of 500r/min for 20min, adjusting the pH value of the solution to 3.5, and reacting at 55 ℃ for 1h to obtain a prepolymerization solution of the shell material.
Step two, microcapsule emulsification:
0.8g of polyethylene glycol (Mw = 600) was dropped into an aqueous solution (10 ml) containing 1wt% of gum arabic at 65 ℃ and pH3.5 and 1400r/min, and stirred for 40min, and then an appropriate amount of water was added and stirred at a rotation speed of more than 1500r/min to emulsify for 15 to 60min, so that the concentration of polyethylene glycol was 3 to 20wt% and the concentration of gum arabic was 0.5 to 2wt%. Obtaining the emulsion B coated with the polyethylene glycol.
Step three, crosslinking the shell layer of the microcapsule:
and (3) slowly dripping the prepolymer solution obtained in the first step into the emulsion B at the temperature of 65 ℃ at 200r/min, reacting for 40min, washing with deionized water/ethanol, performing suction filtration, and performing vacuum drying to obtain the PUF microcapsule B wrapped with polyethylene glycol. Wherein the mass ratio of the prepolymer solution in the first step to the emulsion B prepared in the second step is 1: 0.0375-0.15.
Further, the method can also comprise the following steps:
step four, microcapsule surface modification:
preparing 5wt% polyvinyl alcohol aqueous solution, stirring at the speed of 800r/min for 1h at the temperature of 90 ℃, and cooling to room temperature for later use; slowly adding the microcapsule prepared in the third step into a polyvinyl alcohol solution, stirring and reacting at the speed of 1000r/min for 1.5h at the temperature of 55 ℃, washing with deionized water/alcohol, and drying in vacuum to obtain the polyvinyl alcohol modified self-repairing microcapsule B. Wherein, the particle diameter of the self-repairing microcapsule B is 90nm, and the content of the core material is 82%.
Example 8
The preparation method of the self-repairing microcapsule combination with integrated activity and trust disclosed by the embodiment mainly comprises the following steps:
step one, preparing a microcapsule shell prepolymer:
adding 5g of EMA solution (2.5 wt%), 0.503g of urea, 0.05g of resorcinol and 0.065g of ammonium chloride into 20ml of deionized water, stirring at the rotating speed of 500r/min for 20min, adjusting the pH value of the solution to 3.5, and reacting at 55 ℃ for 1h to obtain a prepolymerization solution of the shell material.
Step two, microcapsule emulsification:
1g of 4,4 '-dicyclohexylmethane diisocyanate was dropped into an aqueous solution (10 ml) containing 2wt% of gum arabic at 55 ℃ and pH3.5 and 900r/min, stirred for 30min, and then emulsified by adding an appropriate amount of water and stirring at a rotation speed of more than 1500r/min for 15 to 60min, so that the concentration of 4,4' -dicyclohexylmethane diisocyanate was 3 to 20wt% and the concentration of gum arabic was 0.5 to 2wt%. Obtaining emulsion A wrapping 4,4' -dicyclohexyl methane diisocyanate; dropping 1g of diethylenetriamine into an aqueous solution (10 ml) containing 2wt% of gum arabic at the conditions of 55 ℃, pH3.5 and 1500r/min, stirring for 30min, then adding proper amount of water, stirring and emulsifying at the rotating speed of more than 1500r/min for 15-60 min, so that the concentration of the diethylenetriamine is 3-20 wt% and the concentration of the gum arabic is 0.5-2 wt%. Obtaining emulsion B wrapping diethylenetriamine.
Step three, crosslinking the shell layer of the microcapsule:
slowly dripping the prepolymer solution in the first step into the emulsion A prepared in the second step at the temperature of 65 ℃ at 500r/min, reacting for 50min, washing with deionized water/ethanol, filtering, and drying in vacuum to obtain the PUF microcapsule A wrapping 4,4' -dicyclohexylmethane diisocyanate. Wherein the mass ratio of the prepolymer solution in the first step to the emulsion A prepared in the second step is 1: 0.0375-0.15.
