Series of self-recovery mechanoluminescent materials based on contact electricity theory and preparation method of series of self-recovery mechanoluminescent materials

Abstract

The invention provides a series of self-recovery mechanoluminescent materials based on a contact electricity theory and a preparation method thereof. The series of self-restoring mechanoluminescent materials based on the contact electricity theory comprise fluorescent powder Ca {1-x} F2: xTb < 3 + > / yEu < 2 + > / zSm < 3 + >, wherein 0% lt; x, y, zlt; 20%; the mechanoluminescent material is composed of an optical function material and a carrier material, the optical function material is calcium fluoride-based fluorescent powder coated with aluminum salt, and the carrier material is polydimethylsiloxane, natural rubber, silica gel, PU and an elastomer material. According to the series of self-recovery mechanoluminescent materials based on the contact electricity theory and the preparation method thereof, the problems that an existing sulfide mechanoluminescent material is unstable, polluted and few in luminescent color variety, and an existing afterglow oxide mechanoluminescent material needs to be charged and cannot be self-recovered are solved through the materials; the key problems that an existing mechanoluminescent material cannot be self-recovered under external stimulation and is extremely poor in luminescence stability are solved.

Description

Technical Field

[0001] The present invention relates to the technical fields of sensing, information collection, and preparation methods of luminescent materials, and particularly relates to a series of self-recoverable force-induced luminescent materials based on the contact electrification theory and a preparation method thereof. Background Art

[0002] In the field of sensors, technologies for converting various physical quantities into electrical signal outputs have been widely applied. However, these devices are usually costly, complex to operate, and not conducive to direct human eye observation. Against this background, the invention of force-induced luminescent materials provides an innovative solution. It can directly convert externally applied force into visible light signals. The advantages of this technology are that its product design is lightweight, the structure is simple, the performance is stable, and it does not require external power supply.

[0003] The preparation of force-induced luminescent materials is relatively easy and has low difficulty in large-scale production. Currently, existing force-induced luminescent materials are mainly divided into two categories: sulfides and afterglow-type oxides. The advantage of sulfide materials is that they can self-recover without charging, but their performance is unstable and there is a certain pollution risk to the environment. At the same time, the types of luminescent colors are also relatively limited. While afterglow-type oxides have good stability and pollution-free characteristics, they need to be charged and lack a self-recovery effect. The luminous efficiency of these two types of materials is generally low, and the stability of their force-induced luminescence is extremely poor. The force-induced luminescence decreases during the stretching process. The force-induced luminescence of these elastomers can self-recover and remain stable after slight scratching, but cannot recover after each hard stretch. Especially after three hard stretches, due to damage to the binding interface between the phosphor and PDMS, the force-induced luminescence brightness of these elastomers has significantly decreased, almost reduced to 0, and cannot recover within a short time, limiting the wide range of their applications.

[0004] Existing sulfide-based force-induced luminescent materials are unstable, polluting, and have few luminescent color types. Existing afterglow-type oxide-based force-induced luminescent materials need to be charged and cannot self-recover. Existing force-induced luminescent materials cannot self-recover under external stimuli and have extremely poor luminescence stability.

[0005] Therefore, it is necessary to provide a series of self-recoverable force-induced luminescent materials based on the contact electrification theory and a preparation method thereof to solve the above technical problems. Summary of the Invention

[0006] The present invention provides a series of self-recoverable force-induced luminescent materials based on the contact electrification theory and a preparation method thereof, which solves the problem that existing sulfide-based force-induced luminescent materials cannot self-recover under external stimuli and have extremely poor luminescence stability.

[0007] To solve the above technical problems, the series of self-recoverable force-induced luminescent materials based on the contact electrification theory provided by the present invention include: phosphor Ca{1-x}F2:xTb3+ / yEu2+ / zSm3+, where 0% < x, y, z < 20%;

[0008] A force-induced luminescent material, which is composed of two parts: a light-functional material and a carrier material. The light-functional material is a calcium fluoride-based phosphor coated with aluminum salt, and the carrier material is polydimethylsiloxane, natural rubber, silica gel, PU, or an elastomeric material. The light-functional material is calcium fluoride doped with terbium ions CaF2:Tb3+, calcium fluoride doped with europium ions CaF2:Eu2+, or calcium fluoride doped with samarium ions CaF2:Sm3+. The light-functional material is calcium fluoride phosphor CaF2, and the product after partially replacing the cation Ca2+ with terbium element Tb3+, europium element Eu2+, and samarium element Sm3+.

