KR102333221B1 - charged body having negative electric charge and artificial generator comprising the same - Google Patents

Abstract

The present invention includes a repeating unit represented by a predetermined formula as a main chain, a C ₆₀ fullerene-containing group as a side chain bonded to the main chain, and a polymer group or a methyl group at one end of the main chain It relates to a negatively charged body and a triboelectric generator comprising the same.

Description

A negatively charged body and a triboelectric generator comprising the same

The present invention relates to a negatively charged body and a triboelectric generator including the same.

Recently, the use of electricity is gradually increasing due to the depletion of fossil fuels, and the energy shortage is getting serious due to the lack of power generation. Energy harvesting technology, which has been developed to efficiently utilize scarce energy resources, is attracting attention in connection with recent energy problems.

Energy harvesting refers to a system that harvests ambient energy that is generated in the surrounding environment, but is consumed and discarded, and converts it into usable electrical energy.

Among these energy harvesting technologies, the fields with the most active technology development are energy harvesting using piezoelectric materials, energy harvesting using triboelectric materials, energy harvesting using thermoelectric materials, and energy harvesting using ferrofluid. technology, etc.

In particular, when energy harvesting technology using triboelectricity is used, there is an advantage in that a high output value can be obtained. The production efficiency is very low, so its application is insignificant.

Accordingly, there is an increasing demand for materials having excellent charge generation efficiency for application to high-efficiency generators.

One aspect is to provide a negatively charged object having a new structure with remarkably improved charge generation efficiency.

Another aspect is to provide a triboelectric generator employing the negatively charged body.

In one aspect, the present invention comprises a repeating unit represented by the following formula (1) as a main chain,

_{A C 60} fullerene-containing group represented by the following Chemical Formula 2 is included as a side chain bonded to the main chain,

A negatively charged body including a polymer group or a methyl group is provided at one end of the main chain:

<Formula 1>

<Formula 2>

In Formulas 1 and 2,

A ₁ and A ₂ are each independently, a substituted or unsubstituted C ₁ -C ₆₀ alkylene group, a substituted or unsubstituted C ₂ -C ₆₀ alkenylene group, a substituted or unsubstituted C ₂ -C ₆₀ alkynylene group, substituted or unsubstituted C ₁ -C ₆₀ heteroalkylene group, substituted or unsubstituted C ₂ -C ₆₀ heteroalkenylene group, substituted or unsubstituted C ₂ -C ₆₀ heteroalkynylene group, substituted or unsubstituted A substituted C ₆ -C ₆₀ arylene group, a substituted or unsubstituted C ₁ -C ₆₀ heteroarylene group, a substituted or unsubstituted divalent non-aromatic cyclic group, or a substituted or unsubstituted divalent non-aromatic hetero cyclic group,

At least one hydrogen included in A ₁ and A ₂ is substituted with a group represented by Formula 2,

0≤n1≤1, 0≤n2≤1, the sum of n1 and n2 is 1,

m1 is selected from an integer of 1 to 5,000,

L ₁ is a substituted or unsubstituted C ₁ -C ₆₀ alkylene group, a substituted or unsubstituted C ₂ -C ₆₀ alkenylene group, a substituted or unsubstituted C ₂ -C ₆₀ alkynylene group, a substituted or unsubstituted C ₁ -C ₆₀ heteroalkylene group, substituted or unsubstituted C ₂ -C ₆₀ heteroalkenylene group, substituted or unsubstituted C ₂ -C ₆₀ heteroalkynylene group, substituted or unsubstituted C ₆ -C ₆₀ an arylene group, a substituted or unsubstituted C ₁ -C ₆₀ heteroarylene group, a substituted or unsubstituted divalent non-aromatic cyclic group, or a substituted or unsubstituted divalent non-aromatic heterocyclic group,

a1 is selected from an integer of 0 to 10,

said substituted C ₁ -C ₆₀ alkylene group, substituted C ₂ -C ₆₀ alkenylene group, substituted C ₂ -C ₆₀ alkynylene group, substituted C ₁ -C ₆₀ heteroalkylene group, substituted C ₂ -C ₆₀ heteroalkenylene group, substituted C ₂ -C ₆₀ heteroalkynylene group, substituted C ₆ -C ₆₀ arylene group, substituted C ₁ -C ₆₀ heteroarylene group, substituted divalent non-aromatic group At least one of the substituents of the click group and the substituted divalent non-aromatic heterocyclic group are independently of each other, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group a group, a hydrazino group, a hydrazono group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and a C ₆ -C ₂₀ aryl group; and

_{C 1} -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group -C ₂₀ aryl group; is selected from

* denotes a binding site with the main chain.