And in the same step, slowly dripping the prepolymer solution in the step one into the emulsion B in the step two at the temperature of 65 ℃ at 500r/min, reacting for 50min, washing with deionized water/ethanol, filtering, and drying in vacuum to obtain the PUF microcapsule B wrapped with diethylenetriamine. Wherein the mass ratio of the prepolymer solution in the first step to the emulsion B prepared in the second step is 1: 0.0375-0.15.
Further, the method can also comprise the following steps:
step four, microcapsule surface modification:
preparing 5wt% polyvinyl alcohol aqueous solution, stirring at the speed of 800r/min for 1h at the temperature of 90 ℃, and cooling to room temperature for later use; slowly adding the two microcapsules into a polyvinyl alcohol solution, stirring and reacting at the speed of 600r/min for 1h at the temperature of 55 ℃, washing with deionized water/alcohol, and drying in vacuum to obtain the polyvinyl alcohol modified self-repairing microcapsule A and the polyvinyl alcohol modified self-repairing microcapsule B. The particle sizes of the polyvinyl alcohol modified self-repairing microcapsule A and the self-repairing microcapsule B are respectively 150nm and 170nm, and the content of the core material is respectively 79% and 82%.
The self-repairing microcapsule A and the self-repairing microcapsule B are added into silicon cathode slurry according to 3wt% (compared with the mass of active substances), a lithium sheet is used as a counter electrode to prepare the lithium ion battery containing the self-repairing microcapsule with the integration of energy and information, and the capacity retention rate is 87% after the lithium ion battery is cycled for 200 circles at 0.2C.
Example 9
The preparation method of the self-repairing microcapsule combination with integrated activity and trust disclosed by the embodiment mainly comprises the following steps:
step one, preparing a microcapsule shell prepolymer:
adding 5g of EMA solution (2.5 wt%), 0.503g of urea, 0.05g of resorcinol and 0.065g of ammonium chloride into 20ml of deionized water, stirring at the rotating speed of 500r/min for 20min, adjusting the pH value of the solution to 3.5, and reacting for 1h to obtain a prepolymerization solution of the shell material.
Step two, microcapsule emulsification:
0.8g of 4,4 '-dicyclohexylmethane diisocyanate was dropped into an aqueous solution (10 ml) containing 1% by weight of gum arabic at 55 ℃ and pH3.5 and 900r/min, and stirred for 20min, followed by addition of an appropriate amount of water and stirring and emulsification at a rotation speed of more than 1500r/min for 15 to 60min, so that the concentration of 4,4' -dicyclohexylmethane diisocyanate was 3 to 20% by weight and the concentration of gum arabic was 0.5 to 2% by weight. Emulsion A coated with 4,4' -dicyclohexylmethane diisocyanate was obtained. 0.8g of polyethylene glycol (Mw = 600) was dropped into an aqueous solution (10 ml) containing 1wt% of gum arabic at 65 ℃ and pH3.5 and 1400r/min, and stirred for 40min, and then an appropriate amount of water was added and stirred at a rotation speed of more than 1500r/min to emulsify for 15 to 60min, so that the concentration of polyethylene glycol was 3 to 20wt% and the concentration of gum arabic was 0.5 to 2wt%. Obtaining the emulsion B coated with the polyethylene glycol.
Step three, crosslinking the shell layer of the microcapsule:
slowly and dropwise adding the prepolymer solution obtained in the first step into the emulsion A at the temperature of 65 ℃ at 200r/min, reacting for 40min, washing with deionized water/ethanol, performing suction filtration, and performing vacuum drying to obtain the PUF microcapsule A wrapping 4,4' -dicyclohexylmethane diisocyanate. Wherein the mass ratio of the prepolymer solution in the first step to the emulsion A prepared in the second step is 1: 0.0375-0.15.