[0009] A preparation method for a series of self-recoverable force-induced luminescent materials based on the contact electrification theory, comprising the following steps;

[0010] First step: Weigh the raw materials according to the stoichiometric ratio of the corresponding elements in the chemical formula Ca{1-x}F2:xTb3+ / yEu2+ / zSm3+: a compound containing calcium ions, a compound containing fluoride ions, a compound containing terbium ions, a compound containing europium ions, and a compound containing samarium ions, and put them into an agate mortar and grind them thoroughly until they are evenly mixed, where 0% < x, y, z < 20%;

[0011] Second step: After mixing the raw materials obtained in the first step, place them in a crucible, and then calcine them through a heating device. The calcination temperature is 800 - 1500 °C, and the calcination time is 3 - 10 hours. Then, naturally cool them to room temperature to obtain the phosphor CaF2:Tb3+ / Eu2+ / Sm3+;

[0012] Third step: Put the raw materials obtained in the second step into a beaker, add distilled water and stir, add the corresponding nitrates, slowly add the aluminum salt / nitrate solution, filter out the product after full reaction, and calcine the product and then naturally cool it to room temperature;

[0013] Fourth step: Mix liquid A and liquid B of polydimethylsiloxane according to a ratio, and liquid B can account for 2% - 30%. Add a certain amount of phosphor CaF2:Tb3+ / Eu2+ / Sm3+ to the obtained polydimethylsiloxane. The mass ratio of the phosphor to polydimethylsiloxane is 0.1 - 1:1;

[0014] Step 5: Stir the mixture of phosphor and polydimethylsiloxane evenly, make a precursor through screen printing technology, put the precursor into an incubator, and keep it warm at a specific temperature for more than 2 hours to obtain a flexible composite material of calcium fluoride-based dynamic luminescent phosphor coated with aluminum salt;

[0015] Step 6: Take out the sample, and the preparation of the force-induced and photo-induced multimode dynamic luminescent composite material is completed.

[0016] Preferably, the carrier material is acrylic, natural rubber, silicone rubber, PU, PET, TPE or TPR material, and x / y / z = 7% in the phosphor Ca{1-x}F2:xTb3+ / yEu2+ / zSm3+.

[0017] Preferably, the sintering temperature range in the second step is 800°C to 1500°C.

[0018] Preferably, a nitrate solution such as aluminum nitrate, barium nitrate or other raw materials needs to be added to the coated oxide in the third step.

[0019] Preferably, the optimal mass ratio of liquid A and liquid B of polydimethylsiloxane in the fourth step is 10:1, and the optimal mass ratio of phosphor and polydimethylsiloxane is 0.5:1. In the fifth step, the temperature at which the precursor is put into the incubator is 60°C, and the holding time is 2 hours.

[0020] Preferably, the heating device includes a bottom plate, a support frame is fixedly connected to the top of the bottom plate, and a heating cabinet is installed on the top of the support frame.

[0021] Preferably, sliding rails are installed on both sides of the inner wall of the heating cabinet. An activity frame is slidably connected between each group of sliding rails through a sliding bar. Placing grooves are formed at the tops of the activity frames, and a plurality of crucibles are placed in the placing grooves through limiting rings;

[0022] The sliding rails at the same height on both sides of the inner wall of the heating cabinet are in a group.

[0023] Preferably, heating devices are installed on both sides of the heating cabinet, heating ports are installed on one side of each heating device, a cabinet door is rotatably connected to the front of the heating cabinet, and a warm air device and a temperature sensor are installed on the top of the heating cabinet respectively;

[0024] The heating ports are located on both sides of the inner wall of the heating cabinet and between the activity frames. The heating device can use resistance heating and can reach a temperature of 1000 - 1500°C. The warm air device can assist in heating up when the heating cabinet is cold.

[0025] Preferably, an operation screen is also installed on the front of the support frame through a mounting base, and a control box with a box door is installed on one side of the support frame;

[0026] Inside the control box, there are installed a power switch and a controller for controlling the operation of the equipment.