In one embodiment, the A ₁ and A ₂ are each independently selected from a methylene group, an ethylene group, a propylene group, and a phenylene group; and

Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group , and a C ₆ -C ₂₀ aryl group; _{and a C 1} -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and C substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group. ₆ -C ₂₀ aryl group; It may be selected from a methylene group, an ethylene group, a propylene group, and a phenylene group, which are substituted with one or more of them.

In one embodiment, the repeating unit represented by Formula 1 may be represented by Formula 1-1 below:

<Formula 1-1>

In Formula 1-1,

For the description of n1, n2 and m1, refer to the bar defined above,

wherein R ₁₁ to R ₁₈ are a binding site with the side chain represented by Formula 2, hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydra a zino group, a hydrazono group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and a C ₆ -C ₂₀ aryl group; and

_{C 1} -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group -C ₂₀ aryl group; is selected from

However, _{at least one of R 11} to R ₁₈ is a binding site with the side chain represented by Formula 2 above.

In one embodiment, the L ₁ is a methylene group, an ethylene group, a propylene group, and a phenylene group; and

Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C ₁ -C ₂₀ alkyl group, and C ₁ -C ₂₀ alkoxy It may be selected from a methylene group, an ethylene group, a propylene group, and a phenylene group substituted with one or more of the groups.

In one embodiment, L ₁ may be a group represented by any one selected from the following Chemical Formulas 3-1 to 3-4:

In Formulas 3-1 to 3-4,

Z ₁ and Z ₂ are each independently, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, C ₁ -C ₂₀ alkyl group, and a C ₁ -C ₂₀ alkoxy group,

d4 is an integer from 0 to 4,

* and *' are binding sites with neighboring atoms.

In an embodiment, the polymer group may have a weight average molecular weight (Mw) of 10 kDa to 100 kDa.

In one embodiment, the polymer group may be a homopolymer or a copolymer.

In an embodiment, the polymer group may be selected from polydimethyl siloxane (PDMS), a polyimide group, and combinations thereof.

In one embodiment, the negatively charged body may be represented by the following Chemical Formulas A to B:

<Formula A>

<Formula B>

<Formula 4>

In Formulas A to B, 0≤n11≤1, 0≤n12≤1, the sum of n11 and n12 is 1,

P ₁ is selected from the group represented by Formulas B-1 to B-8,

d1 is selected from an integer of 1 to 10,

x is an integer selected from 1 to 50,

R ₂₁ to R ₂₆ are a group represented by Formula 4, hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazo no group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and a C ₆ -C ₂₀ aryl group; and

_{C 1} -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group -C ₂₀ aryl group; is selected from

c3 is an integer selected from 0 to 3,

c4 is an integer selected from 0 to 4,

L ₃₁ is *-C(R ₃₂ )(R ₃₃ )-*', *-Si(R ₃₂ )(R ₃₃ )-*', *-N(R ₃₂ )-*', *-O-*' , and *-S-*',

a31 is an integer selected from 0 to 5;

R ₃₁ to R ₃₃ are hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, an azide group (-N ₃ ), C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group, -B(Q ₁₁ )(Q ₁₂ ), -N(Q ₁₁ )(Q ₁₂ ), -C (Q ₁₁ )(Q ₁₂ )(Q ₁₃ ), —Si(Q ₁₁ )(Q ₁₂ )(Q ₁₃ ), and —Ge(Q ₁₁ )(Q ₁₂ )(Q ₁₃ ); and

_{C 1} -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group -C ₂₀ aryl group; is selected from

The Q ₁₁ to Q ₁₃ are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a a zide group (-N ₃ ), a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and a C ₆ -C ₂₀ aryl group; and

_{C 1} -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group -C ₂₀ aryl group; is selected from

* and *' are binding sites with neighboring atoms.

In another aspect, the present invention provides a triboelectric generator including the negatively charged body.

