A self-healing microcapsule, capsule combination and preparation method

Abstract

An embodiment of the present invention discloses a self-healing microcapsule integrating actuation and signal transmission, a capsule combination and a preparation method thereof. The self-healing microcapsule integrating actuation and signal transmission includes a core material and a shell material. The core material is a high Gibbs free energy substance; the shell material is wrapped around the outer periphery of the core material. The self-healing microcapsules and the self-healing microcapsule combination of the embodiments of the present invention have high adhesiveness, a high core material ratio, high spontaneity, etc., enabling them to act as a self-healing microcapsule and a self-healing microcapsule combination integrating actuation and signal transmission. With a small addition amount, through stress, the microcapsules rupture - the core material flows - the free energy drives the crack to close, realizing the rapid closing and repair of micro-damage inside the lithium-ion battery and the adhesion of the crack interface, and finally restoring the capacity of the lithium-ion battery.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium batteries, and more particularly to a self-healing microcapsule, a capsule combination and a preparation method thereof. Background Art

[0002] Lithium-ion batteries are the most commonly used energy storage devices. However, micro-damages generated inside the battery during use, such as electrode cracks and interface peeling, will seriously affect the service life and safety of the battery. In particular, the micro-damage problem of flexible lithium-ion batteries is particularly prominent. Lightweight and high-strength lithium-ion batteries will also generate micro-damages inside when bearing external forces. Therefore, how to effectively solve the micro-damage inside the lithium-ion battery has become a research hotspot.

[0003] The generation and expansion of electrode cracks will cause damages such as the shedding of active materials, seriously affecting the electrochemical performance of the battery. At present, most of the research focuses on enhancing the mechanical properties and adhesion properties of the binder to prevent the generation of electrode cracks. For example, self-healing binders can perform self-repair when cracks occur to maintain a complete electrode structure. However, the research effect of the above-mentioned binders is poor, and it is difficult to truly solve the electrode crack problem. In flexible lithium-ion batteries, due to the special use scenario, the electrode crack problem is more serious. Although the flexibility of the electrode and the design of the new flexible battery structure have better solved the electrode crack problem, the energy density is sacrificed, and the battery manufacturing difficulty and cost are increased. In addition, there has been no effective solution to the interface peeling problem inside the battery. Summary of the Invention

[0004] In order to effectively solve the micro-damage problem inside the lithium-ion battery, the present invention discloses a simple, efficient self-healing material and its preparation method, which can affect the battery structure and energy density to a lesser extent.

[0005] Among them, one aspect of the present invention discloses a self-healing microcapsule integrating mobility and signal function.

[0006] The self-healing microcapsule integrating mobility and signal function includes a core material and a shell material. The core material is a substance with high Gibbs free energy; the shell material is wrapped around the outer periphery of the core material.

[0007] According to a preferred embodiment of the present invention, the self-healing microcapsule integrating mobility and signal function includes a surface-modified shell layer; the surface-modified shell layer is wrapped around the outer periphery of the shell material, so as to form a high-adhesion functional layer on the outer periphery of the shell material.

[0008] According to a preferred embodiment of the present invention, the surface-modified shell layer is a polyvinyl alcohol layer.

[0009] According to a preferred embodiment of the present invention, the mass fraction of the core material is 60-80%.

[0010] According to a preferred embodiment of the present invention, the particle size of the self-healing microcapsules is 20 nm to 1 μm.

[0011] According to a preferred embodiment of the present invention, the core material is isocyanate, polyamine or polyethylene glycol.

[0012] 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.

[0013] Another aspect of the present invention discloses a self-healing microcapsule combination integrating actuation and signal function.

[0014] The self-healing microcapsule combination integrating actuation and signal function includes self-healing microcapsule A and self-healing microcapsule B; wherein, both the self-healing microcapsule A and the self-healing microcapsule B are formed by the self-healing microcapsules integrating actuation and signal function as described in any one of the above; and, the core material of the self-healing microcapsule A is different from the core material of the self-healing microcapsule B.

[0015] Another aspect of the present invention discloses a preparation method of the self-healing microcapsules integrating actuation and signal function. The preparation method of the self-healing microcapsules integrating actuation and signal function includes the following steps:

[0016] Step 1, preparation of microcapsule shell layer prepolymer:

[0017] Dissolve the shell material raw material of the self-healing microcapsules integrating actuation and signal function as described above in water, and stir at a speed of 400 - 800 r / min at room temperature to 55 °C and pH 3 - 7 until 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%.

[0018] Step 2, microcapsule emulsification:

[0019] Stir the core material raw material of the self-healing microcapsules integrating actuation and signal function as described above and an emulsifier at a speed of 800 - 1500 r / min at 55 - 80 °C and pH 3 - 7 for 10 - 45 min, then add water and stir for emulsification at a speed greater than 1500 r / min for 15 - 60 min to obtain a 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%.