[0027] Compared with the related technologies, the series of self - recoverable force - induced luminescence materials based on the contact electrification theory and their preparation methods provided by the present invention have the following beneficial effects:

[0028] The present invention provides a series of self - recoverable force - induced luminescence materials based on the contact electrification theory and their preparation methods. In order to increase the stability and durability of the force - induced luminescence materials, the raw materials used include the phosphor Ca{1 - x}F2:xTb3 + / yEu2 + / zSm3 +, where 0% < x, y, z < 20%. The force - induced luminescence material consists of two parts: a light - functional material and a carrier material. The light - functional material is a calcium fluoride - based phosphor coated with aluminum salt, and the carrier material is an elastomer material such as polydimethylsiloxane, natural rubber, silica gel, PU, etc. Only when the carrier material and the light - functional material are combined can a significant force - induced luminescence effect be achieved. And the above - mentioned luminescence materials have the advantages of being pollution - free, energy - free, self - recoverable, and high luminous efficiency. Only after the carrier material and the calcium fluoride phosphor are combined can a significant force - induced luminescence effect be achieved. Moreover, the raw materials required for preparing the product are simple, the process is convenient, large - scale equipment is not needed, mass production is easy, and the performance is stable. The product has good elasticity, flexibility, good thermal stability and good water stability. It can respond to actions such as stretching, scratching, bending, and tearing under force and convert them into visible light. The luminous intensity is positively correlated with the degree of deformation. Through this material, the key problems of the existing sulfur - based force - induced luminescence materials being unstable, polluted, and having few luminescence color types, the existing afterglow - type oxide force - induced luminescence materials requiring energy charging and not being self - recoverable, and the existing force - induced luminescence materials being unable to self - recover under external stimuli and having extremely poor luminous stability are solved. Brief Description of the Drawings

[0029] Figure 1 Schematic diagram of the first embodiment of the series of self - recoverable force - induced luminescence materials based on the contact electrification theory and their preparation methods provided by the present invention;

[0030] Figure 2 Schematic diagram of the force - induced luminescence intensity of the friction - test material provided by the present invention;

[0031] Figure 3 Schematic diagram of the force - induced luminescence intensity of the ball - dropping - test material provided by the present invention;

[0032] Figure 4 Flowchart of the preparation method provided by the present invention;

[0033] Figure 5 Schematic diagram of the self - recoverable stretching test provided by the present invention;

[0034] Figure 6Schematic diagram of the self - restoring force - induced luminescence data graph provided by the present invention;

[0035] Figure 7 Schematic diagram of the structure of the second embodiment of the series of self - restoring force - induced luminescence materials and their preparation methods based on the contact electrification theory provided by the present invention;

[0036] Figure 8 Schematic diagram of the structure of the movable frame provided by the present invention;

[0037] Figure 9 Provided by the present invention Figure 8 Enlarged view of the part marked A as shown.

[0038] Reference numerals in the figure: 1, bottom plate; 2, heating cabinet; 3, operation screen; 4, installation base; 5, support frame; 6, control box; 7, cabinet door; 8, heating device; 9, temperature sensor; 10, warm air device; 11, cabinet door; 12, placement groove; 13, movable frame; 14, slide bar; 15, limit ring; 16, crucible; 17, heating port; 18, slide rail. Detailed implementation manners

[0039] The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

[0040] Please refer to in conjunction with Figure 1 、 Figure 2 、 Figure 3 、 Figure 4 、 Figure 5 、 Figure 6 , wherein, Figure 1 Schematic diagram of the first embodiment of the series of self - restoring force - induced luminescence materials and their preparation methods based on the contact electrification theory provided by the present invention; Figure 2 Schematic diagram of the force - induced luminescence intensity of the friction - test material provided by the present invention; Figure 3 Schematic diagram of the force - induced luminescence intensity of the ball - drop test material provided by the present invention; Figure 4 Flow chart of the preparation method process provided by the present invention; Figure 5 Schematic diagram shown by the self - restoring tensile test provided by the present invention; Figure 6 Schematic diagram of the self - restoring force - induced luminescence data graph provided by the present invention. The series of self - restoring force - induced luminescence materials based on the contact electrification theory include: phosphor Ca{1 - x}F2:xTb3+ / yEu2+ / zSm3+, where 0% < x, y, z < 20%;

