Stretchable solid-state ion electrodes, triboelectric nanogenerators and their applications

Abstract

This invention provides a stretchable solid-state ion electrode, a triboelectric nanogenerator, and their applications. The stretchable solid-state ion electrode is fabricated from an ion conductor and a stretchable polymer material. The ion conductor comprises a polymer and a salt in a mass ratio of 1:19 to 1:4, wherein the polymer is selected from a first compound as shown in general formula I and / or a second compound as shown in general formula II. In this invention, the ion conductor and the stretchable polymer material in the stretchable solid-state ion electrode are cross-linked through hydrogen bonds and electrostatic forces, effectively improving the stretchability and conductivity of the composite solid-state ion electrode, thereby further enhancing the lifespan and power output performance of the triboelectric nanogenerator during energy harvesting.

Description

Technical Field

[0001] This invention relates to the field of triboelectric nanogenerator technology, specifically to a stretchable solid-state ion electrode, a triboelectric nanogenerator, and their applications. Background Technology

[0002] Triboelectric nanogenerators are energy harvesting devices that effectively convert mechanical energy into electrical energy through the coupling of triboelectric effect and electrostatic induction. A triboelectric nanogenerator consists of a triboelectric layer and electrodes. When positive and negative triboelectric materials come into contact, electrons transfer from the surface of the positive triboelectric material to the surface of the negative triboelectric material. When they separate, positive charges remain on the surface of the positive triboelectric material, and negative charges remain on the surface of the negative triboelectric material; simultaneously, due to electrostatic induction, a potential difference appears between the positive and negative electrodes. Due to its simple structure, low cost, safety, and high electrical output, stretchable triboelectric nanogenerators have significant potential applications in wearable devices, effectively harvesting mechanical energy generated by human movement (such as the bending of fingers, wrists, and elbows).

[0003] Currently, researchers are focusing on hydrogels to develop stretchable electrodes. Although hydrogels possess excellent stretchability and conductivity, hydrogel-based triboelectric nanogenerators face the risk of moisture evaporation and leakage, limiting device lifespan. Furthermore, the adhesion between the hydrogel and the friction layer is poor, leading to easy separation of the electrode and friction material after repeated stretching, resulting in device deformation. Currently, there are no stretchable, safe, wearable power devices on the market for collecting human motion data. Summary of the Invention

[0004] To address the aforementioned technical problems, the present invention aims to provide a stretchable solid-state ion electrode, a triboelectric nanogenerator, and their applications. The solid-state ion electrode exhibits excellent conductivity and stretchability, and the triboelectric nanogenerator fabricated based on this solid-state ion electrode possesses high output efficiency and broad application potential.

[0005] To achieve the above objectives, the present invention provides a stretchable solid-state ion electrode, which is prepared from an ion conductor and a stretchable polymer material; the ion conductor comprises a polymer and a salt in a mass ratio of 1:19 to 1:4, wherein the polymer is selected from a first compound as shown in general formula I and / or a second compound as shown in general formula II.

[0006]

[0007] R1 and R3 are independently selected from hydrogen atom, hydroxyl group, carboxyl group, mercapto group, amino group or N,N'-bis-[(3-triethoxysilylpropyl)aminocarbonyl] group, R2 is selected from C1-C10 alkyl or C1-C10 alkoxy, and m is selected from 10 to 5 × 105 Positive integers;

[0008]

[0009] Wherein, R4, R6, and R7 are independently selected from hydrogen atom, hydroxyl, mercapto, or amino atom, R5 is selected from C1-C10 alkyl or C1-C10 alkoxy, and n is selected from 10 4 Up to 10 7 Positive integers.

[0010] According to a specific embodiment of the present invention, in the above-mentioned stretchable solid ion electrode, preferably, R2 and R5 are each independently selected from C1-C5 alkyl or C1-C5 alkoxy.

