Leather ion piezoelectric device and preparation method and application thereof

Abstract

The invention provides a leather ion piezoelectric device and a preparation method and application thereof, and belongs to the technical field of new energy conversion, the leather ion piezoelectric device comprises a device body, and two sides of the bottom of the device body are respectively provided with a stress electrode and a reference electrode; the preparation method of the leather ion piezoelectric device comprises the steps that raw hide obtained after pickling is subjected to tanning, retanning and electrolyte treatment, ion leather is obtained, the ion leather is cut, a device body is manufactured, a stress electrode and a reference electrode are attached to the two sides of the bottom of the device body respectively, and the leather ion piezoelectric device is obtained. The leather ion piezoelectric device provided by the invention has excellent mechanical property, damp-heat-resistant stability, durability and corrosion resistance, and is convenient to transport, store and reuse; the ion piezoelectric device prepared through the preparation method is good in mechanical performance and durable temperature performance, suitable for mechanical energy collection and power generation in a more complex special environment and an actual scene bearing large pressure, and wide in application range.

Description

Technical Field

[0001] The present invention relates to the technical field of new energy conversion, and in particular to a leather ion piezoelectric device and a preparation method and application thereof. Background Art

[0002] Ion piezoelectric technology is a green power generation technology that converts mechanical energy into electrical energy based on the ion piezoelectric effect. Ion piezoelectric technology has great practical significance for the development of mechanical energy collection and power generation, human-computer interaction systems, and self-powered sensor equipment. The ion piezoelectric effect is a phenomenon in which a piezoelectric material composed of a polymer matrix and mobile ions induces a temporary charge separation between cations and anions in the material by applying pressure, thereby generating voltage or current. At present, ion piezoelectric materials are mainly gels containing electrolytes. However, most gels have insufficient mechanical properties, durability and ion piezoelectric properties, making it difficult to adapt to more complex special environments. It is also difficult to maintain stable ion piezoelectric properties under conditions of high pressure and frequent use, which greatly limits the practical application of ion piezoelectric devices. Summary of the invention

[0003] The purpose of the present invention is to provide a leather ion piezoelectric device and its preparation method and application. In view of the problems that the mechanical properties, durability stability and ion piezoelectric properties of the ion piezoelectric devices in the prior art are insufficient, it is difficult to adapt to more complex special environments, and it is difficult to maintain stable ion piezoelectric properties under conditions of high pressure and frequent use, the leather ion piezoelectric device provided by the present invention can have excellent mechanical properties, moisture and heat stability, durability and corrosion resistance, and is easy to transport, store and reuse; by connecting the force electrodes and reference electrodes of several different leather ion piezoelectric devices in sequence, a closed-loop circuit can be formed to output current and realize the effective conversion of mechanical energy into electrical energy; compared with traditional ion piezoelectric materials, it also has the advantages of simple culture conditions, large biomass, renewable and biodegradable; the preparation method of the leather ion piezoelectric device provided by the present invention is to obtain ion leather by tanning, retanning and electrolyte treatment of raw hides after acid immersion; the ion leather is cut and made into a device body; finally, the force electrode and the reference electrode are respectively attached to the two ends below the device body to complete the preparation of the leather ion piezoelectric device; the raw materials of the preparation method of the present invention are cheap and easy to obtain, the preparation cost is low, The process is simple and can be mass-produced. The prepared ion piezoelectric device has good mechanical properties and temperature durability, is suitable for mechanical energy collection and power generation in more complex special environments and actual scenarios with greater pressure, and has a wide range of applications. The ion piezoelectric generator provided by the present invention adopts a leather ion piezoelectric device as a core power generation unit, and the generator can effectively convert external mechanical energy (such as pressure, vibration, etc.) into electrical energy. The leather material not only has good flexibility and durability, but also due to its unique ion transmission characteristics, it can significantly promote ion migration when under pressure, thereby achieving efficient piezoelectric effect. The preparation method of the ion piezoelectric generator provided by the present invention significantly enhances the output voltage of the generator by connecting the force electrodes and reference electrodes of several leather ion piezoelectric devices in series through a voltage regulator. The series connection can accumulate the voltage generated by each device, thereby improving the stability and efficiency of the overall power output, and meeting more electronic devices or systems with higher voltage requirements. The application of a leather ion piezoelectric device provided by the present invention in assembling an ion piezoelectric generator is intended to collect unused mechanical energy of the human body or machine for power generation, and has the advantages of small size, light weight, easy to carry and low cost.

[0004] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0005] A method for preparing a leather ion piezoelectric device comprises the following steps:

[0006] (1) subjecting the pickled raw hide to tanning, retanning and electrolyte treatment to obtain ionic leather;

[0007] (2) Cutting the ion leather to make a device body;

[0008] (3) attaching the force-bearing electrode and the reference electrode to the two sides of the bottom of the device body respectively to obtain a leather ion piezoelectric device;

[0009] Furthermore, the step 1 is specifically as follows:

[0010] (1-1) placing the pickled hide into a salt and water system, adding alkali and rotating the system to adjust the pH value, thereby forming a first mixed system;

[0011] (1-2) adding tannin extract to the first mixed system in two portions to form a second mixed system, and continuing to rotate;

[0012] (1-3) After the tannin extract has fully penetrated into the leather, acid is added to the second mixed system in four equal portions, and the pH value is adjusted again to form a third mixed system, followed by liquid expansion, temperature increase, continued rotation, stopping the drum, and standing to obtain vegetable tanned leather;