[0020] Step 3, microcapsule shell layer crosslinking:

[0021] Slowly add the prepolymer solution or homogeneous polymer solution prepared in Step 1 to the oil-in-water emulsion prepared in Step 2; then, adjust the stirring rate to 100 - 500 r / min and continue the reaction for 0.5 - 4 h; after the reaction is completed, wash repeatedly with deionized water and alcohol for 2 - 5 times, filter by suction and dry in vacuum to obtain the microcapsules; wherein, the mass ratio of the prepolymer solution or homogeneous polymer solution prepared in Step 1 to the oil-in-water emulsion prepared in Step 2 is 1∶(0.0375 - 0.15).

[0022] According to a preferred embodiment of the present invention, the method for preparing the self-healing microcapsules with integrated energy and signal function further includes:

[0023] Step 4, surface modification of microcapsules:

[0024] Add the microcapsules in Step 3 to the surface modification shell material solution of the self-healing microcapsules with integrated energy and signal function as described above at 2 - 18 wt% under the stirring conditions of 50 - 90 °C and 300 - 1000 r / min, stir for 1 - 3 h, wash with deionized water and ethanol, and dry in vacuum to obtain the self-healing microcapsules.

[0025] Compared with the prior art, the self-healing microcapsules with integrated energy and signal function, capsule combination and preparation method in the embodiments of the present invention have the following beneficial effects:

[0026] The self-healing microcapsules with integrated energy and signal function and the self-healing microcapsule combination in the embodiments of the present invention can receive stress signals generated by micro-damage, rupture in time in response, and complete spontaneous repair. The specific process is as follows: under stress, with the generation of micro-damage in the lithium-ion battery, it causes the microcapsule shell layer to rupture and release the core material with high Gibbs free energy. The core material spontaneously flows to the damage site and mixes, and under the drive of free energy, it undergoes spontaneous reactions such as supramolecular interactions or polycondensation reactions through hydrogen bonds, coordination bonds, electrostatic interactions, etc., to form a high-conductivity and high-adhesion repair layer, realizing the repair of micro-cracks, and then restoring the battery capacity. Further, a high-adhesion functional layer can be modified on the outside of the microcapsules as active bonding sites to enhance the integrity of the electrode structure and improve its cycle stability without affecting the energy density of the battery.

[0027] Therefore, the self-healing microcapsules with integrated energy and signal function and the self-healing microcapsule combination in the embodiments of the present invention have high adhesion, high core material ratio, high spontaneity, etc., making them behave as a self-healing microcapsule and self-healing microcapsule combination with integrated energy and signal function. They can, with a small addition amount, cause the microcapsules to rupture - the core material to flow - the free energy to drive the crack to close under stress, realize the rapid closure repair of micro-damage inside the lithium-ion battery and the adhesion of the crack interface, and finally restore the capacity of the lithium-ion battery.

[0028] Some additional features of the present invention can be described in the following description. By examining the following description and the corresponding drawings, or by understanding the production or operation of the embodiments, some additional features of the present invention will be apparent to those skilled in the art. The features disclosed in the present invention can be realized and achieved by practicing or using various methods, means, and combinations of the specific embodiments described below. Description of the Drawings

[0029] The drawings described herein are used to provide a further understanding of the present invention and form a part of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute a limitation to the present invention. In each figure, the same reference numerals represent the same components. Among them,

[0030] Figure 1 is a working schematic diagram of the self-healing microcapsule combination of the active letter integration according to some embodiments of the present invention. Detailed Embodiments

[0031] In order to enable those skilled in the art to better understand the solution of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

[0032] It should be noted that if the terms "first", "second", etc. are involved in the description, claims, and the above-mentioned drawings of the present invention, they are used to distinguish similar objects and do not necessarily need to describe a specific order or sequence. It should be understood that such data can be interchanged under appropriate circumstances for the embodiments of the present invention described herein. In addition, if the terms "comprising" and "having" and any of their variations are involved, the intention is to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units does not necessarily have to be limited to those steps or units clearly listed, but may include other steps or units not clearly listed or inherent to these processes, methods, products, or devices.

[0033] In the present invention, if terms such as "upper", "lower", "left", "right", "front", "rear", "top", "bottom", "inner", "outer", "middle", "vertical", "horizontal", "lateral", "longitudinal", etc. are involved, the orientation or positional relationship indicated is based on the orientation or positional relationship shown in the drawings. These terms are mainly used to better describe the present invention and its embodiments, and are not used to limit that the indicated device, element or component must have a specific orientation, or be constructed and operated in a specific orientation.

[0034] Moreover, in addition to being able to represent the orientation or positional relationship, some of the above terms may also be used to represent other meanings. For example, the term "upper" may also be used to represent a certain attachment relationship or connection relationship in some cases. For those of ordinary skill in the art, the specific meanings of these terms in the present invention can be understood according to specific circumstances.

[0035] In addition, in the present invention, if terms such as "installation", "setting", "provided with", "connection", "connected", "socketed", etc. are involved, they should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral structure; it can be a mechanical connection or an electrical connection; it can be directly connected, or indirectly connected through an intermediate medium, or there is internal communication between two devices, elements or components. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0036] In the embodiments of the present invention, the active signal means that a liquid substance flows under the induction of an external stress signal, and triggers the spontaneous reaction of the core material with high Gibbs free energy as the driving force, promoting the core material to change from a flowing state to a fixed state, realizing the self-repair of damages such as cracks.