[0011] According to a specific embodiment of the present invention, in the above-mentioned stretchable solid-state ion electrode, preferably, the first compound is selected from polyethylene oxide, polyethylene propylene oxide, polyethylene propylene oxide, amino polyethylene oxide, mercapto polyethylene oxide, or N,N'-bis-[(3-triethoxysilylpropyl)aminocarbonyl] polyethylene oxide (CAS: 178884-91-8), more preferably polyethylene oxide.

[0012] According to a specific embodiment of the present invention, in the above-described stretchable solid-state ion electrode, preferably, the molecular weight of the first compound is 10. 3 -10 7 .

[0013] According to a specific embodiment of the present invention, in the above-mentioned stretchable solid ion electrode, preferably, the second compound is selected from polyvinyl alcohol, polyacryl alcohol, aminopolyvinyl alcohol or mercaptopolyvinyl alcohol, more preferably polyvinyl alcohol.

[0014] According to a specific embodiment of the present invention, in the above-described stretchable solid-state ion electrode, preferably, the molecular weight of the second compound is 10. 3 -10 7 .

[0015] According to a specific embodiment of the present invention, in the above-mentioned stretchable solid ion electrode, preferably, the salt is selected from lithium salt, sodium salt, potassium salt, calcium salt or zinc salt, and preferably lithium salt.

[0016] According to a specific embodiment of the present invention, in the above-mentioned stretchable solid ion electrode, preferably, the salt is selected from one or more of sodium chloride (NaCl), potassium chloride (KCl), calcium chloride (CaCl2), sodium sulfate (Na2SO4), zinc sulfate (ZnSO4), lithium chloride (LiCl), lithium bis(fluorosulfonyl)imide (LiFSI), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), more preferably lithium chloride (LiCl), lithium bis(fluorosulfonyl)imide (LiFSI), or lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).

[0017] According to a specific embodiment of the present invention, in the above-described stretchable solid-state ion electrode, preferably, the stretchable polymer material is selected from a third compound as shown in general formula III or a fourth compound as shown in general formula IV.

[0018]

[0019] R8 is selected from

[0020] R9 is selected from polymerization degrees of 1-10. 4 Polyethylene glycol groups or a degree of polymerization of 1-10 4 The polytetrahydrofuran group, more preferably a polyethylene glycol group or a polytetrahydrofuran group with a degree of polymerization of 1-500, is preferred.

[0021] R 10 for

[0022] x and y are each independently selected from positive integers from 1 to 100,000, preferably positive integers from 10 to 10,000;

[0023]

[0024] Among them, R 11 R 12 Each is independently selected from C1-C10 alkyl or C1-C10 alkoxy, preferably C1-C5 alkyl or C1-C5 alkoxy; i is selected from positive integers from 10 to 10000, preferably positive integers from 10 to 5000.

[0025] In the stretchable solid-state ion electrode of the present invention, the stretchable polymer material does not simultaneously contain a third compound and a fourth compound.

[0026] According to a specific embodiment of the present invention, in the above-mentioned stretchable solid-state ion electrode, preferably, in general formula III, R8 is... R9 is a polyethylene glycol group with a degree of polymerization of 1-500, and x and y are both 80. In this case, the third compound is a water-soluble polyurethane compound.

[0027] According to a specific embodiment of the present invention, in the above-described stretchable solid-state ion electrode, preferably, in general formula IV, R 11 and R 12 Methyl groups are respectively denoted as i, which is 2000. At this point, the fourth compound is polydimethylsiloxane.

[0028] According to a specific embodiment of the present invention, in the above-mentioned stretchable solid ion electrode, preferably, the mass ratio of the ion conductor to the stretchable polymer material is 1:4-4:1.

[0029] According to a specific embodiment of the present invention, preferably, the stretchable solid-state ion electrode is composed of the following components by mass percentage: 45 wt% polymer, 5 wt% salt, and 50 wt% stretchable polymer material.

[0030] According to a specific embodiment of the present invention, the stretchable solid-state ion electrode is preferably prepared by a method comprising: uniformly mixing a polymer, a salt, and a stretchable polymer material in a solvent, and drying to remove the solvent, thereby obtaining the stretchable solid-state ion electrode. Preferably, the drying temperature does not exceed 80°C.