[0013] (1-4) taking out the vegetable tanned leather, washing it and then putting it into a system of aldehyde tanning agent and water to form a fourth mixed system, heating it, and continuously rotating it to obtain the vegetable-aldehyde tanned leather;

[0014] (1-5) taking out the vegetable-aldehyde tanned leather, washing it again, and then putting it into an electrolyte and water system and rotating it to form a fifth mixed system. After the ions fully penetrate the leather, taking it out of the drum to obtain the ion leather;

[0015] Furthermore, the mass ratio of raw hide, salt, water, alkali, tannin and acid in (1-1) to (1-3) is (100-200):(8-16):(100-200):(1-2):(20-40):(0.5-1); the mass ratio of aldehyde tanning agent and water in (1-4) is (5-10):(100-200); the mass ratio of electrolyte and water in (1-5) is (20-40):(100-200);

[0016] Further, the salt in (1-1) is NaCl, Na2SO4 or NaNO3; the alkali in (1-1) is Na2CO3 or NaHCO3; the rotation in (1-1) is specifically: rotating at 20-25°C for 0.5-1h; the pH value in (1-1) is adjusted to 4.5; the tannin extract in (1-2) is balsam pear, quebracho, larch, emblica, bayberry, oak, acacia mangium or tara; the tannin extract in (1-2) is added twice, with an interval of 1h; the continued rotation in (1-2) is specifically: continuing to rotate at 20-25°C for 2-3h;

[0017] Furthermore, the acid in (1-3) is HCOOH, CH3COOH or H2SO4; the acid is added in (1-3) in four equal portions, with an interval of 15 minutes between each addition; the pH value is adjusted to 3.5 again in (1-3); the rotation time in (1-3) is 2 to 3 hours; the liquid ratio of the expansion liquid in (1-3) is 200%; the temperature of the heating in (1-3) is 40 to 45°C; the standing time in (1-3) is 12 hours; the aldehyde tanning agent in (1-4) is CH2O, C5H8O2 or modified C5H8O2; the rotation time in (1-4) is 3 to 4 hours; the temperature of the heating in (1-4) is 40 to 45°C;

[0018] Furthermore, the electrolyte in (1-5) is an ionic liquid, an acid, a base, a strong electrolyte salt or a weak electrolyte salt; the ionic liquid is BMIM:Cl, EMIM:BF4 or EMIM:DCA; the acid is HCl, H2SO4 or HNO3; the base is NaOH or KOH; the strong electrolyte salt is LiCl, NaCl, KCl, Na2SO4, NaNO3 or NaTFSI; the weak electrolyte salt is HCOONa, CH3COONa, Na3C6H5O7, NaKC4H4O6, Na2CO3 or NaHCO3; the rotation in (1-5) is specifically: rotating at 20-25°C for 2-3h;

[0019] A leather ion piezoelectric device is obtained based on the above-mentioned method for preparing a leather ion piezoelectric device, comprising a device body, wherein a force electrode and a reference electrode are respectively installed on both sides of the bottom of the device body.

[0020] A method for preparing an ion piezoelectric generator, based on the above-mentioned leather ion piezoelectric device, comprises the following steps:

[0021] (1) connecting the force electrodes and reference electrodes of several leather ion piezoelectric devices in series in sequence;

[0022] (2) An asymmetric pressure plate is installed on the top of several leather ion piezoelectric devices connected in series, and then a flexible packaging film is used to encapsulate them, thereby obtaining an ion piezoelectric generator integrated by several leather ion piezoelectric devices.

[0023] An ion piezoelectric generator is obtained based on the above-mentioned preparation method of an ion piezoelectric generator, including a flexible packaging film, a plurality of leather ion piezoelectric devices are arranged inside the flexible packaging film, and an asymmetric pressure plate is installed on the upper part of the plurality of leather ion piezoelectric devices; the force electrodes and reference electrodes of the plurality of leather ion piezoelectric devices are connected in series through a voltage regulator.

[0024] An application of the leather ion piezoelectric device described above in assembling an ion piezoelectric generator is used to collect unused mechanical energy of the human body or a machine to generate electricity.

[0025] The above technical solution has the following advantages or beneficial effects:

[0026] The invention provides a method for preparing a leather ion piezoelectric device. The raw hide after acid immersion is tanned, and the tanning makes the leather stable and durable. The tanning agent can combine with collagen fibers in the leather to form a stable cross-linked structure. The structure and performance of the leather can be further strengthened on the basis of tanning through retanning. In order to give the leather ion conductivity, electrolyte treatment is required. By introducing an electrolyte solution, the interior of the leather is filled with freely movable ions, so that a potential difference can be generated when pressure is applied. The ion leather after the electrolyte treatment is cut into a device body of appropriate size and shape, and the flatness and dimensional accuracy of the leather are ensured during the cutting process to meet the requirements of subsequent electrode attachment.

[0027] Furthermore, after the acid-soaked raw hides are tanned with tannin extract and aldehyde tanning agent, tannin extract forms multi-point hydrogen bonds with carboxyl, amino and hydroxyl groups on the hide collagen fibers, while aldehyde tanning agent reacts with amino groups on the hide collagen fibers to form Schiff base reaction, significantly enhancing the electronegativity of the hide collagen fibers. The tanned leather has excellent mechanical properties, moisture and heat stability, durability and corrosion resistance, and is easy to transport, store and reuse. After the electrolyte solution is introduced, the multi-pore size and multi-level structure of the leather collagen fibers provide a good channel for the rapid movement of ions. When the leather material is subjected to external pressure and produces non-uniform mechanical deformation, the ions will diffuse rapidly from the deformed area to the undeformed area. Due to the presence of a large number of electronegative functional groups (such as carboxyl and hydroxyl groups) in the plant-aldehyde combined tanned leather, cations and anions will produce a brief charge separation during the diffusion process, thereby generating a potential difference between the deformed area and the undeformed area.