And in the same step, slowly dropwise adding the prepolymer solution in the step one into the emulsion B at the temperature of 65 ℃ at 200r/min, reacting for 40min, washing with deionized water/ethanol, performing suction filtration, and performing vacuum drying to obtain the PUF microcapsule B wrapped with polyethylene glycol. Wherein the mass ratio of the prepolymer solution in the first step to the emulsion B prepared in the second step is 1: 0.0375-0.15.
Further, the method can also comprise the following steps:
step four, microcapsule surface modification:
preparing 5wt% polyvinyl alcohol aqueous solution, stirring at the speed of 800r/min for 1h at the temperature of 90 ℃, and cooling to room temperature for later use; slowly adding the two microcapsules into a polyvinyl alcohol solution, stirring and reacting at the speed of 1000r/min for 1.5h at the temperature of 55 ℃, washing by deionized water/alcohol, and drying in vacuum to obtain the polyvinyl alcohol modified self-repairing microcapsule A and the polyvinyl alcohol modified self-repairing microcapsule B. The particle sizes of the self-repairing microcapsule A and the self-repairing microcapsule B are respectively 70nm and 90nm, and the content of the core material is respectively 86% and 82%.
The self-repairing microcapsule A and the self-repairing microcapsule B are added into silicon cathode slurry according to 5wt% (compared with the mass of active substances), a lithium sheet is used as a counter electrode to prepare the lithium ion battery containing the self-repairing microcapsule with the integration of energy and information, and the capacity retention rate is 90% after the lithium ion battery is cycled for 200 circles at 0.2C.
It should be noted that all of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except for mutually exclusive features and/or steps.
In addition, the above-described embodiments are exemplary, and those skilled in the art, having benefit of this disclosure, will appreciate numerous solutions that are within the scope of the disclosure and that fall within the scope of the invention. It should be understood by those skilled in the art that the present specification and figures are illustrative only and are not limiting upon the claims. The scope of the invention is defined by the claims and their equivalents.
Claims (10)
1. A mobile and trusted self-repairing microcapsule is characterized by comprising:
the core material is Gao Ji Booth free energy substance;
and
a shell material wrapped around the outer periphery of the core material.
2. The mobile beacon-integrated self-healing microcapsule of claim 1, comprising a surface modifying shell layer;
the surface modification shell layer is wrapped on the periphery of the shell material, so that a high-adhesion functional layer is formed on the periphery of the shell material.
3. The dynamic and trusted self-repairing microcapsule according to claim 2, wherein the surface modification shell layer is a polyvinyl alcohol layer.
4. The self-repairing microcapsule with integrated dynamic and credibility function according to claim 2, characterized in that the mass fraction of the core material is 60-80%.
5. The energy and signal integrated self-repairing microcapsule according to claim 2, wherein the particle size of the self-repairing microcapsule is 20nm to 1um.
6. The mobile and trusted self-healing microcapsule according to any one of claims 1 to 5, wherein said core material is isocyanate, polyamine or polyethylene glycol.
7. The dynamic and trusted self-repairing microcapsule according to any one of claims 1 to 5, wherein the shell material is melamine-formaldehyde resin, polyurethane, epoxy resin, polyurea, polyvinyl alcohol, silicone, chitosan or guar gum.
8. The energy and signal integrated self-repairing microcapsule combination is characterized by comprising a self-repairing microcapsule A and a self-repairing microcapsule B;
wherein the self-healing microcapsule A and the self-healing microcapsule B are both formed from the mobile and integral self-healing microcapsule of any one of claims 1 to 7;
and the core material of the self-repairing microcapsule A is different from that of the self-repairing microcapsule B.