[0031] The present invention also provides a triboelectric nanogenerator, which is assembled from a positive friction layer, a negative friction layer and an electrode layer bonded to either friction layer; the electrode layer is selected from the above-mentioned stretchable solid ion electrode, and the material of the friction layer bonded to the electrode layer is the same as the stretchable polymer material in the solid ion electrode.

[0032] In conventional technologies, the electrode layer and friction layer of a triboelectric nanogenerator are made of two different materials and are bonded together with adhesive tape. When the tape ages or under significant external force, the electrode layer and friction layer easily separate, damaging the device. In the triboelectric nanogenerator of this invention, a stretchable polymer material is uniformly distributed in the electrode layer, and the stretchable polymer material in both the friction layer and the electrode layer is the same substance. This same polymer readily undergoes chemical bonding during device casting, forming a unified whole. During device casting, the friction layer and the stretchable polymer form chemical bonds, creating a unified structure that is difficult to separate.

[0033] The stretchable solid-state ion electrode of the present invention is applicable to four different modes of triboelectric nanogenerators: contact-separation mode, contact-sliding mode, single electrode mode, and independent triboelectric layer mode.

[0034] According to a specific embodiment of the present invention, in the above-mentioned triboelectric nanogenerator, preferably, the material of the other triboelectric layer not attached to the electrode layer is selected from one or more of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), silicone rubber, polydimethylsiloxane (PDMS), polyvinyl chloride (PVC), polyethylene (PE), polyvinyl alcohol (PVA), protein, chitin, chitosan, cellulose, sodium lignosulfonate, and polyurethane (PU); the protein is selected from soybean protein or silk protein.

[0035] In the triboelectric nanogenerator of the present invention, the positive friction layer is selected from materials with high electron-donating ability, and the negative friction layer is selected from materials with high electron-withdrawing ability. For example, water-soluble polyurethane compounds have high electron-donating ability, and polydimethylsiloxane has high electron-withdrawing ability.

[0036] The present invention also provides an application of the above-described stretchable solid-state ion electrode or the above-described triboelectric nanogenerator in harvesting biomechanical energy.

[0037] According to a specific embodiment of the present invention, in the above application, preferably, the triboelectric nanogenerator is used as a wearable power source.

[0038] The primary application of the triboelectric nanogenerator of this invention is to provide a stretchable, high-output wearable power source by collecting human motion, such as the flexion and release of fingers, elbows, and knees. This device is safer than lithium batteries. Therefore, the triboelectric nanogenerator of this invention can replace lithium batteries to power small electronic devices, such as Bluetooth devices and digital watches; the triboelectric nanogenerator of this invention can also act as a generator to charge batteries during human movement.

[0039] The technical solution provided by this invention has the following beneficial effects:

[0040] (1) In the stretchable solid ion electrode of the present invention, the ion conductor and the stretchable polymer material are cross-linked with each other through hydrogen bonding and electrostatic force, which effectively improves the stretchability of the composite solid ion electrode and further improves the service life of the triboelectric nanogenerator in the energy harvesting process.

[0041] (2) The stretchable solid ion electrode of the present invention overcomes the problem of low conductivity caused by high crystallinity of ion conductor by mixing stretchable polymer material into ion conductor, thereby improving the conductivity of solid ion electrode and further improving the power output performance of triboelectric nanogenerator.

[0042] (3) Since the solid ion electrode does not contain any liquid, the solid ion electrode and triboelectric nanogenerator of the present invention overcome the risks of solvent evaporation and leakage. Detailed Implementation

[0043] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0044] The compound A used in this embodiment of the invention is a water-soluble polyurethane compound having the structure shown in general formula III, wherein R8 is... R9 is a polyethylene glycol group with a degree of polymerization of 22, and x and y are 80 respectively.

[0045] The compound B used in this embodiment of the invention is a polydimethylsiloxane having the structure shown in general formula IV, wherein R 11 and R 12 Methyl groups, i = 2000.

[0046] The present invention will now be described in conjunction with specific embodiments.