[0037] It should be noted that, without conflict, the embodiments in the present invention and the features in the embodiments can be combined with each other.

[0038] The present invention will be described in detail below with reference to the drawings and in conjunction with the embodiments.

[0039] Embodiment 1

[0040] This embodiment discloses a self-healing microcapsule integrated with an active signal.

[0041] As Figure 1 shown, the self-healing microcapsule integrated with an active signal may include a core material 1 and a shell material 2. The shell material 2 is wrapped around the outer periphery of the core material 1.

[0042] Among them, the core material 1 can adopt a substance with high Gibbs free energy. Exemplarily, the core material can adopt isocyanate, polyamine or polyethylene glycol.

[0043] Among them, the shell material 2 can be a material that can rupture and respond in a timely manner with the generation of micro-damage in a lithium-ion battery under stress. Exemplarily, the shell material can be melamine-formaldehyde resin, polyurethane, epoxy resin, polyurea, polyvinyl alcohol, silicone, chitosan or guar gum.

[0044] By adopting the above technical solution, the self-healing microcapsules with integrated energy and signal functions in this embodiment can receive stress signals generated by micro-damage, rupture and respond in a timely manner, and complete spontaneous repair. The specific process is as follows: under stress, with the generation of micro-damage in the lithium-ion battery, it causes the rupture of the microcapsule shell layer and releases the core material with high Gibbs free energy. The core material spontaneously flows to the damage site and mixes, and under the drive of free energy, it undergoes spontaneous reactions such as supramolecular interactions or polycondensation reactions through hydrogen bonds, coordination bonds, electrostatic interactions, etc., to form a high-conductivity and high-adhesion repair layer, realizing the repair of microcracks, and thus restoring the battery capacity.

[0045] Embodiment 2

[0046] This embodiment discloses a self-healing microcapsule with integrated energy and signal functions.

[0047] As Figure 1 shown, the self-healing microcapsule with integrated energy and signal functions disclosed in this embodiment can include a core material 1, a shell material 2, and a surface-modified shell layer 3. The shell material 2 is wrapped around the outer periphery of the core material 1. The surface-modified shell layer 3 is wrapped around the outer periphery of the shell material 2, so as to form a high-adhesion functional layer on the outer periphery of the shell material 2.

[0048] Among them, the core material 1 can be a material with high Gibbs free energy. Exemplarily, the core material can be isocyanate, polyamine or polyethylene glycol.

[0049] Among them, the shell material 2 can be a material that can rupture and respond in a timely manner with the generation of micro-damage in a lithium-ion battery under stress. Exemplarily, the shell material can be melamine-formaldehyde resin, polyurethane, epoxy resin, polyurea, polyvinyl alcohol, silicone, chitosan or guar gum.

[0050] Among them, the surface-modified shell layer 3 can be a material that can form a high-adhesion functional layer outside the microcapsule shell material 2. Exemplarily, the surface-modified shell layer can be a polyvinyl alcohol layer.

[0051] By forming a surface-modified shell layer with high adhesion function outside the shell material 2, it can serve as an active bonding site to improve the integrity of the electrode structure and enhance its cycle stability without affecting the battery energy density.

[0052] Furthermore, in this embodiment, the mass fraction of the core material 1 is 60-80%.

[0053] Further, in this embodiment, the particle size of the self-healing microcapsules integrating actuation and signal transduction is 20 nm to 1 μm.

[0054] The self-healing microcapsules integrating actuation and signal transduction in this embodiment have high adhesiveness, a high core material ratio, high spontaneity, etc. With a small addition amount, stress can cause the microcapsules to rupture - the core material to flow - and the free energy to drive the crack closure, achieving rapid closure repair of micro-damage inside the lithium-ion battery and adhesion at the crack interface, ultimately restoring the capacity of the lithium-ion battery. In addition, the self-healing microcapsules integrating actuation and signal transduction in this embodiment can receive stress signals generated by micro-damage, rupture in a timely manner in response, and complete spontaneous repair. The specific process is as follows: under stress, with the generation of micro-damage in the lithium-ion battery, the shell layer of the microcapsules ruptures and releases the core material with high Gibbs free energy. The core material spontaneously flows to the damaged area and mixes. Driven by free energy, it undergoes spontaneous reactions through supramolecular interactions such as hydrogen bonds, coordination bonds, and electrostatic interactions or condensation reactions to form a high-conductivity and high-adhesion repair layer, achieving the repair of micro-cracks and thus restoring the battery capacity. And by forming a surface-modified shell layer with high adhesion function outside the shell material 2, it can serve as an active bonding site to enhance the integrity of the electrode structure and improve its cycling stability without affecting the energy density of the battery.

[0055] Example 3

[0056] This embodiment discloses a combination of self-healing microcapsules integrating actuation and signal transduction.

[0057] As Figure 1 shown, the combination of self-healing microcapsules integrating actuation and signal transduction disclosed in this embodiment includes self-healing microcapsule A and self-healing microcapsule B.