[0028] Furthermore, the dosage ratio of raw hides, salt, water, alkali, tannin and acid has been carefully designed to ensure the uniformity and consistency of the leather during tanning, retanning and electrolyte treatment; the uniformity not only improves the mechanical strength of the leather, but also ensures the uniformity of its internal ion distribution, thereby improving the stability of the ionic leather in the piezoelectric effect; the dosage ratio of aldehyde tanning agent to water is properly controlled, which helps to form a stable cross-linked structure in the leather while maintaining the softness and elasticity of the leather. In this process, the aldehyde tanning agent also promotes the formation of ion channels inside the leather, allowing ions to move more smoothly when under pressure, thereby improving the ionic conductivity of the leather; after the dosage ratio of electrolyte to water is optimized, the electrolyte is more evenly distributed in the leather and the concentration is moderate, so that when under pressure, the ions inside the leather can migrate and redistribute more effectively, thereby generating a stronger potential difference and higher piezoelectric output.

[0029] Furthermore, using NaCl, Na2SO4 or NaNO3 as the salt in (1-1) has good solubility and permeability in leather processing, which helps to remove impurities in raw hides and promote the subsequent tanning process; selecting Na2CO3 or NaHCO3 as the base in (1-1) can not only effectively neutralize the acidic substances in raw hides, but also promote the expansion and softening of leather, creating favorable conditions for subsequent tanning; rotating at 20-25°C for 0.5-1h is conducive to maintaining the activity of the enzyme and the smooth progress of the chemical reaction, avoiding the adverse effects of high or low temperature on the quality of leather; adjusting the pH value to 4.5, this pH The value is conducive to the combination of metal ions and leather collagen fibers during the tanning process to form a stable cross-linked structure; natural plant tannins such as wattle, quercetin, larch, emblica, bayberry, oak, acacia mangium or tara are selected as the tanning agent in (1-2), which is not only environmentally friendly but also rich in tannins, and can closely combine with the collagen fibers in the leather to improve the shrinkage temperature and moisture and heat resistance of the leather; adding tannins in two times with an interval of 1 hour is conducive to the uniform distribution and full penetration of tannins in the leather, thereby improving the tanning effect; continuing to rotate at 20-25°C for 2-3 hours ensures the full reaction and combination of tannins and leather, further consolidating the structure and performance of the leather.

[0030] Furthermore, HCOOH, CH3COOH or H2SO4 is selected as the acid in (1-3) to adjust the pH value to 3.5, which can more effectively remove impurities and loosen collagen fibers in the leather, creating better conditions for subsequent treatment; the acid is added in four times, each time with an interval of 15 minutes. The step-by-step acid addition method helps the acid to be evenly distributed and fully penetrated in the leather, avoiding the local over-acidification caused by adding too much acid at one time; the liquid ratio of the expansion liquid is set to 200%, which helps to increase the contact area between the leather and the acid or subsequent treatment liquid, thereby improving the treatment effect; the temperature is increased The temperature of 40-45°C promotes the dissolution and diffusion of the internal substances of the leather, while avoiding the damage of high temperature to the leather; the long-term static process allows the internal substances of the leather to fully react and precipitate, further improving the quality and stability of the leather; CH2O, C5H8O2 or modified C5H8O2 is selected as the aldehyde tanning agent in (1-4), and the aldehyde tanning agent can cross-link with the collagen fibers in the leather to form a stable structure; the continuous rotation time is 3-4 hours and the temperature is raised at 40-45°C, which ensures the full contact and reaction between the aldehyde tanning agent and the leather, and improves the aldehyde tanning effect. After the above optimization treatment, the internal structure of the leather is denser and the ion channels are more unobstructed. In the subsequent electrolyte treatment process, the electrolyte can more easily penetrate into the leather and be evenly distributed, thereby improving the ionic conductivity of the leather.

[0031] Furthermore, the wide range of electrolyte selection allows the preparation process to adjust the type and concentration of electrolytes according to specific needs, thereby optimizing the ionic conductivity, mechanical strength and piezoelectric effect of the leather. Specific ionic liquids and other electrolytes have good permeability and solubility, and can more easily penetrate into the leather and interact with the collagen fibers in the leather, which helps to form a more uniform and stable ion distribution network inside the leather, and improve the migration efficiency and piezoelectric output performance of ions under pressure; rotating at 20-25°C for 2-3h is conducive to the uniform distribution and full penetration of electrolytes in the leather, while also avoiding potential damage to the leather by high temperature, ensuring the safety and controllability of the processing process.

[0032] The present invention also provides a leather ion piezoelectric device, the device body is made of leather material, the leather has a three-dimensional porous structure, and is composed of multiple layers of collagen fiber bundles, which provides a large number of excellent aperture channels for the movement of ions; the force electrode is installed on one side of the bottom of the device body, for receiving the external pressure signal and converting it into an electrical signal, when the external pressure acts on the device body, the ion distribution inside the leather will change, thereby generating an electric potential difference, and then generating an electrical signal on the force electrode; the reference electrode is installed on the other side of the bottom of the device body, but is not directly connected to the force electrode, and can provide a stable reference potential for comparison and measurement with the electrical signal generated on the force electrode; the leather ion piezoelectric device of the present invention can have a high sensitivity to changes in external pressure, and has excellent mechanical properties, moisture and heat stability, durability and corrosion resistance, and is easy to transport, store and reuse. At the same time, the rapid movement of ions enables the device to respond quickly to external pressure signals and realize real-time monitoring and measurement.