[0041] Stress-luminescent material, the stress-luminescent material consists of two parts: a light-functional material and a carrier material. The light-functional material is a calcium fluoride-based phosphor coated with aluminum salt, and the carrier material is polydimethylsiloxane, natural rubber, silica gel, PU, or an elastomeric material. The light-functional material is calcium fluoride doped with terbium ions CaF2:Tb3+, calcium fluoride doped with europium ions CaF2:Eu2+, or calcium fluoride doped with samarium ions CaF2:Sm3+. The light-functional material is calcium fluoride phosphor CaF2, and the product after partially replacing the cation Ca2+ with terbium element Tb3+, europium element Eu2+, and samarium element Sm3+;

[0042] Only when the carrier material and the light-functional material are combined can a significant stress-luminescent effect be achieved. The light-functional material can be the product after partially replacing cations or anions with other elements.

[0043] A preparation method of a series of self-recovery stress-luminescent materials based on the contact electrification theory, comprising the following steps:

[0044] First step: Weigh the raw materials according to the stoichiometric ratio of the corresponding elements in the chemical formula Ca{1-x}F2:xTb3+ / yEu2+ / zSm3+: a compound containing calcium ions, a compound containing fluoride ions, a compound containing terbium ions, a compound containing europium ions, and a compound containing samarium ions, and put them into an agate mortar and grind them thoroughly until they are mixed evenly, where 0% < x, y, z < 20%;

[0045] Second step: After mixing the raw materials obtained in the first step, place them in a crucible, and then calcine them through a heating device. The calcination temperature is 800 - 1500 °C, and the calcination time is 3 - 10 hours. Then naturally cool them to room temperature to obtain the phosphor CaF2:Tb3+ / Eu2+ / Sm3+;

[0046] Third step: Put the raw materials obtained in the second step into a beaker, add distilled water and stir, add the corresponding nitrates, slowly add the aluminum salt / nitrate solution, filter out the product after sufficient reaction, and calcine the product and then naturally cool it to room temperature;

[0047] Fourth step: Mix the A liquid and B liquid of polydimethylsiloxane according to a ratio, and the B liquid can account for 2% - 30%. Add a certain amount of phosphor CaF2:Tb3+ / Eu2+ / Sm3+ to the obtained polydimethylsiloxane, and the mass ratio of the phosphor to polydimethylsiloxane is 0.1 - 1:1;

[0048] Fifth step: Stir the mixture of the phosphor and polydimethylsiloxane evenly, make a precursor through screen printing technology, put the precursor into an incubator, and keep it warm at a specific temperature for more than 2 hours to obtain a flexible composite material of an aluminum salt-coated calcium fluoride-based dynamic luminescent phosphor;

[0049] Step 6: Take out the sample, and the preparation of the force-induced and photo-induced multimode dynamic luminescent composite material is completed.

[0050] The carrier material is acrylic, natural rubber, silicone rubber, PU, PET, TPE or TPR material, and x / y / z in the phosphor Ca{1-x}F2:xTb3+ / yEu2+ / zSm3+ is 7%.

[0051] In the second step, the sintering temperature range is 800°C to 1500°C.

[0052] In the third step, nitrate solution such as aluminum nitrate, barium nitrate or other raw materials needs to be added to coat the oxide.

[0053] In the fourth step, the optimal mass ratio of liquid A and liquid B of polydimethylsiloxane is 10:1, and the optimal mass ratio of phosphor and polydimethylsiloxane is 0.5:1. In the fifth step, the temperature of the precursor placed in the incubator is 60°C, and the heat preservation time is 2 hours.