[0058] Among them, both self-healing microcapsule A and self-healing microcapsule B are formed by the self-healing microcapsules described in Example 1 or Example 2. And the core material of self-healing microcapsule A is different from that of self-healing microcapsule B.

[0059] For example, in some embodiments, the core material of self-healing microcapsule A can be isocyanate (such as 4,4'-dicyclohexylmethane diisocyanate), and the core material of self-healing microcapsule B can be polyamine (such as diethylenetriamine).

[0060] For another example, in some embodiments, the core material of self-healing microcapsule A can be isocyanate (such as 4,4'-dicyclohexylmethane diisocyanate), and the core material of self-healing microcapsule B can be polyol (such as polyethylene glycol).

[0061] The self-healing microcapsule combination with integrated actuation and signal function in this embodiment can receive stress signals generated by micro-damage, rupture in a timely manner in response, and complete spontaneous repair. The specific process is as follows: Under stress, with the generation of micro-damage in the lithium-ion battery, the microcapsule shell layer ruptures and releases two core materials with high Gibbs free energy. The core materials spontaneously flow to the damaged area and mix, and under the drive of free energy, they undergo spontaneous reactions through supramolecular interactions such as hydrogen bonds, coordination bonds, and electrostatic interactions or polycondensation reactions to form a high-conductivity and high-adhesion repair layer, realizing the repair of micro-cracks and thus restoring the battery capacity.

[0062] Furthermore, the self-healing microcapsules with integrated actuation and signal function in this embodiment have high adhesion, high core material ratio, high spontaneity, etc. With a small addition amount, through stress-induced microcapsule rupture - core material flow - free energy-driven crack closure, rapid closure repair of micro-damage inside the lithium-ion battery and adhesion of the crack interface can be achieved, ultimately restoring the capacity of the lithium-ion battery. And by forming a surface-modified shell layer with high adhesion function outside the shell material 2, it can serve as an active bonding site to enhance the integrity of the electrode structure and improve its cycling stability without affecting the battery energy density.

[0063] The embodiment of the present invention also discloses a preparation method of self-healing microcapsules with integrated actuation and signal function. The preparation method of the self-healing microcapsules mainly includes the following steps:

[0064] Step 1, preparation of microcapsule shell layer prepolymer:

[0065] Dissolve the shell material raw materials of the self-healing microcapsules with integrated actuation and signal function in Embodiment 1, Embodiment 2 or Embodiment 3 in water, and stir at a speed of 400 - 800 r / min at room temperature to 55 °C and pH 3 - 7 until 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%.

[0066] Step 2, microcapsule emulsification:

[0067] Stir the core material raw materials of the self-healing microcapsules with integrated actuation and signal function in Embodiment 1, Embodiment 2 or Embodiment 3 and an emulsifier at a speed of 800 - 1500 r / min for 10 - 45 min at 55 - 80 °C and pH 3 - 7, then add water and stir for emulsification at a speed greater than 1500 r / min for 15 - 60 min to obtain a stable oil-in-water emulsion; wherein, the concentration of the core material raw materials is 3 - 20 wt%, and the concentration of the emulsifier is 0.5 - 2 wt%.

[0068] Step 3, microcapsule shell layer crosslinking:

[0069] Slowly add the prepolymer solution or homogeneous polymer solution prepared in Step 1 to the oil-in-water emulsion prepared in Step 2; then, adjust the stirring rate to 100 - 500 r / min and continue the reaction for 0.5 - 4 h; after the reaction is completed, wash repeatedly with deionized water and alcohol for 2 - 5 times, filter by suction and dry in vacuum to obtain the microcapsules; wherein, the mass ratio of the prepolymer solution or homogeneous polymer solution prepared in Step 1 to the oil-in-water emulsion prepared in Step 2 is 1∶(0.0375 - 0.15).

[0070] Further, the preparation method of the self-healing microcapsules with integrated mobility and signal function may further include:

[0071] Step 4, surface modification of microcapsules:

[0072] Add the microcapsules prepared in Step 3 to the surface modification shell material solution of the self-healing microcapsules of Example 1, Example 2 or Example 3 with a concentration of 2 - 18 wt% under the stirring conditions of 50 - 90 °C and 300 - 1000 r / min, stir for 1 - 3 h, wash with deionized water and ethanol, and dry in vacuum to obtain the self-healing microcapsules.

[0073] The following combines examples to detail the preparation method of the self-healing microcapsules with integrated mobility and signal function of the present invention.

[0074] Example 4

[0075] The preparation method of the self-healing microcapsules with integrated mobility and signal function disclosed in this example mainly includes the following steps:

[0076] Step 1, preparation of microcapsule shell prepolymer:

[0077] Add 5 g of EMA solution (2.5 wt%), 0.503 g of urea, 0.05 g of resorcinol, and 0.065 g of ammonium chloride to 20 ml of deionized water, stir at 500 r / min for 20 min, adjust the solution pH to 3.5, and react at 55 °C for 1 h to obtain the prepolymer solution of the shell material.