[0033] The present invention also provides a method for preparing an ion piezoelectric generator with clear steps and easy operation. By connecting the force-bearing electrodes and reference electrodes of several leather ion piezoelectric devices in series in sequence, installing an asymmetric pressure plate on the upper part, and finally encapsulating it with a flexible packaging film, a complete ion piezoelectric generator can be obtained, which simplifies the preparation process and improves production efficiency. By integrating multiple leather ion piezoelectric devices in series, the integration of the generator is significantly improved, which not only makes the generator more compact in size, but also can provide more piezoelectric conversion units in the same volume, thereby improving the overall output power and energy conversion efficiency of the generator.

[0034] The present invention also provides an ion piezoelectric generator, which can more effectively capture and convert external mechanical energy into electrical energy by integrating several leather ion piezoelectric devices inside a flexible packaging film; the unique piezoelectric effect and ionic conductivity of the leather ion piezoelectric device enable this generator to generate significant voltage and current output when subjected to pressure from an asymmetric pressure plate; the flexible packaging film provides good protection for the internal leather ion piezoelectric device, preventing damage to the device by external environmental factors (such as humidity, dust, impact, etc.); by connecting the force electrodes and reference electrodes of several leather ion piezoelectric devices in series through a voltage regulator, the overall output voltage of the generator can be further improved, so that the voltages generated by multiple piezoelectric devices can be superimposed on each other, thereby improving the energy collection efficiency of the generator.

[0035] The present invention also provides an application of a leather ion piezoelectric device in assembling an ion piezoelectric generator, which can efficiently recycle and reuse the mechanical energy originally wasted by human or machine movement, and convert it into electrical energy through the leather ion piezoelectric device, thereby realizing effective energy recovery and utilization and improving energy utilization efficiency; the device is installed in the insole interlayer, and generates electricity using the pressure generated by human walking, and can also monitor the human body's movement status in real time. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is a schematic flow chart of a method for preparing a leather ion piezoelectric device according to the present invention;

[0037] Figure 2 It is a structural schematic diagram of an ion piezoelectric generator of the present invention;

[0038] Figure 3 It is a schematic flow chart of a method for preparing an ion piezoelectric generator of the present invention;

[0039] Figure 4 This is a schematic diagram of a leather ion piezoelectric device of the present invention;

[0040] In the figure, 1-device body; 2-force-bearing electrode; 3-reference electrode; 4-asymmetric pressure plate; 5-flexible packaging film. DETAILED DESCRIPTION

[0041] The present invention is further described in detail below in conjunction with specific embodiments, which are intended to explain the present invention rather than to limit it.

[0042] In order to enable those skilled in the art to better understand the scheme of the present invention, the technical scheme 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 part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0043] It should be noted that the terms "first", "second", etc. in the specification and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the data used in this way can be interchanged where appropriate, so that the embodiments of the present invention described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units that are clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.

[0044] Embodiment 1:

[0045] like Figure 2 As shown, the present invention provides a leather ion piezoelectric device, including a device body 1, and a force electrode 2 and a reference electrode 3 are respectively installed on both sides of the bottom of the device body 1.

[0046] The present invention also provides an ion piezoelectric generator, which is an integrated device based on the above-mentioned leather ion piezoelectric device, including a flexible packaging film 5, a plurality of leather ion piezoelectric devices are arranged inside the flexible packaging film 5, an asymmetric pressure plate 4 is installed on the upper part of the plurality of leather ion piezoelectric devices, and the force electrodes 2 and reference electrodes 3 of the plurality of leather ion piezoelectric devices are connected in series through a voltage regulator.

[0047] The present invention also provides an application of a leather ion piezoelectric device in assembling an ion piezoelectric generator, which is based on the above-mentioned leather ion piezoelectric device and is used to collect unused mechanical energy of the human body or machines to generate electricity.

[0048] Embodiment 2:

[0049] like Figure 2 As shown, the present invention provides a leather ion piezoelectric device, comprising a device body 1, and a force electrode 2 and a reference electrode 3 are respectively installed on both sides of the bottom of the device body 1;

[0050] Preferably, the material of the device body 1 is leather that has been tanned with tannin extract and aldehyde tanning agent and then introduced with electrolyte solution;

[0051] Preferably, the device body 1 is a planar structure;

[0052] Preferably, the material of the force-bearing electrode 2 and the reference electrode 3 is gold, silver, platinum, titanium, copper, iron, aluminum or carbon fiber cloth.

[0053] The present invention also provides an ion piezoelectric generator, which is an integrated device based on the above-mentioned leather ion piezoelectric device, comprising a flexible packaging film 5, a plurality of leather ion piezoelectric devices are arranged inside the flexible packaging film 5, an asymmetric pressure plate 4 is installed on the upper part of the plurality of leather ion piezoelectric devices, and the force electrodes 2 and reference electrodes 3 of the plurality of leather ion piezoelectric devices are connected in series through a voltage device;

[0054] Preferably, the number of leather ion piezoelectric devices is 10 to 100;

[0055] Preferably, the material of the asymmetric pressure plate 4 is polyvinyl chloride, polytetrafluoroethylene, polypropylene, polymethyl methacrylate, polyurethane or polycarbonate;

[0056] Preferably, the material of the flexible packaging film 5 is polyethylene, polypropylene, polyurethane or polydimethylsiloxane.

[0057] The present invention also provides an application of a leather ion piezoelectric device in assembling an ion piezoelectric generator, which is based on the above-mentioned leather ion piezoelectric device and is used to collect unused mechanical energy of the human body or machines to generate electricity.