In this case, the output value of the triboelectric generator may be 16 μA to 70 μA.

The triboelectric generator may satisfy the following conditions 1 and 2:

<Condition 1>

Q ₁ ≥ 4 × Q ₀

<Condition 2>

Q ₂ ≥ 0.5 × Q ₁

Among the conditions 1 and 2, Q ₀ is the charge amount of the triboelectric generator before charge injection, Q ₁ is the initial charge amount of the triboelectric generator after charge injection, and Q ₂ is the charge amount of the triboelectric generator 2 hours after charge injection.

After the charge injection of the triboelectric generator, the initial charge is about 200μC / m ² or more, two hours after the amount of charges may be the about 117μC / m ² or more holding about 58.3% based on the initial charge amount.

In addition, the negatively charged body may be in the form of a thin film.

In this case, the thickness of the thin film may be 0.1 μm to 1000 μm.

The negatively charged body according to the present invention has an improved dielectric constant and a remarkably increased electron trapping ability, and has excellent charge generation efficiency when applied to a triboelectric generator.

1 shows an example of a triboelectric generator according to the present invention.
2(a) to 2(e) exemplarily show the operating principle of the triboelectric generator according to the present invention.
3A shows the measurement result of the charge-collecting ability of the triboelectric generator manufactured according to Comparative Example 1. Referring to FIG.
3B shows the measurement result of the charge-collecting ability of the triboelectric generator manufactured according to Example 1. Referring to FIG.
<Explanation of symbols for main parts of the drawing>
10: lower electrode
20: negatively charged object
30: upper electrode
100: external load
200: triboelectric generator

Hereinafter, with reference to the accompanying drawings, various embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement them. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In order to clearly explain the present invention, parts irrelevant to the description are omitted, and the same reference numerals are given to the same or similar elements throughout the specification.

In addition, since the size and thickness of each component shown in the drawings are arbitrarily indicated for convenience of description, the present invention is not necessarily limited to the illustrated bar.

In addition, throughout the specification, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

Energy harvesting technology using triboelectricity is to harvest energy based on the electrostatic induction phenomenon. In other words, it is based on the phenomenon that external mechanical energy creates a potential difference, which results in the formation of a compensating charge, and the flow of electrons, that is, current.

In the case of using the energy harvesting technology using mechanical micro-energy as described above, it is very useful because it is possible to implement an eco-friendly high-output generator.

In order to effectively apply the energy harvesting technology using triboelectricity to various fields, it is necessary to develop a negatively charged body having excellent electron affinity and/or trapping properties.

On the other hand, materials for negatively charged materials generally applied to energy harvesting technology using triboelectricity include PDMS, PTFE, PVDF, and Kapton, a commercially available polyimide.

However, these materials have a problem in that it is difficult to obtain a desired effect when applied to a generator because the charge generation efficiency is limited.

Accordingly, the inventors of the present invention, as a result of repeated research to develop a negatively charged object with improved charge generation efficiency, in order to increase electron trapping properties, LUMO and HOMO energy levels are at a deep level to be advantageous for collecting electrons. It was found that the above object can be achieved when a C ₆₀ fullerene-containing group of is introduced into a negatively charged body.

That is, the negatively charged body according to the present invention includes a repeating unit represented by the following Chemical Formula 1 as a main chain, and a C ₆₀ fullerene-containing group represented by the following Chemical Formula 2 as a side chain coupled to the main chain, , It is characterized in that it contains a polymer group or a methyl group at one end of the main chain:

<Formula 1>

<Formula 2>

In Formula 1,

A ₁ and A ₂ are each independently, a substituted or unsubstituted C ₁ -C ₆₀ alkylene group, a substituted or unsubstituted C ₂ -C ₆₀ alkenylene group, a substituted or unsubstituted C ₂ -C ₆₀ alkynylene group, substituted or unsubstituted C ₁ -C ₆₀ heteroalkylene group, substituted or unsubstituted C ₂ -C ₆₀ heteroalkenylene group, substituted or unsubstituted C ₂ -C ₆₀ heteroalkynylene group, substituted or unsubstituted A substituted C ₆ -C ₆₀ arylene group, a substituted or unsubstituted C ₁ -C ₆₀ heteroarylene group, a substituted or unsubstituted divalent non-aromatic cyclic group, or a substituted or unsubstituted divalent non-aromatic hetero cyclic group,

At least one hydrogen included in A ₁ and A ₂ is substituted with a group represented by Formula 2 above.