[0054] The working principle of the series of self-recoverable force-induced luminescent materials and their preparation methods based on the contact electrification theory provided by the present invention is as follows:

[0055] The force-induced luminescent materials made of calcium fluoride-based phosphors exhibit more excellent properties. As Figure 1 shown, to keep the lateral and longitudinal tensile forces symmetric when stretching the elastomer, we made the sample into a four-leaf clover shape. To quantitatively analyze the force-induced luminescence characteristics during the stretching process, the stretching speed, step size and frequency are set to 10.0 mm / s, 6.0 mm and 1.0 Hz respectively. The material can still clearly observe the bright green of the elastomer after being repeatedly stretched more than 30 times in the stretching mode of the tensile machine, and the luminescence intensity can self-recover to about 60-75% before stretching in a short time. As Figure 2 shown, a friction machine controlled by a motor is applied, and the load pressure on the nail is set to 30 g. Under continuous scratching, the luminescence of the elastomer is very stable. Even after 200 scratches, the force-induced luminescence intensity can fully self-recover. In addition, a ball-drop experiment was also carried out. As Figure 3As shown, an electromagnet is used to place a 15.0g iron ball on top of the elastomer. Then, the iron ball falls freely from a height of 0.5m, hits the elastomer and emits bright green mechanoluminescence. After 50 impacts, the mechanoluminescence efficiency and luminescence intensity of the elastomer can still remain stable, indicating that the material has excellent self-recovery properties under continuous impacts. The material not only has high luminescence efficiency and good self-recovery, but more importantly, it does not require charging during the mechanoluminescence process. Fluoride-based phosphors are non-piezoelectric, and the doped rare earth elements will not destroy the symmetry of the crystal. Therefore, the composite material does not need pre-irradiation to emit a strong green color and has self-recovery properties. These advantages make calcium fluoride-based mechanoluminescent materials show broad prospects and potential in future sensor applications.

[0056] The preparation method of a series of self-recovering mechanoluminescent materials based on contact electricity theory: S1. Mix liquid A and liquid B of polydimethylsiloxane in a certain proportion, with liquid B accounting for 2%-30%; S2. Add a certain amount of aluminum salt-coated calcium fluoride-doped rare earth ion phosphor to the mixed polydimethylsiloxane, and the ratio of phosphor to polydimethylsiloxane can be 0.1-1:1. S3. Stir the mixture of phosphor and polydimethylsiloxane evenly, spin coat or extrude it onto a mold to make a precursor; S4. Put the precursor into a constant temperature box and keep it warm at a certain temperature for more than two hours; S5. Take out the sample, and the mechanoluminescent material is prepared.

[0057] Compared with the related art, the series of self-recovering mesoluminescent materials based on contact electricity theory and the preparation method thereof provided by the present invention have the following beneficial effects:

[0058] In order to increase the stability and durability of the mechanoluminescent material, the raw materials used include the phosphor Ca{1-x}F2:xTb3+ / yEu2+ / zSm3+, where 0% < x, y, z < 20%. The mechanoluminescent material consists of two parts: a light-functional material and a carrier material. The light-functional material is a calcium fluoride-based phosphor coated with aluminum salt, and the carrier material is an elastomeric material such as polydimethylsiloxane, natural rubber, silica gel, PU, etc. Only when the carrier material and the light-functional material are combined can a significant mechanoluminescent effect be achieved. Moreover, the above-mentioned luminescent material has the advantages of being pollution-free, energy-free, self-recovering, and having high luminous efficiency. Only after the carrier material and the calcium fluoride phosphor are combined can a significant mechanoluminescent effect be achieved. And the raw materials required for preparing the product are simple, the process is convenient, large equipment is not needed, mass production is convenient, and the performance is stable. The product has good elasticity, flexibility, good thermal stability, and good water stability. It can respond to actions such as stretching, scratching, bending, and tearing under force and convert them into visible light. The luminous intensity is positively correlated with the degree of deformation. By using this material, the key problems of the existing sulfur-based mechanoluminescent materials being unstable, polluted, and having few luminescent color types, the existing afterglow-type oxide mechanoluminescent materials requiring energy and not being able to self-recover, and the existing mechanoluminescent materials being unable to self-recover under external stimuli and having extremely poor luminous stability are solved.

[0059] Second Embodiment

[0060] Please refer to Figures 7 - 8 - Figure 9 , Figure 7 is a schematic structural diagram of the second embodiment of the series of self-recovering mechanoluminescent materials and their preparation methods based on the contact electrification theory provided by the present invention; Figure 8 is a schematic structural diagram of the movable frame provided by the present invention; Figure 9 The present invention provides Figure 8 The enlarged view of the A position shown in; Based on the first embodiment of the present application, a series of self-recovering mechanoluminescent materials and their preparation methods based on the contact electrification theory are provided. The second embodiment of the present application proposes another series of self-recovering mechanoluminescent materials and their preparation methods based on the contact electrification theory. The second embodiment is merely a preferred manner of the first embodiment, and the implementation of the second embodiment will not affect the independent implementation of the first embodiment.