[0047] Example 1

[0048] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0049] (1) Preparation of solid-state ion electrodes:

[0050] 4.5g of polyethylene oxide (PEO) (molecular weight: 10) 5 0.5g LiFSI and 5g compound A were poured into 20g water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours. After molding, a stretchable solid-state ion electrode was obtained.

[0051] (2) Fabrication of triboelectric nanogenerators:

[0052] Mix 10g of water-soluble polyurethane A with 100g of water and pour it into the mold of step (1). Dry at 100℃ for 6h. After molding, a positive friction layer and an electrode layer that adhere to each other are obtained.

[0053] 10g of polydimethylsiloxane (PDMS) and 1g of curing agent (Dow Corning 184) were mixed and stirred and poured into another mold of the same size. The mixture was dried at 80°C for 6 hours to obtain a negative friction layer after molding.

[0054] After assembly, a triboelectric nanogenerator was obtained.

[0055] Example 2

[0056] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0057] (1) Preparation of solid-state ion electrodes:

[0058] 4.75g of polyethylene oxide (PEO) (molecular weight: 10) 5 0.25g LiFSI and 5g compound A were poured into 20g water and stirred for 2h. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2h. After molding, a stretchable solid-state ion electrode was obtained.

[0059] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0060] Example 3

[0061] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0062] (1) Preparation of solid-state ion electrodes:

[0063] 4g of polyethylene oxide (PEO) (molecular weight: 10) 5 ), 1g LiFSI and 5g compound A were poured into 20g water and stirred for 2h. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2h. After molding, a stretchable solid ion electrode was obtained.

[0064] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0065] Example 4

[0066] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0067] (1) Preparation of solid-state ion electrodes:

[0068] 1.8g of polyethylene oxide (PEO) (molecular weight: 10) 5 0.2g LiFSI and 8g compound A were poured into 20g water and stirred for 2h. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2h. After molding, a stretchable solid-state ion electrode was obtained.

[0069] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0070] Example 5

[0071] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0072] (1) Preparation of solid-state ion electrodes:

[0073] 7.2g of polyethylene oxide (PEO) (molecular weight: 10) 50.8g LiFSI and 2g compound A were poured into 20g water and stirred for 2h. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2h. After molding, a stretchable solid-state ion electrode was obtained.

[0074] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0075] Example 6

[0076] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0077] (1) Preparation of solid-state ion electrodes:

[0078] 4.5g of polyvinyl alcohol (PVA) (molecular weight: 10) 5 0.5g LiFSI and 5g compound A were poured into 20g water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours. After molding, a stretchable solid-state ion electrode was obtained.

[0079] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0080] Example 7

[0081] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0082] (1) Preparation of solid-state ion electrodes:

[0083] 4.5g of polyethylene oxide (PEO) (molecular weight: 10) 5 0.5g LiCl and 5g compound A were poured into 20g water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours. After molding, a stretchable solid ion electrode was obtained.

[0084] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0085] Example 8

[0086] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0087] (1) Preparation of solid-state ion electrodes:

[0088] 4.5g of polyethylene oxide (PEO) (molecular weight: 10) 50.5g LiFSI and 5g compound B were poured into 20g water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours. After molding, a stretchable solid-state ion electrode was obtained.

[0089] (2) Fabrication of triboelectric nanogenerators:

[0090] Mix 10g of polydimethylsiloxane B with 100g of water and pour it into the mold of step (1). Dry at 100℃ for 6h. After molding, a negative friction layer and an electrode layer that adhere to each other are obtained.

[0091] 10g of polyvinyl alcohol (PVA) and 1g of curing agent (Dow Corning 184) were mixed and stirred and poured into another mold of the same size. The mixture was dried at 100℃ for 6 hours and a positive friction layer was obtained after molding.

[0092] After assembly, a triboelectric nanogenerator was obtained.