9. A preparation method of the energy and signal integrated self-repairing microcapsule is characterized by comprising the following steps:
step one, preparing a microcapsule shell prepolymer:
dissolving the shell material raw material of the energy and signal integrated self-repairing microcapsule of any one of claims 1 to 8 in water, and stirring the mixture at the room temperature of 55 ℃ and the pH value of 3 to 7 at the rotating speed of 400 to 800r/min until the mixture is uniform to obtain a prepolymer solution or a homogeneous polymer solution; wherein the mass fraction of the prepolymer solution or the homogeneous polymer solution is 5-20%;
step two, microcapsule emulsification:
stirring the core material raw material of the energy and signal integrated self-repairing microcapsule of any one of claims 1 to 8 and an emulsifier at the temperature of 55-80 ℃ and the pH value of 3-7 for 10-45 min at the rotating speed of 800-1500 r/min, then adding water and stirring and emulsifying at the rotating speed of more than 1500r/min for 15-60 min to obtain a stable oil-in-water type emulsion; wherein, the concentration of the core material raw material is 3-20 wt%, and the concentration of the emulsifier is 0.5-2 wt%;
step three, crosslinking the shell layer of the microcapsule:
slowly adding the prepolymer solution or the homogeneous polymer solution prepared in the step one into the oil-in-water type emulsion prepared in the step two; then, adjusting the stirring speed to be 100-500 r/min, and continuing to react for 0.5-4 h; after the reaction is finished, repeatedly cleaning the microcapsule for 2 to 5 times by using deionized water and alcohol, and performing suction filtration and vacuum drying to obtain the microcapsule; wherein the mass ratio of the prepolymer solution or homogeneous polymer solution prepared in the first step to the oil-in-water emulsion prepared in the second step is 1: 0.0375-0.15.
10. The method of claim 9, wherein the method further comprises:
step four, microcapsule surface modification:
adding the microcapsules in the third step into 2-18 wt% of the surface modification shell layer material solution of the energy and communication integrated self-repairing microcapsules of one of claims 2 to 8 under the stirring conditions of 50-90 ℃ and 300-1000 r/min, stirring for 1-3 h, washing with deionized water and ethanol, and vacuum drying to obtain the energy and communication integrated self-repairing microcapsules.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116811375A (en) * | 2023-06-21 | 2023-09-29 | 湖北三峡实验室 | Self-repairing fiber reinforced laminate and preparation method thereof |
| CN117080449A (en) * | 2023-10-16 | 2023-11-17 | 瑞浦兰钧能源股份有限公司 | Self-repairing binder for battery and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106943969A (en) * | 2017-04-07 | 2017-07-14 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate |
| CN111790325A (en) * | 2020-07-17 | 2020-10-20 | 中山纳微新材料科技有限公司 | Double-shell self-repairing microcapsule and preparation method and application thereof |
| CN112271278A (en) * | 2020-09-30 | 2021-01-26 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Self-healing branched polyethylene diamine hydrogel microcapsule composite material, and preparation method and application thereof |
-
2022
- 2022-06-27 CN CN202210744006.4A patent/CN115395110A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106943969A (en) * | 2017-04-07 | 2017-07-14 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of the self-repairing microcapsule of composite shell cladding liquid isocyanate |
| CN111790325A (en) * | 2020-07-17 | 2020-10-20 | 中山纳微新材料科技有限公司 | Double-shell self-repairing microcapsule and preparation method and application thereof |
| CN112271278A (en) * | 2020-09-30 | 2021-01-26 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Self-healing branched polyethylene diamine hydrogel microcapsule composite material, and preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116811375A (en) * | 2023-06-21 | 2023-09-29 | 湖北三峡实验室 | Self-repairing fiber reinforced laminate and preparation method thereof |
| CN116811375B (en) * | 2023-06-21 | 2024-07-05 | 湖北三峡实验室 | Self-repairing fiber reinforced laminate and preparation method thereof |
| CN117080449A (en) * | 2023-10-16 | 2023-11-17 | 瑞浦兰钧能源股份有限公司 | Self-repairing binder for battery and preparation method thereof |
| CN117080449B (en) * | 2023-10-16 | 2024-02-06 | 瑞浦兰钧能源股份有限公司 | Self-repairing binder for battery and preparation method thereof |
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