[0061] Specifically, the difference between the series of self-recovering mechanoluminescent materials and their preparation methods based on the contact electrification theory provided by the second embodiment of the present application is that the heating device includes a bottom plate 1, and a support frame 5 is fixedly connected to the top of the bottom plate 1, and a heating cabinet 2 is installed on the top of the support frame 5;

[0062] The structures on the heating cabinet 2 and the support frame 5 are both made of high-temperature resistant materials.

[0063] On both sides of the inner wall of the heating cabinet 2, slide rails 18 are installed. Between each group of the slide rails 18, a movable frame 13 is slidably connected through a slide bar 14. On the top of the movable frame 13, placing grooves 12 are respectively formed. Inside the placing grooves 12, a plurality of crucibles 16 are placed through limiting rings 15;

[0064] The slide rails 18 at the same height on both sides of the inner wall of the heating cabinet 2 are in a group. At the bottom of the inner wall of the placing groove 12, an opening is formed for the crucible 16 to be placed. The limiting ring 15 plays a limiting role.

[0065] On both sides of the heating cabinet 2, heating devices 8 are installed. On one side of each heating device 8, a heating port 17 is installed. The front surface of the heating cabinet 2 is rotatably connected with a cabinet door 11. On the top of the heating cabinet 2, a warm air device 10 and a temperature sensor 9 are respectively installed;

[0066] The heating ports 17 are located on both sides of the inner wall of the heating cabinet 2, and the heating ports 17 are located between the movable frames 13. The heating devices 8 can adopt resistance heating and can reach a temperature of 1000 - 1500 °C. The warm air device 10 can assist in heating up when the heating cabinet 2 is cold heated. The temperature sensor 9 can monitor the temperature in the heating cabinet 2.

[0067] On the front surface of the support frame 5, an operation screen 3 is also installed through a mounting base 4. On one side of the support frame 5, a control box 6 with a box door 7 is installed;

[0068] Inside the control box 6, a power switch and a controller for controlling the operation of the equipment are installed. A lock is set on the box door 7. The operation screen 3 can set the operation parameters of the equipment on the base plate 1.

[0069] Compared with the related technology, the series of self - recoverable force - induced luminescent materials based on the contact electricity theory and the preparation method provided by the present invention have the following beneficial effects:

[0070] In order to increase the preparation efficiency of the luminescent material, on both sides of the heating cabinet 2, a heating device 8 with a heating port 17 is installed. Then, a plurality of movable frames 13 are installed between the slide rails 18 inside the heating cabinet 2 through slide bars 14, so as to facilitate the taking and placing of the crucibles 16 containing the luminescent material. When actually in use, first

[0071] The above are only the embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. Any equivalent structural or equivalent process transformation made by using the content of the specification and drawings of the present invention, or directly or indirectly applied in other related technical fields, shall be similarly included in the patent protection scope of the present invention.

Claims

1. A series of self-recovering mechanoluminescent materials based on contact electricity theory, characterized in that: include: Phosphor Ca{1-x}F2:xTb 3+ / yEu 2+ / zSm 3+ , of which 0% <x,y,z<20%; The mechanoluminescent material is composed of a light-functional material and a carrier material. The light-functional material is a calcium fluoride-based phosphor coated with aluminum salt. The carrier material is polydimethylsiloxane, natural rubber, silica gel, PU, ​​or an elastomeric material. The light-functional material is calcium fluoride doped with terbium ions CaF2:Tb 3+ 、Calcium fluoride doped with europium ions CaF2:Eu 2+ , or calcium fluoride doped with samarium ions CaF2:Sm 3+ The optical functional material is calcium fluoride phosphor CaF2, and terbium element Tb 3+ , Europium 2+ and samarium 3+ Partially replace cation Ca 2+ The product after.