For example, A ₁ and A ₂ may be each independently selected from a methylene group, an ethylene group, a propylene group, and a phenylene group; and deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and a C ₆ -C ₂₀ aryl group; _{and a C 1} -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and C substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group. ₆ -C ₂₀ aryl group; It may be selected from a methylene group, an ethylene group, a propylene group, and a phenylene group, which are substituted with one or more of them.

In Formula 1, 0≤n1≤1, 0≤n2≤1, the sum of n1 and n2 is 1, and m1 is an integer selected from 1 to 5,000.

For example, the repeating unit represented by Formula 1 may be represented by Formula 1-1 below:

<Formula 1-1>

In Formula 1-1, the description of n1, n2, and m1 is as defined above, and R ₁₁ to R ₁₈ are a binding site to the side chain represented by Formula 2, hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ - C ₂₀ aryl group; _{and a C 1} -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and C substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group. ₆ -C ₂₀ aryl group; selected from, provided _{that at least one of R 11} to R ₁₈ is a binding site with the side chain represented by Formula 2 above.

In Formula 2, L ₁ is a substituted or unsubstituted C ₁ -C ₆₀ alkylene group, a substituted or unsubstituted C ₂ -C ₆₀ alkenylene group, a substituted or unsubstituted C ₂ -C ₆₀ alkynylene group, substituted or unsubstituted C ₁ -C ₆₀ heteroalkylene group, substituted or unsubstituted C ₂ -C ₆₀ heteroalkenylene group, substituted or unsubstituted C ₂ -C ₆₀ heteroalkynylene group, substituted or unsubstituted C ₆ -C ₆₀ arylene group, substituted or unsubstituted C ₁ -C ₆₀ heteroarylene group, substituted or unsubstituted divalent non-aromatic cyclic group, or substituted or unsubstituted divalent non-aromatic heterocyclic is a group

For example, L ₁ is a methylene group, an ethylene group, a propylene group, and a phenylene group; and deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C ₁ -C ₂₀ alkyl group, and C ₁ -C ₂₀ It may be selected from a methylene group, an ethylene group, a propylene group, and a phenylene group substituted with one or more of the alkoxy groups.

For example, L ₁ may be a group represented by any one selected from Formulas 3-1 to 3-4:

In Formulas 3-1 to 3-4, Z ₁ and Z ₂ are each independently selected from deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydra a zino group, a hydrazono group, a C ₁ -C ₂₀ alkyl group, and a C ₁ -C ₂₀ alkoxy group, d4 is an integer from 0 to 4, and * and *' are bonding sites with neighboring atoms.

As described above, the negatively charged body of the present invention can exhibit high charge trapping ability by introducing a _{C 60 fullerene-containing group.}

In one embodiment, the polymer group may be a homopolymer or a copolymer.

For example, the polymer group may be a homopolymer including the same repeating unit.

For example, the polymer group may be a copolymer including two or more different repeating units.

In one embodiment, the negatively charged body may be represented by the following Chemical Formulas A to B:

<Formula A>

<Formula B>

In Formula B, P ₁ is the aforementioned polymer group.

For example, 0≤n11≤1, 0≤n12≤1, and the sum of n11 and n12 may be 1.

For example, d1 may be selected from an integer of 1 to 10.

In this case, the polymer group may include a repeating unit represented by one or more selected from the following Chemical Formulas B-1 to B-8:

<Formula 4>

In Formulas B-1 to B-8,

x is an integer selected from 1 to 50,

R ₂₁ to R ₂₆ are a group represented by Formula 4, hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazo no group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and a C ₆ -C ₂₀ aryl group; and

_{C 1} -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group -C ₂₀ aryl group; is selected from

c3 is an integer selected from 0 to 3,

c4 is an integer selected from 0 to 4,

L ₃₁ is *-C(R ₃₂ )(R ₃₃ )-*', *-Si(R ₃₂ )(R ₃₃ )-*', *-N(R ₃₂ )-*', *-O-*' , and *-S-*',

a31 is an integer selected from 0 to 5;