[0093] Example 9

[0094] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0095] (1) Preparation of solid-state ion electrodes:

[0096] 2.5g of polyethylene oxide (PEO) (molecular weight: 10) 5 ), 2.0g polyvinyl alcohol (PVA) (molecular weight: 10) 5 ), 0.5g LiFSI and 5g compound A were poured into 20g water and stirred for 2h. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2h. After molding, a stretchable solid ion electrode was obtained.

[0097] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0098] Example 10

[0099] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0100] (1) Preparation of solid-state ion electrodes:

[0101] 4.5g of aminopolyethylene oxide (molecular weight: 10) 5 0.5g LiFSI and 5g compound A were poured into 20g water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours. After molding, a stretchable solid-state ion electrode was obtained.

[0102] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0103] Example 11

[0104] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0105] (1) Preparation of solid-state ion electrodes:

[0106] 4.75g of aminopolyethylene oxide (molecular weight: 10) 5 0.25g LiFSI and 5g compound A were poured into 20g water and stirred for 2h. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2h. After molding, a stretchable solid-state ion electrode was obtained.

[0107] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0108] Example 12

[0109] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0110] (1) Preparation of solid-state ion electrodes:

[0111] 4g of aminopolyethylene oxide (molecular weight: 10) 5 ), 1g LiFSI and 5g compound A were poured into 20g water and stirred for 2h. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2h. After molding, a stretchable solid ion electrode was obtained.

[0112] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0113] Example 13

[0114] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0115] (1) Preparation of solid-state ion electrodes:

[0116] 1.8g of aminopolyethylene oxide (molecular weight: 10) 5 0.2g LiFSI and 8g compound A were poured into 20g water and stirred for 2h. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2h. After molding, a stretchable solid-state ion electrode was obtained.

[0117] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0118] Example 14

[0119] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0120] (1) Preparation of solid-state ion electrodes:

[0121] 7.2g of aminopolyethylene oxide (molecular weight: 10) 5 0.8g LiFSI and 2g compound A were poured into 20g water and stirred for 2h. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2h. After molding, a stretchable solid-state ion electrode was obtained.

[0122] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0123] Example 15

[0124] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0125] (1) Preparation of solid-state ion electrodes:

[0126] 4.5g of mercaptopolyethylene oxide (molecular weight: 10) 5 0.5g LiFSI and 5g compound A were poured into 20g water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours. After molding, a stretchable solid-state ion electrode was obtained.

[0127] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0128] Example 16

[0129] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0130] (1) Preparation of solid-state ion electrodes:

[0131] 4.5g of N,N'-bis-[(3-triethoxysilylpropyl)aminocarbonyl]polyethylene oxide (molecular weight: 10) 5 0.5g LiFSI and 5g compound A were poured into 20g water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours. After molding, a stretchable solid-state ion electrode was obtained.

[0132] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0133] Example 17

[0134] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0135] (1) Preparation of solid-state ion electrodes:

[0136] 4.5g of polyacrylol (molecular weight: 10) 5 0.5g LiFSI and 5g compound A were poured into 20g water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours. After molding, a stretchable solid-state ion electrode was obtained.

[0137] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0138] Example 18

[0139] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0140] (1) Preparation of solid-state ion electrodes:

[0141] 4.5g of aminopolyvinyl alcohol (molecular weight: 10) 5 0.5g LiFSI and 5g compound A were poured into 20g water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours. After molding, a stretchable solid-state ion electrode was obtained.

[0142] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0143] Example 19

[0144] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0145] (1) Preparation of solid-state ion electrodes:

[0146] 4.5g of mercaptopolyvinyl alcohol (molecular weight: 10) 5 0.5g LiFSI and 5g compound A were poured into 20g water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours. After molding, a stretchable solid-state ion electrode was obtained.

[0147] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0148] Example 20

[0149] This embodiment provides a stretchable solid-state ion electrode and a triboelectric nanogenerator, the preparation method of which is as follows:

[0150] (1) Preparation of solid-state ion electrodes:

[0151] 2.5g of mercaptopolyvinyl alcohol (molecular weight: 10) 5 ), 2g aminopolyethylene oxide, 0.5g LiFSI and 5g compound A were poured into 20g water and stirred for 2h. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2h. After molding, a stretchable solid ion electrode was obtained.