[0078] Step 2, microcapsule emulsification:

[0079] At 55 °C, under the conditions of pH 3.5 and 900 r / min, drop 1 g of 4,4'-dicyclohexylmethane diisocyanate into an aqueous solution (10 ml) containing 2 wt% of gum arabic, stir for 30 min, then add an appropriate amount of water and stir and emulsify at a speed greater than 1500 r / min for 15 - 60 min, so that the concentration of 4,4'-dicyclohexylmethane diisocyanate is 3 - 20 wt% and the concentration of gum arabic is 0.5 - 2 wt%. Obtain emulsion A encapsulating 4,4'-dicyclohexylmethane diisocyanate.

[0080] Step 3, crosslinking of the microcapsule shell layer:

[0081] Under the conditions of 500 r / min and 65 °C, the prepolymer solution obtained in Step 1 was slowly dropped into Emulsion A prepared in Step 2. After reacting for 50 min, it was washed with deionized water / ethanol, filtered by suction, and dried under vacuum to obtain PUF microcapsules A encapsulating 4,4'-dicyclohexylmethane diisocyanate. Among them, the mass ratio of the prepolymer solution in Step 1 to Emulsion A prepared in Step 2 is 1:(0.0375 - 0.15).

[0082] Furthermore, it may further include:

[0083] Step 4, surface modification of the microcapsules:

[0084] Prepare an aqueous solution of polyvinyl alcohol with a concentration of 5 wt%. Stir at a rate of 800 r / min at 90 °C for 1 h and then cool to room temperature for standby; slowly add the microcapsules prepared in Step 3 above to the polyvinyl alcohol solution, stir and react at a rate of 600 r / min at 55 °C for 1 h. After washing with deionized water / alcohol and drying under vacuum, self-healing microcapsules A modified with polyvinyl alcohol are obtained. Among them, the particle size of the self-healing microcapsules A modified with polyvinyl alcohol is 150 nm, and the core material content is 79%.

[0085] Example 5

[0086] The preparation method of the active information-integrated self-healing microcapsules disclosed in this example mainly includes the following steps:

[0087] Step 1, preparation of the microcapsule shell layer prepolymer:

[0088] Add 5 g of EMA solution (2.5 wt%), 0.503 g of urea, 0.05 g of resorcinol, and 0.065 g of ammonium chloride to 20 ml of deionized water, stir at a speed of 500 r / min for 20 min, adjust the pH of the solution to 3.5, and react at 55 °C for 1 h to obtain the prepolymer solution of the shell material.

[0089] Step 2, microencapsulation emulsification:

[0090] Under the conditions of 55 °C, pH 3.5, and 1500 r / min, 1 g of diethylenetriamine was dropped into an aqueous solution (10 ml) containing 2 wt% of gum arabic, stirred for 30 min, and then an appropriate amount of water was added and stirred and emulsified at a speed greater than 1500 r / min for 15 - 60 min, so that the concentration of diethylenetriamine was 3 - 20 wt% and the concentration of gum arabic was 0.5 - 2 wt%. Emulsion B encapsulating diethylenetriamine was obtained.

[0091] Step 3, crosslinking of the microcapsule shell layer:

[0092] Under the conditions of 500 r / min and 65 °C, the prepolymer solution in Step 1 was slowly added dropwise to Emulsion B in Step 2. After reacting for 50 min, it was washed with deionized water / ethanol, filtered by suction, and dried in vacuum to obtain PUF microcapsules B encapsulating diethylenetriamine. Among them, the mass ratio of the prepolymer solution in Step 1 to Emulsion B prepared in Step 2 was 1∶(0.0375 - 0.15).

[0093] Furthermore, it may further include:

[0094] Step 4, surface modification of microcapsules:

[0095] Prepare an aqueous solution of polyvinyl alcohol with a concentration of 5 wt%. Stir at a rate of 800 r / min at 90 °C for 1 h and then cool to room temperature for standby; slowly add the microcapsules prepared in Step 3 above to the polyvinyl alcohol solution, stir and react at a rate of 600 r / min at 55 °C for 1 h. After washing with deionized water / alcohol and drying in vacuum, self-healing microcapsules B modified with polyvinyl alcohol were obtained. Among them, the particle size of the self-healing microcapsules B modified with polyvinyl alcohol was 170 nm, and the core material content was 82%.

[0096] Example 6

[0097] The preparation method of the active information-integrated self-healing microcapsules disclosed in this example mainly includes the following steps:

[0098] Step 1, preparation of microcapsule shell prepolymer:

[0099] Add 5 g of EMA solution (2.5 wt%), 0.503 g of urea, 0.05 g of resorcinol, and 0.065 g of ammonium chloride to 20 ml of deionized water, stir at a speed of 500 r / min for 20 min, adjust the pH of the solution to 3.5, and react at 55 °C for 1 h to obtain a prepolymer solution of the shell material.