[0058] Embodiment 3:

[0059] like Figure 1 As shown, the present invention provides a method for preparing a leather ion piezoelectric device, based on the above-mentioned leather ion piezoelectric device, comprising the following steps:

[0060] (1) subjecting the pickled raw hide to tanning, retanning and electrolyte treatment to obtain ionic leather;

[0061] The tanning process is as follows: putting the pickled raw hide into a drum of salt and water, adding alkali, rotating at 20-25°C for 0.5-1h, adjusting the pH value to 4.5, and forming a first mixed system; adding tannin extract to the first mixed system twice to form a second mixed system, and continuing to rotate at 20-25°C for 2-3h; after the tannin extract fully penetrates the skin, adding acid to the second mixed system four times on average, adjusting the pH value to 3.5 again, and forming a third mixed system, and then expanding the liquid with a liquid ratio of 200%, heating to 40-45°C, and continuing to rotate for 2-3h, stopping the drum, and standing for 12h to obtain vegetable tanned leather;

[0062] Preferably, the rawhide is cowhide, sheepskin or pigskin;

[0063] Preferably, the salt is NaCl, Na2SO4 or NaNO3;

[0064] Preferably, the base is Na2CO3 or NaHCO 3；

[0065] Preferably, the tannin extract is wattle, quebracho, larch, emblica, bayberry, oak bowl, acacia mangium or tara;

[0066] Preferably, tannin extract is added twice, with an interval of 1 hour;

[0067] Preferably, the acid is HCOOH, CH3COOH or H2SO4;

[0068] Preferably, the acid is added in four equal portions, each time interval being 15 minutes;

[0069] Preferably, the usage ratio of raw hide, salt, water, alkali, tannin extract and acid is (100-200):(8-16):(100-200):(1-2):(20-40):(0.5-1);

[0070] The retanning is specifically as follows: the vegetable tanned leather is fished out, washed with water, and then put into a rotating drum containing an aldehyde tanning agent and water to form a fourth mixed system, the temperature is raised to 40-45° C., and the system is continuously rotated for 3-4 hours to obtain the vegetable-aldehyde tanned leather;

[0071] Preferably, the aldehyde tanning agent is CH2O, C5H8O2 or modified C5H8O2;

[0072] Preferably, the dosage ratio of aldehyde tanning agent to water is (5-10):(100-200);

[0073] The electrolyte treatment is specifically as follows: the vegetable-aldehyde tanned leather is fished out, washed with water again, and then put into a drum containing electrolyte and water and rotated at 20-25° C. for 2-3 hours to form a fifth mixed system, and after the ions fully penetrate the interior of the leather, the leather is taken out of the drum to obtain the ion leather;

[0074] Preferably, the electrolyte is an ionic liquid, an acid, a base, a strong electrolyte salt or a weak electrolyte salt; the ionic liquid is BMIM:Cl, EMIM:BF4 or EMIM:DCA; the acid is HCl, H2SO4 or HNO3; the base is NaOH or KOH; the strong electrolyte salt is LiCl, NaCl, KCl, Na2SO4, NaNO3 or NaTFSI; the weak electrolyte salt is HCOONa, CH3COONa, Na3C6H5O7, NaKC4H4O6, Na2CO3 or NaHCO3;

[0075] Preferably, the ratio of electrolyte to water is (20-40):(100-200).

[0076] (2) Cutting the ion leather to form a device body 1;

[0077] Preferably, the ion leather is cut into a rectangle with a length of 20 mm and a width of 8 mm;

[0078] Preferably, the thickness of the device body 1 is 2 to 3 mm;

[0079] (3) The force-bearing electrode 2 and the reference electrode 3 are respectively attached to the two sides of the bottom of the device body 1 to obtain a leather ion piezoelectric device.

[0080] Embodiment 4:

[0081] like Figure 1 As shown, the present invention provides a method for preparing a leather ion piezoelectric device, based on the above-mentioned leather ion piezoelectric device, comprising the following steps:

[0082] (1) tanning, retanning and electrolyte treatment of pickled raw hide to obtain ion leather;

[0083] 200 parts of raw cattle hides soaked in acid were placed in a drum by weight, and 16 parts of NaCl, 2 parts of NaHCO3 and 200 parts of water were added. The drum was rotated at 25°C for 1 hour, and the pH value of the cattle hide was adjusted to 4.5 to form a first mixed system. 20 parts of emblica were added to the first mixed system, and 20 parts of emblica were added after an interval of 1 hour to form a second mixed system, which was further rotated at 25°C for 3 hours. After the emblica fully penetrated the skin, 1 part of HCOOH was added to the second mixed system in four times on average, with an interval of 15 minutes each time, and the pH value of the cattle hide was adjusted to 3.5 to form a third mixed system. Then, 200 parts of water are added and the temperature is increased to 45°C. After continuing to rotate for 2 hours, the drum is stopped and allowed to stand for 12 hours to obtain vegetable tanned leather; the vegetable tanned leather is fished out of the drum, washed with water and placed in the drum again, 10 parts of modified C5H8O2 and 200 parts of water are added to form a fourth mixed system, the temperature is increased to 45°C, and the drum is rotated for 4 hours to obtain vegetable-aldehyde tanned leather; the vegetable-aldehyde tanned leather is fished out of the drum, washed with water again and placed in the drum, 40 parts of strong electrolyte salt LiCl are added, and the drum is rotated at 25°C for 3 hours to form a fifth mixed system, and after the ions fully penetrate the leather, the leather is taken out of the drum to obtain ionic cowhide leather;

[0084] Preferably, the obtained ionic cowhide leather has a shrinkage temperature of 91.3°C, a compressive strength of 16.3 MPa at 60% strain, and an elongation at break of 89.2%;

[0085] (2) Taking 40 parts by mass of the obtained ion cowhide leather and cutting them into 40 rectangles with a length of 20 mm and a width of 8 mm, a device body 1 was obtained;

[0086] (3) attaching the force-bearing electrode 2 and the reference electrode 3 to the two sides of the bottom of the device body 1 respectively, and obtaining 40 leather ion piezoelectric devices;

[0087] Preferably, the material of the force-bearing electrode 2 and the reference electrode 3 is copper metal.