[0152] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0153] Comparative Example 1

[0154] This comparative example provides a solid-state ion electrode and a triboelectric nanogenerator, which are prepared using the same method as in Example 1. The main difference is that the solid-state ion electrode in this comparative example does not contain polyethylene oxide (PEO), as detailed below:

[0155] (1) Preparation of solid-state ion electrodes:

[0156] 1g of LiFSI and 9g of compound A were poured into 20g of water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours to obtain a solid ion electrode.

[0157] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0158] Comparative Example 2

[0159] This comparative example provides a solid-state ion electrode and a triboelectric nanogenerator, which are prepared using the same method as in Example 1. The main difference is that the solid-state ion electrode in this comparative example does not contain lithium salt, as detailed below:

[0160] (1) Preparation of solid-state ion electrodes:

[0161] 5g of polyethylene oxide (PEO) (molecular weight: 10) 5 ) and 5g of compound A were poured into 20g of water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours. After molding, a solid ion electrode was obtained.

[0162] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0163] Comparative Example 3

[0164] This comparative example provides a solid-state ion electrode and a triboelectric nanogenerator, which are prepared using the same method as in Example 1. The main difference is that compound A is not added to the solid-state ion electrode in this comparative example, as detailed below:

[0165] (1) Preparation of solid-state ion electrodes:

[0166] 9g of polyethylene oxide (PEO) (molecular weight: 10) 5 1g of LiFSI was added to 20g of water and stirred for 2 hours. The mixture was then poured into a mold (10cm long and 5cm wide) and dried at 80℃ for 2 hours to obtain a solid ion electrode.

[0167] (2) Preparation of triboelectric nanogenerator: Same as in Example 1.

[0168] The triboelectric nanogenerators prepared in the above embodiments and comparative examples were cut into 4cm×2cm pieces. Then, two pieces of foam (3cm thick) were used to stretch the positive and negative friction layers apart and adhere them to the fingers to collect the energy generated by the bending motion of the fingers.

[0169] The above-mentioned triboelectric nanogenerator was tested. The tensile properties and adhesive force of the material were measured by a tensile tester (speed 2 cm / min), the ionic conductivity was measured by the crosslinking impedance (EIS) method of an electrochemical workstation, and the electrical output performance was measured by an oscilloscope.

[0170] The component ratios and performance test results of the triboelectric nanogenerators in the above embodiments and comparative examples are shown in Table 1.

[0171] Table 1. Component composition and performance test results of triboelectric nanogenerators

[0172]

[0173]

[0174] According to Table 1, comparing Examples 1-5, the triboelectric nanogenerator of Example 1 has the best elongation, conductivity, adhesion and electrical output, indicating that the optimal composition ratio of the stretchable solid ion electrode is: PEO 45wt%, LiFSI 5wt%, and compound A 50wt%.

[0175] Comparing Examples 1 and 6-8, the triboelectric nanogenerator of Example 1 exhibits the best elongation, conductivity, adhesion, and electrical output, indicating that the optimal composition of the stretchable solid-state ion electrode is PEO, LiFSI, and compound A.

[0176] Comparing Example 1 with Comparative Examples 1-3, the triboelectric nanogenerator of Example 1 still has the best elongation, conductivity, adhesion and electrical output. It can be seen that all materials are indispensable in the stretchable solid ion electrode.

[0177] Comparing Examples 1, 6, and 9, and Examples 10, 19, and 20, the triboelectric nanogenerator of Example 1 exhibits the best elongation, conductivity, adhesion, and electrical output, indicating that the optimal composition of the stretchable solid-state ion electrode is a single component of PEO, LiFSI, and compound A.

[0178] Comparative Examples 10-14 and Example 10 show that the triboelectric nanogenerator has the best elongation, conductivity, adhesion and electrical output. The triboelectric nanogenerator with a composition of 45 wt% aminopolyethylene oxide, 5 wt% LiFSI and 50 wt% compound A has the best elongation, conductivity, adhesion and electrical output.