[0100] Step 2, microcapsule emulsification:

[0101] Under the conditions of 55 °C, pH 3.5, and 900 r / min, 0.8 g of 4,4'-dicyclohexylmethane diisocyanate was dropped into an aqueous solution (10 ml) containing 1 wt% gum arabic, stirred for 20 min, and then an appropriate amount of water was added and stirred and emulsified at a speed greater than 1500 r / min for 15 - 60 min, so that the concentration of 4,4'-dicyclohexylmethane diisocyanate was 3 - 20 wt% and the concentration of gum arabic was 0.5 - 2 wt%. Emulsion A encapsulating 4,4'-dicyclohexylmethane diisocyanate was obtained.

[0102] Step 3, microcapsule shell crosslinking:

[0103] Under the conditions of 200 r / min and 65 °C, the prepolymer solution from Step 1 was slowly added dropwise to Emulsion A. After reacting for 40 min, it was washed with deionized water / ethanol, filtered by suction, and dried under vacuum to obtain PUF microcapsules A encapsulating 4,4'-dicyclohexylmethane diisocyanate. Among them, the mass ratio of the prepolymer solution in Step 1 to Emulsion A prepared in Step 2 was 1:(0.0375 - 0.15).

[0104] Furthermore, it may also include:

[0105] Step 4, surface modification of microcapsules:

[0106] Prepare an aqueous solution of polyvinyl alcohol with a concentration of 5 wt%. Stir it at a rate of 800 r / min at 90 °C for 1 h and then cool it to room temperature for standby; slowly add the microcapsules prepared in Step 3 above to the polyvinyl alcohol solution, and stir and react at a rate of 1000 r / min at 55 °C for 1.5 h. After washing with deionized water / alcohol and drying under vacuum, self-healing microcapsules A modified with polyvinyl alcohol are obtained. Among them, the particle size of the self-healing microcapsules A is 70 nm, and the core material content is 86%.

[0107] Example 7

[0108] The preparation method of the self-healing microcapsules with integrated actuation and communication disclosed in this example mainly includes the following steps:

[0109] Step 1, preparation of microcapsule shell prepolymer:

[0110] Add 5 g of EMA solution (2.5 wt%), 0.503 g of urea, 0.05 g of resorcinol, and 0.065 g of ammonium chloride to 20 ml of deionized water. Stir at a speed of 500 r / min for 20 min, adjust the pH of the solution to 3.5, and react at 55 °C for 1 h to obtain a prepolymer solution of the shell material.

[0111] Step 2, microcapsule emulsification:

[0112] Under the conditions of 65 °C, pH 3.5, and 1400 r / min, 0.8 g of polyethylene glycol (Mw = 600) was dropped into an aqueous solution (10 ml) containing 1 wt% of gum arabic, stirred for 40 min, and then an appropriate amount of water was added and stirred and emulsified at a speed greater than 1500 r / min for 15 - 60 min, so that the concentration of polyethylene glycol was 3 - 20 wt% and the concentration of gum arabic was 0.5 - 2 wt%. Emulsion B encapsulating polyethylene glycol was obtained.

[0113] Step 3, microcapsule shell crosslinking:

[0114] Under the conditions of 200 r / min and 65 °C, the prepolymer solution from Step 1 was slowly added dropwise to Emulsion B. After reacting for 40 min, it was washed with deionized water / ethanol, filtered by suction, and dried in vacuum to obtain PUF microcapsules B encapsulated with polyethylene glycol. Among them, the mass ratio of the prepolymer solution in Step 1 to Emulsion B prepared in Step 2 was 1:(0.0375 - 0.15).

[0115] Further, it may also include:

[0116] Step 4, surface modification of microcapsules:

[0117] Prepare an aqueous solution of polyvinyl alcohol with a concentration of 5 wt%. Stir at a rate of 800 r / min at 90 °C for 1 h and then cool to room temperature for standby; slowly add the microcapsules prepared in Step 3 above to the polyvinyl alcohol solution, stir and react at a rate of 1000 r / min at 55 °C for 1.5 h. After washing with deionized water / alcohol and drying in vacuum, self-healing microcapsules B modified with polyvinyl alcohol are obtained. Among them, the particle size of the self-healing microcapsules B is 90 nm, and the core material content is 82%.

[0118] Example 8

[0119] The preparation method of the self-healing microcapsule combination of the active information integration disclosed in this example mainly includes the following steps:

[0120] Step 1, preparation of microcapsule shell layer prepolymer:

[0121] Add 5 g of EMA solution (2.5 wt%), 0.503 g of urea, 0.05 g of resorcinol, and 0.065 g of ammonium chloride to 20 ml of deionized water, stir at a speed of 500 r / min for 20 min, adjust the pH of the solution to 3.5, and react at 55 °C for 1 h to obtain a prepolymer solution of the shell material.

[0122] Step 2, microcapsule emulsification:

[0123] Under the conditions of 55 °C, pH 3.5, and 900 r / min, 1 g of 4,4'-dicyclohexylmethane diisocyanate was dropped into an aqueous solution (10 ml) containing 2 wt% gum arabic, stirred for 30 min, and then an appropriate amount of water was added and stirred at a speed greater than 1500 r / min for emulsification for 15 - 60 min, so that the concentration of 4,4'-dicyclohexylmethane diisocyanate was 3 - 20 wt% and the concentration of gum arabic was 0.5 - 2 wt%. An emulsion A encapsulating 4,4'-dicyclohexylmethane diisocyanate was obtained; under the conditions of 55 °C, pH 3.5, and 1500 r / min, 1 g of diethylenetriamine was dropped into an aqueous solution (10 ml) containing 2 wt% gum arabic, stirred for 30 min, and then an appropriate amount of water was added and stirred at a speed greater than 1500 r / min for emulsification for 15 - 60 min, so that the concentration of diethylenetriamine was 3 - 20 wt% and the concentration of gum arabic was 0.5 - 2 wt%. An emulsion B encapsulating diethylenetriamine was obtained.