[0088] Embodiment 5:

[0089] like Figure 1 As shown, the present invention provides a method for preparing a leather ion piezoelectric device, based on the above-mentioned leather ion piezoelectric device, comprising the following steps:

[0090] (1) tanning, retanning and electrolyte treatment of pickled raw sheepskin to obtain ion leather;

[0091] In terms of mass, 100 parts of raw cattle hides soaked in acid were placed in a drum, 8 parts of NaCl and 1 part of NaHCO3, and 100 parts of water were added, and the drum was rotated at 25°C for 1 hour, and the pH value of the sheep hide was adjusted to 4.5 to form a first mixed system; 10 parts of bayberry were added to the first mixed system, and 10 parts of bayberry were added after an interval of 1 hour to form a second mixed system, and the drum was rotated at 25°C for 2 hours; after the bayberry fully penetrated the skin, 0.5 parts of HCOOH were added to the second mixed system in four times on average, with an interval of 15 minutes each time, and the pH value of the cattle hide was adjusted to 3.5 to form a third mixed system, Then, 100 parts of water were added and the temperature was increased to 45°C. After continuing to rotate for 2 hours, the drum was stopped and allowed to stand for 12 hours to obtain vegetable tanned leather; the vegetable tanned leather was fished out of the drum, washed with water and placed in the drum again, 5 parts of C5H8O2 and 100 parts of water were added to form a fourth mixed system, the temperature was increased to 45°C, and the drum was continuously rotated for 3 hours to obtain vegetable-aldehyde tanned leather; the vegetable-aldehyde tanned leather was fished out of the drum, washed with water again and placed in the drum, 20 parts of ionic liquid EMIM:DCA were added, and the leather was rotated at 25°C for 3 hours to form a fifth mixed system, and after the ions fully penetrated the leather, the leather was taken out of the drum to obtain ionic sheepskin leather;

[0092] Preferably, the obtained ionic sheepskin leather has a shrinkage temperature of 89.1°C, a compressive strength of 13.6MPa at 60% strain, and an elongation at break of 92.5%;

[0093] (2) Taking 30 parts by mass of the obtained ion sheepskin leather, cutting them into 30 rectangles with a length of 20 mm and a width of 8 mm, to obtain a device body 1;

[0094] (3) attaching the force-bearing electrode 2 and the reference electrode 3 to the two sides of the bottom of the device body 1 respectively, and obtaining 30 leather ion piezoelectric devices;

[0095] Preferably, the material of the force-bearing electrode 2 and the reference electrode 3 is silver metal.

[0096] Embodiment 6:

[0097] like Figure 1 As shown, the present invention provides a method for preparing a leather ion piezoelectric device, based on the above-mentioned leather ion piezoelectric device, comprising the following steps:

[0098] (1) subjecting the pickled pigskin to tanning, retanning and electrolyte treatment to obtain ion leather;

[0099] In terms of mass, 100 parts of pickled pig skins were placed in a drum, 8 parts of NaCl and 1 part of NaHCO3, and 100 parts of water were added, and the drum was rotated at 20°C for 0.5h, and the pH value of the pig skin was adjusted to 4.5 to form a first mixed system; 10 parts of quercetin were added to the first mixed system, and 10 parts of quercetin were added after an interval of 1h to form a second mixed system, and the drum was rotated at 20°C for 3h; after the quercetin fully penetrated the skin, 0.5 parts of HCOOH were added to the second mixed system in four equal portions, each time with an interval of 15min, and the pH value of the pig skin was adjusted to 3.5 to form a third mixed system system, then add 100 parts of water and raise the temperature to 40°C, continue to rotate for 3 hours, stop the drum, and let it stand for 12 hours to obtain vegetable tanned leather; the vegetable tanned leather is fished out of the drum, washed with water and placed in the drum again, 5 parts of C5H8O2 and 100 parts of water are added to form a fourth mixed system, the temperature is raised to 40°C, and the drum is rotated for 3 hours to obtain vegetable-aldehyde tanned leather; the vegetable-aldehyde tanned leather is fished out of the drum, washed with water again and placed in the drum, 20 parts of weak electrolyte salt HCOONa are added, and the leather is rotated at 20°C for 2 hours to form a fifth mixed system, and after the ions fully penetrate the leather, the leather is taken out of the drum to obtain ionic pig leather;

[0100] (2) Taking 30 parts by mass of the obtained ion pig leather, cutting them into 30 rectangles with a length of 20 mm and a width of 8 mm, to obtain a device body 1;

[0101] (3) attaching the force-bearing electrode 2 and the reference electrode 3 to the two sides of the bottom of the device body 1 respectively, and obtaining 30 leather ion piezoelectric devices;

[0102] Preferably, the material of the force-bearing electrode 2 and the reference electrode 3 is aluminum metal.