2. A method for preparing a series of self-recovering mechanoluminescent materials based on contact electricity theory, characterized in that: The steps include: Step 1: According to the chemical formula Ca{1-x}F2:xTb 3+ / yEu 2+ / zSm 3+ The raw materials are weighed in the chemical stoichiometric ratio of the corresponding elements: the compound containing calcium ions, the compound containing fluorine ions, the compound containing terbium ions, the compound containing europium ions and the compound containing samarium ions are put into an agate mortar and ground thoroughly until mixed evenly, wherein 0% <x,y,z<20%; Step 2: Mix the raw materials obtained in the first step and place them in a crucible, then calcine them through a heating device at a temperature of 800-1500°C for 3-10 hours, and then cool them naturally to room temperature to obtain the phosphor CaF2:Tb 3+ / Eu 2+ / Sm 3+ ; Step 3: put the raw materials obtained in the second step into a beaker, add distilled water and stir, add the corresponding nitrate, slowly add the aluminum salt / nitrate solution, filter out the product after sufficient reaction, calcine the product and then naturally cool it to room temperature; Step 4: Mix the polydimethylsiloxane A liquid and B liquid according to the proportion, with B liquid accounting for 2%-30%. Add a certain amount of phosphor CaF2:Tb to the obtained polydimethylsiloxane. 3+ / Eu 2+ / Sm 3+ , the mass ratio of phosphor to polydimethylsiloxane is 0.1-1:1; Step 5: Evenly stir the mixture of phosphor and polydimethylsiloxane, make a precursor by screen printing technology, put the precursor into an incubator, and keep it at a specific temperature for more than 2 hours to obtain a flexible composite material of aluminum salt-coated calcium fluoride-based dynamic luminescent phosphor; Step 6: Take out the sample, and the preparation of the photoinduced multi-mode dynamic luminescent composite material is completed.

3. The method for preparing a series of self-recovering mesoluminescent materials based on contact electricity theory according to claim 2, characterized in that: The carrier material is acrylic acid, natural rubber, silicone rubber, PU, ​​PET, TPE or TPR material, and the phosphor Ca{1-x}F2:xTb 3+ / yEu 2+ / zSm 3+ Where x / y / z=7%.

4. The method for preparing a series of self-recovering mesoluminescent materials based on contact electricity theory according to claim 2, characterized in that: The sintering temperature in the second step ranges from 800°C to 1500°C.

5. The method for preparing a series of self-recovering mesoluminescent materials based on contact electricity theory according to claim 2, characterized in that: In the third step, a nitrate solution, such as aluminum nitrate, barium nitrate or other raw materials, needs to be added to coat the oxide.

6. The method for preparing a series of self-recovering mesoluminescent materials based on contact electricity theory according to claim 2, characterized in that: In the fourth step, the optimal mass ratio of polydimethylsiloxane liquid A and liquid B is 10:1, and the optimal mass ratio of phosphor and polydimethylsiloxane is 0.5:

1. In the fifth step, the temperature of the precursor in the incubator is 60° C. and the insulation time is 2 hours.

7. The method for preparing a series of self-recovering mesoluminescent materials based on contact electricity theory according to claim 2, characterized in that: The heating device comprises a bottom plate, the top of the bottom plate is fixedly connected with a support frame, and the top of the support frame is equipped with a heating cabinet.

8. The method for preparing a series of self-recovering mesoluminescent materials based on contact electricity theory according to claim 7, characterized in that: Slide rails are installed on both sides of the inner wall of the heating cabinet, and a movable frame is slidably connected between each group of the slide rails through a slide bar. A placement groove is opened on the top of the movable frame, and multiple crucibles are placed inside the placement groove through a limiting ring.

9. The method for preparing a series of self-recovering mesoluminescent materials based on contact electricity theory according to claim 7, characterized in that: Heating devices are installed on both sides of the heating cabinet, a heating port is installed on one side of the heating device, a cabinet door is rotatably connected to the front of the heating cabinet, and a warm air device and a temperature sensor are respectively installed on the top of the heating cabinet.

10. The method for preparing a series of self-recovering mesoluminescent materials based on contact electricity theory according to claim 7, characterized in that: An operation screen is also installed on the front of the support frame through a mounting base, and a control box with a box door is installed on one side of the support frame.

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