[0124] Step three, cross-linking of the microcapsule shell layer:

[0125] Under the conditions of 500 r / min and 65 °C, the prepolymer solution from step one was slowly dropped into emulsion A prepared in step two. After reacting for 50 min, it was washed with deionized water / ethanol, filtered by suction, and dried in vacuum to obtain PUF microcapsules A encapsulating 4,4'-dicyclohexylmethane diisocyanate. Among them, the mass ratio of the prepolymer solution from step one to emulsion A prepared in step two was 1:(0.0375 - 0.15).

[0126] Under the same steps, under the conditions of 500 r / min and 65 °C, the prepolymer solution from step one was slowly dropped into emulsion B from step two. After reacting for 50 min, it was washed with deionized water / ethanol, filtered by suction, and dried in vacuum to obtain PUF microcapsules B encapsulating diethylenetriamine. Among them, the mass ratio of the prepolymer solution from step one to emulsion B prepared in step two was 1:(0.0375 - 0.15).

[0127] Furthermore, it may further include:

[0128] Step four, surface modification of the microcapsules:

[0129] Prepare an aqueous solution of polyvinyl alcohol with a concentration of 5 wt%. Stir it at a rate of 800 r / min at 90 °C for 1 h and then cool it to room temperature for later use. Slowly add the above two kinds of microcapsules into the polyvinyl alcohol solution, stir and react at a rate of 600 r / min at 55 °C for 1 h. After washing with deionized water / alcohol and vacuum drying, self-healing microcapsule A and self-healing microcapsule B modified with polyvinyl alcohol are obtained. Among them, the particle sizes of self-healing microcapsule A and self-healing microcapsule B modified with polyvinyl alcohol are 150 nm and 170 nm respectively, and the core material contents are 79% and 82% respectively.

[0130] Add self-healing microcapsule A and self-healing microcapsule B into the silicon anode slurry at 3 wt% (compared with the mass of the active material), and use a lithium sheet as the counter electrode to prepare a lithium-ion battery containing self-healing microcapsules with integrated active information. The capacity retention rate is 87% after 200 cycles at 0.2C.

[0131] Example 9

[0132] The preparation method of the integrated active information self-healing microcapsule combination disclosed in this example mainly includes the following steps:

[0133] Step 1, preparation of microcapsule shell prepolymer:

[0134] Add 5 g of EMA solution (2.5 wt%), 0.503 g of urea, 0.05 g of resorcinol, and 0.065 g of ammonium chloride into 20 ml of deionized water, stir at a speed of 500 r / min for 20 min, adjust the pH of the solution to 3.5, and react for 1 h to obtain a prepolymer solution of the shell material.

[0135] Step 2, microcapsule emulsification:

[0136] Under the conditions of 55 °C, pH 3.5, and 900 r / min, drop 0.8 g of 4,4'-dicyclohexylmethane diisocyanate into an aqueous solution (10 ml) containing 1 wt% gum arabic, stir for 20 min, then add an appropriate amount of water and stir and emulsify at a speed greater than 1500 r / min for 15 - 60 min, so that the concentration of 4,4'-dicyclohexylmethane diisocyanate is 3 - 20 wt% and the concentration of gum arabic is 0.5 - 2 wt%. Emulsion A encapsulating 4,4'-dicyclohexylmethane diisocyanate is obtained. Under the conditions of 65 °C, pH 3.5, and 1400 r / min, drop 0.8 g of polyethylene glycol (Mw = 600) into an aqueous solution (10 ml) containing 1 wt% gum arabic, stir for 40 min, then add an appropriate amount of water and stir and emulsify at a speed greater than 1500 r / min for 15 - 60 min, so that the concentration of polyethylene glycol is 3 - 20 wt% and the concentration of gum arabic is 0.5 - 2 wt%. Emulsion B encapsulating polyethylene glycol is obtained.

[0137] Step 3, crosslinking of the microcapsule shell layer:

[0138] Under the conditions of 200 r / min and 65 °C, the prepolymer solution from Step 1 was slowly added dropwise to Emulsion A. After reacting for 40 min, it was washed with deionized water / ethanol, filtered by suction, and dried under vacuum to obtain PUF microcapsules A encapsulating 4,4'-dicyclohexylmethane diisocyanate. Among them, the mass ratio of the prepolymer solution from Step 1 to Emulsion A prepared in Step 2 was 1∶(0.0375 - 0.15).