[0103] Embodiment 7:

[0104] like Figure 2 As shown, the present invention provides an ion piezoelectric generator, based on the above-mentioned leather ion piezoelectric device, including a flexible packaging film 5, a plurality of leather ion piezoelectric devices are arranged inside the flexible packaging film 5, and an asymmetric pressure plate 4 is installed on the upper part of the plurality of leather ion piezoelectric devices; the force electrodes 2 and the reference electrodes 3 of the plurality of leather ion piezoelectric devices are connected in series through a voltage device;

[0105] Preferably, the ion piezoelectric generator has a planar structure.

[0106] Embodiment 8:

[0107] like Figure 3 As shown, the present invention provides a method for preparing an ion piezoelectric generator, based on the above-mentioned ion piezoelectric generator, comprising the following steps:

[0108] (1) connecting the force electrodes 2 and the reference electrodes 3 of several leather ion piezoelectric devices in series in sequence;

[0109] (2) An asymmetric pressure plate 4 is installed on the upper part of a plurality of leather ion piezoelectric devices connected in series, and then a flexible packaging film 5 is used for packaging to obtain an ion piezoelectric generator integrated with a plurality of leather ion piezoelectric devices;

[0110] Preferably, the number of leather ion piezoelectric devices is 10 to 100;

[0111] The present invention also provides an application of a leather ion piezoelectric device in assembling an ion piezoelectric generator, which is used to collect unused mechanical energy of the human body or a machine to generate electricity.

[0112] Embodiment 9:

[0113] like Figure 3 As shown, the present invention provides a method for preparing an ion piezoelectric generator, based on the above-mentioned ion piezoelectric generator, comprising the following steps:

[0114] (1) Take 40 leather ion piezoelectric devices obtained in Example 4, and connect the force-bearing electrodes 2 and the reference electrodes 3 of the 40 leather ion piezoelectric devices in series in sequence;

[0115] (2) An asymmetric pressure plate 4 is installed on the top of 40 leather ion piezoelectric devices connected in series, and then a flexible packaging film 5 is used for packaging to obtain an ion piezoelectric generator with a planar structure integrated by 40 leather ion piezoelectric devices.

[0116] The present invention also provides an application of a leather ion piezoelectric device in assembling an ion piezoelectric generator, which is used to collect unused mechanical energy of the human body or a machine to generate electricity.

[0117] When the planar-structured ion piezoelectric generator obtained by Example 9 of the present invention collects unused mechanical energy of the human body to generate electricity, the device is installed in the insole interlayer to generate electricity using the pressure generated by human walking. The movement state of the human body can also be monitored in real time. The force-bearing electrode 2 and the reference electrode 3 are respectively connected to wires and an external voltmeter to measure the voltage across the electrodes to be 3.6V, which can light up the LED lamp.

[0118] Embodiment 10:

[0119] like Figure 3 As shown, the present invention provides a method for preparing an ion piezoelectric generator, based on the above-mentioned ion piezoelectric generator, comprising the following steps:

[0120] (1) Take 30 leather ion piezoelectric devices obtained in Example 5, and connect the force-bearing electrodes 2 and the reference electrodes 3 of the 30 leather ion piezoelectric devices in series in sequence;

[0121] (2) An asymmetric pressure plate 4 is installed on the top of the 30 leather ion piezoelectric devices connected in series, and then a flexible packaging film 5 is used to encapsulate them, thereby obtaining an ion piezoelectric generator with a planar structure integrated by 30 leather ion piezoelectric devices.

[0122] The present invention also provides an application of a leather ion piezoelectric device in assembling an ion piezoelectric generator, which is used to collect unused mechanical energy of the human body or a machine to generate electricity.

[0123] When the planar-structured ion piezoelectric generator obtained by Example 10 of the present invention collects unused mechanical energy of the human body to generate electricity, the device is installed in the insole interlayer to generate electricity using the pressure generated by human walking. The movement state of the human body can also be monitored in real time. The force electrode 2 and the reference electrode 3 are respectively connected to wires and an external voltmeter to measure the voltage across the electrodes to be 3.6V, which can light up the LED lamp.

[0124] The structure and working principle of the present invention are further described below:

[0125] like Figure 4 As shown, the purpose of the present invention is to provide a leather ion piezoelectric device. When the device is used, when the device body 1 is free of external pressure, the cations and anions in the material are evenly distributed; when the device body 1 is subjected to non-uniform mechanical deformation due to external pressure, the ions will rapidly diffuse from the deformed area to the undeformed area. Due to the presence of a large number of electronegative functional groups (such as carboxyl and hydroxyl) in the plant-aldehyde combined tanned leather, the cations and anions will produce a short-term charge separation during the diffusion process, so that the device body 1 generates a potential difference between the deformed area and the undeformed area; at this time, a closed-loop circuit can be formed by connecting the force-bearing electrode 2 and the reference electrode 3 attached to the two ends below the device body 1 to output current and realize the effective conversion of mechanical energy into electrical energy.

[0126] The purpose of the present invention is also to provide an ion piezoelectric generator, in which the force electrodes 2 and the reference electrodes 3 on both sides of the bottom of 10 to 100 leather ion piezoelectric devices 1 are connected in series in sequence, and then an asymmetric pressure plate 4 is installed above the 10 to 100 leather ion piezoelectric devices, and then a flexible film 5 is used for packaging to assemble them into an ion piezoelectric generator for collecting and generating mechanical energy from the human body and machines. The device is installed in the insole interlayer, and generates electricity using the pressure generated by human walking. It can also monitor the movement status of the human body in real time. The force electrode 2 and the reference electrode 3 are respectively connected to wires and an external voltmeter is used to measure the voltage across the electrodes to be 3.6V, which can light up the LED lamp.