[0179] Comparing Examples 1, 10, and 15-19, the triboelectric nanogenerator of Example 1 exhibits the best elongation, conductivity, adhesion, and electrical output, indicating that the optimal ionic polymer for the stretchable solid-state ionic electrode is PEO.

Claims

1. A stretchable solid-state ion electrode, characterized in that, The stretchable solid-state ion electrode is made of an ion conductor and a stretchable polymer material; the ion conductor comprises a polymer and a salt in a mass ratio of 1:19 to 1:4, and the polymer is selected from a first compound and / or a second compound; The first compound is selected from polyethylene oxide, polyethylene propylene oxide, polyethylene butane oxide, amino polyethylene oxide, mercapto polyethylene oxide, or N,N'-bis-[(3-triethoxysilylpropyl)aminocarbonyl] polyethylene oxide; The second compound is selected from polyvinyl alcohol, polyacryl alcohol, aminopolyvinyl alcohol, or mercaptopolyvinyl alcohol; The salt is selected from lithium salts, sodium salts, potassium salts, calcium salts, or zinc salts; The stretchable polymer material is selected from the third compound as shown in general formula III or the fourth compound as shown in general formula IV. General Formula (III) R8 is selected from or , R9 is selected from polymerization degrees of 1-10. 4 Polyethylene glycol groups or a degree of polymerization of 1-10 4 polytetrahydrofuranyl, R 10 for , x and y are each independently selected from positive integers between 1 and 100000. General Formula (IV) Among them, R 11 R 12 Each is independently selected from C1-C10 alkyl or C1-C10 alkoxy, and i is selected from positive integers from 10 to 10000.

2. The stretchable solid-state ion electrode according to claim 1, characterized in that, The molecular weight of the first compound is 10. 3 -10 7 .

3. The stretchable solid-state ion electrode according to claim 1, characterized in that, The molecular weight of the second compound is 10. 3 -10 7 .

4. The stretchable solid-state ion electrode according to claim 1, characterized in that, The salt is a lithium salt.

5. The stretchable solid-state ion electrode according to claim 1, characterized in that, In general formula III, R9 is selected from polyethylene glycol group or polytetrahydrofuran group with a degree of polymerization of 1-500, and x and y are each independently selected from positive integers of 10-10000. In general formula IV, R 11 R 12 Each is independently selected from C1-C5 alkyl or C1-C5 alkoxy groups, and i is selected from positive integers from 10 to 5000.

6. The stretchable solid-state ion electrode according to claim 5, characterized in that, In general formula III, R8 is R9 is a polyethylene glycol group with a degree of polymerization of 1-500, and x and y are 80 respectively.

7. The stretchable solid-state ion electrode according to claim 5, characterized in that, In general formula IV, R 11 and R 12 Methyl groups, i = 2000.

8. The stretchable solid-state ion electrode according to any one of claims 5-7, characterized in that, The mass ratio of ionic conductor to stretchable polymer material is 1:4-4:

1.

9. A triboelectric nanogenerator, characterized in that, This triboelectric nanogenerator is assembled from a positive friction layer, a negative friction layer, and an electrode layer attached to either friction layer; The electrode layer is selected from the stretchable solid ion electrode according to any one of claims 1-8, and the material of the friction layer that is attached to the electrode layer is the same as the stretchable polymer material in the solid ion electrode.

10. The triboelectric nanogenerator according to claim 9, characterized in that, The material of the other friction layer not attached to the electrode layer is selected from one or more of polytetrafluoroethylene, polyvinyl fluoride, silicone rubber, polydimethylsiloxane, polyvinyl chloride, polyethylene, polyvinyl alcohol, protein, chitin, chitosan, cellulose, sodium lignosulfonate, and polyurethane.

11. The application of the stretchable solid-state ion electrode according to any one of claims 1-8 or the triboelectric nanogenerator according to claim 9 or 10 in harvesting biomechanical energy.

12. The application according to claim 11, wherein the triboelectric nanogenerator is used as a wearable power source.

Images