[0139] Under the same steps, under the conditions of 200 r / min and 65 °C, the prepolymer solution from Step 1 was slowly added dropwise to Emulsion B. After reacting for 40 min, it was washed with deionized water / ethanol, filtered by suction, and dried under vacuum to obtain PUF microcapsules B encapsulating polyethylene glycol. Among them, the mass ratio of the prepolymer solution from Step 1 to Emulsion B prepared in Step 2 was 1∶(0.0375 - 0.15).

[0140] Further, it may also include:

[0141] Step 4, surface modification of the microcapsules:

[0142] Prepare an aqueous solution of polyvinyl alcohol with a concentration of 5 wt%. Stir at a rate of 800 r / min at 90 °C for 1 h and then cool to room temperature for standby; slowly add the above two kinds of microcapsules to the polyvinyl alcohol solution, stir and react at a rate of 1000 r / min at 55 °C for 1.5 h. After washing with deionized water / alcohol and drying under vacuum, self-healing microcapsules A and self-healing microcapsules B modified with polyvinyl alcohol were obtained. Among them, the particle sizes of self-healing microcapsules A and self-healing microcapsules B were 70 nm and 90 nm respectively, and the core material contents were 86% and 82% respectively.

[0143] Self-healing microcapsules A and self-healing microcapsules B were added to the silicon anode slurry at 5 wt% (compared with the mass of the active substance), and a lithium-ion battery containing self-healing microcapsules with an active information unit was prepared using a lithium sheet as the counter electrode. The capacity retention rate was 90% after 200 cycles at 0.2C.

[0144] It should be noted that all the features disclosed in this specification, or all the steps in the disclosed methods or processes, except for mutually exclusive features and / or steps, can be combined in any way.

[0145] In addition, the above specific embodiments are exemplary. Those skilled in the art can come up with various solutions inspired by the disclosed content of the present invention, and these solutions also fall within the scope of the disclosure of the present invention and within the protection scope of the present invention. Those skilled in the art should understand that the specification and drawings of the present invention are illustrative and do not constitute a limitation on the claims. The protection scope of the present invention is defined by the claims and their equivalents.

Claims

1. A preparation method of a self-repairing microcapsule combination integrating motility and signal transduction, characterized in that, It includes the following steps: Step 1, preparation of microcapsule shell prepolymer: Add 5 g of EMA solution with a concentration of 2.5 wt%, 0.503 g of urea, 0.05 g of resorcinol, and 0.065 g of ammonium chloride into 20 ml of deionized water, stir at a speed of 500 r / min for 20 min, adjust the pH of the solution to 3.5, and react for 1 h to obtain the prepolymer solution of the shell material; Step 2, microcapsule emulsification: Under the conditions of 55 °C, pH 3.5, and 900 r / min, drop 0.8 g of 4,4'-dicyclohexylmethane diisocyanate into 10 ml of an aqueous solution containing 1 wt% of gum arabic, stir for 20 min, then add an appropriate amount of water and stir and emulsify at a speed greater than 1500 r / min for 15 - 60 min, so that the concentration of 4,4'-dicyclohexylmethane diisocyanate is 3 - 20 wt% and the concentration of gum arabic is 0.5 - 2 wt% to obtain emulsion A encapsulating 4,4'-dicyclohexylmethane diisocyanate; under the conditions of 65 °C, pH 3.5, and 1400 r / min, drop 0.8 g of polyethylene glycol (Mw = 600) into 10 ml of an aqueous solution containing 1 wt% of gum arabic, stir for 40 min, then add an appropriate amount of water and stir and emulsify at a speed greater than 1500 r / min for 15 - 60 min, so that the concentration of polyethylene glycol is 3 - 20 wt% and the concentration of gum arabic is 0.5 - 2 wt% to obtain emulsion B encapsulating polyethylene glycol; Step 3, microcapsule shell crosslinking: Under the conditions of 200 r / min and 65 °C, drop the prepolymer solution in Step 1 into emulsion A, after reacting for 40 min, wash with deionized water / ethanol, filter by suction, and dry in vacuum to obtain PUF microcapsule A encapsulating 4,4'-dicyclohexylmethane diisocyanate; among them, the mass ratio of the prepolymer solution in Step 1 to emulsion A prepared in Step 2 is 1∶(0.0375 - 0.15); Under the same steps, under the conditions of 200 r / min and 65 °C, drop the prepolymer solution in Step 1 into emulsion B, after reacting for 40 min, wash with deionized water / ethanol, filter by suction, and dry in vacuum to obtain PUF microcapsule B encapsulating polyethylene glycol; among them, the mass ratio of the prepolymer solution in Step 1 to emulsion B prepared in Step 2 is 1∶(0.0375 - 0.15); Step 4, microcapsule surface modification: Prepare a 5 wt% aqueous solution of polyvinyl alcohol, stir at a rate of 800 r / min at 90 °C for 1 h and then cool to room temperature for standby; add the above two kinds of microcapsules into the polyvinyl alcohol solution, stir and react at a rate of 1000 r / min at 55 °C for 1.5 h, after washing with deionized water / alcohol and drying in vacuum, obtain polyvinyl alcohol-modified self-healing microcapsule A and self-healing microcapsule B.

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