[0127] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a leather ion piezoelectric device, characterized in that: The following steps are involved: S1, tanning, retanning and electrolyte treatment of the pickled raw hide to obtain ionic leather; S2, cutting the ion leather to form a device body (1); S3, attaching the force-bearing electrode (2) and the reference electrode (3) to the two sides of the bottom of the device body (1) respectively, to obtain a leather ion piezoelectric device.

2. The method for preparing a leather ion piezoelectric device according to claim 1, characterized in that: The S1 is specifically: S1-1, putting the pickled hide into a salt and water system, adding alkali and rotating, adjusting the pH value, and forming a first mixed system; S1-2, adding tannin extract to the first mixed system twice to form a second mixed system, and continuing to rotate; S1-3, after the tannin extract has fully penetrated into the leather, acid is added to the second mixed system in four equal portions, the pH value is adjusted again to form a third mixed system, and then the liquid is expanded, the temperature is increased, the drum is continuously rotated, the drum is stopped, and the drum is allowed to stand to obtain vegetable tanned leather; S1-4, taking out the vegetable tanned leather, washing it and putting it into a system of aldehyde tanning agent and water to form a fourth mixed system, heating it, and continuously rotating it to obtain the vegetable-aldehyde tanned leather; S1-5, the vegetable-aldehyde tanned leather is fished out, washed again and put into an electrolyte and water system and rotated to form a fifth mixed system, and after the ions fully penetrate the interior of the leather, the leather is taken out of the drum to obtain the ion leather.

3. The method for preparing a leather ion piezoelectric device according to claim 2, characterized in that: The mass ratio of raw hide, salt, water, alkali, tannin and acid in S1-1 to S1-3 is (100-200):(8-16):(100-200):(1-2):(20-40):(0.5-1); the mass ratio of aldehyde tanning agent and water in S1-4 is (5-10):(100-200); the mass ratio of electrolyte and water in S1-5 is (20-40):(100-200).

4. The method for preparing a leather ion piezoelectric device according to claim 2, characterized in that: The salt in S1-1 is NaCl, Na2SO4 or NaNO3; the alkali in S1-1 is Na2CO3 or NaHCO3; the rotation in S1-1 is specifically: rotating at 20-25°C for 0.5-1h; the pH value in S1-1 is adjusted to 4.5; the tannin extract in S1-2 is balsam pear, quebracho, larch, emblica, bayberry, oak, acacia mangium or tara; tannin extract is added to S1-2 twice with an interval of 1h; the continued rotation in S1-2 is specifically: continuing to rotate at 20-25°C for 2-3h.

5. The method for preparing a leather ion piezoelectric device according to claim 2, characterized in that: The acid in S1-3 is HCOOH, CH3COOH or H2SO4; the acid is added in S1-3 in four times on average, with an interval of 15 minutes each time; the pH value in S1-3 is adjusted to 3.5 again; the rotation time in S1-3 is 2 to 3 hours; the liquid ratio of the expansion liquid in S1-3 is 200%; the heating temperature in S1-3 is 40 to 45°C; the standing time in S1-3 is 12 hours; the aldehyde tanning agent in S1-4 is CH2O, C5H8O2 or modified C5H8O2; the rotation time in S1-4 is 3 to 4 hours; the heating temperature in S1-4 is 40 to 45°C.

6. The method for preparing a leather ion piezoelectric device according to claim 2, characterized in that: The electrolyte in S1-5 is an ionic liquid, an acid, a base, a strong electrolyte salt or a weak electrolyte salt; the ionic liquid is BMIM:Cl, EMIM:BF4 or EMIM:DCA; the acid is HCl, H2SO4 or HNO3; the base is NaOH or KOH; the strong electrolyte salt is LiCl, NaCl, KCl, Na2SO4, NaNO3 or NaTFSI; the weak electrolyte salt is HCOONa, CH3COONa, Na3C6H5O7, NaKC4H4O6, Na2CO3 or NaHCO3; the rotation in S1-5 is specifically: rotating at 20-25°C for 2-3h.

7. A leather ion piezoelectric device, obtained based on the preparation method of a leather ion piezoelectric device according to claim 1, characterized in that: The device comprises a device body (1), wherein a force-bearing electrode (2) and a reference electrode (3) are respectively installed on both sides of the bottom of the device body (1).

8. A method for preparing an ionic piezoelectric generator, based on the leather ionic piezoelectric device according to claim 7, characterized in that: The following steps are involved: S1, connecting the force electrodes (2) and the reference electrodes (3) of a plurality of leather ion piezoelectric devices in series in sequence; S2, installing an asymmetric pressure plate (4) on the upper part of a plurality of leather ion piezoelectric devices connected in series, and then using a flexible packaging film (5) to package them, thereby obtaining an ion piezoelectric generator integrated by a plurality of leather ion piezoelectric devices.

9. An ion piezoelectric generator, obtained based on the preparation method of an ion piezoelectric generator according to claim 8, characterized in that: The invention comprises a flexible packaging film (5), wherein a plurality of leather ion piezoelectric devices are arranged inside the flexible packaging film (5), and an asymmetric pressure plate (4) is installed on the upper part of the plurality of leather ion piezoelectric devices; the force electrodes (2) and the reference electrodes (3) of the plurality of leather ion piezoelectric devices are connected in series via a voltage regulator.

10. An application of a leather ion piezoelectric device according to claim 7 in assembling an ion piezoelectric generator, characterized in that: Used to collect unused mechanical energy from the human body or machines to generate electricity.

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