R ₃₁ to R ₃₃ are hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, an azide group (-N ₃ ), C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group, -B(Q ₁₁ )(Q ₁₂ ), -N(Q ₁₁ )(Q ₁₂ ), -C (Q ₁₁ )(Q ₁₂ )(Q ₁₃ ), —Si(Q ₁₁ )(Q ₁₂ )(Q ₁₃ ), and —Ge(Q ₁₁ )(Q ₁₂ )(Q ₁₃ ); and

_{C 1} -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group -C ₂₀ aryl group; is selected from

The Q ₁₁ to Q ₁₃ are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a a zide group (-N ₃ ), a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and a C ₆ -C ₂₀ aryl group; and

_{C 1} -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group -C ₂₀ aryl group; is selected from

* and *' are binding sites with neighboring atoms.

For example, the repeating units indicated by B-7 and B-8 may be selected from the following group I:

<Group I>

.

.

A method of manufacturing the negatively charged body may be understood with reference to Korean Patent Publication No. KR10-2019-0005381.

Meanwhile, the negatively charged body according to the present invention may be applied to a triboelectric generator. Accordingly, the triboelectric generator according to the present invention is characterized in that it includes the negatively charged body. That is, the above-described negatively charged body can be applied to the triboelectric generator according to the present invention based on a charge pump.

More specifically, a negatively charged body may be formed using a solution prepared using the compound having the above-described chemical structure.

That is, after ultraviolet (UV) and/or ozone treatment of an electrode made of aluminum, etc., a solution prepared using a compound having the above-described chemical structure on at least one surface of the electrode is subjected to drop coating, doctor blade, spin coating, etc. It is possible to form a negatively charged body in the form of a thin film by applying and curing it using

1 shows an example of a triboelectric generator according to the present invention.

Referring to FIG. 1 , a triboelectric generator 200 according to the present invention includes a lower electrode 10 and an upper electrode 30 disposed to face each other and positioned between them, the lower electrode 10 and the upper electrode ( 30) characterized in that it comprises a negatively charged body 20 according to the present invention in direct contact with at least one surface. In this case, the negatively charged body may be positioned in the form of a thin film.

1 shows a form in which the negatively charged body 20 is in contact with the upper electrode 10 for convenience, but the negatively charged body 20 may be in direct contact with the lower electrode 30 if necessary.

2(a) to 2(e) exemplarily show the operating principle of the triboelectric generator according to the present invention.

In more detail, first, Figure 2 (a) shows the initial state of the triboelectric generator according to the present invention. In the initial state, there is no friction inside the generator based on external loads and friction, so the whole system is in charge equilibrium state because there is no surface charge.

Next, Figure 2 (b) shows a state in which an external load is applied to the triboelectric generator according to the present invention. When a load 100 is applied from the outside, friction occurs between the negatively charged thin film and the lower electrode 30 inside the generator. The electrons move to the lower electrode 30, and the negative charge on the lower electrode 30 and the negative charge on the surface of the negatively charged body 20 become.

Figure 2 (c) shows a state in which the external load is removed in the triboelectric generator according to the present invention. When the external load 100 is removed, the two rubbed surfaces, that is, the negatively charged object 20 and the lower electrode 30 are separated, and the upper electrode 10 and the lower electrode 30 are separated to form a charge balance between the upper and lower electrodes. Electrons move from the electrode 10 to the lower electrode 30 through an external circuit to generate an output current.

Figure 2 (d) shows a state in which the external load is completely removed in the triboelectric generator according to the present invention. When the external load 100 is completely removed, each layer inside the generator is restored to its initial state, but the negatively charged body 20 according to the present invention maintains a negative charge on the surface due to insulating properties and the upper electrode 10 is in a positively charged state is maintained as

2(e) shows a state in which an external load is applied again to the triboelectric generator according to the present invention. When an external load 10 is repeatedly applied to the upper part of the generator as shown in FIG. 2(e), the distance between the negatively charged body 20 layer and the lower electrode 30 is reduced and the negative charges on the surface are reduced to the lower electrode 30. By electrostatic induction of positive charges, electrons move from the lower electrode 30 to the upper electrode 10, thereby generating an output current in the opposite direction to that shown in FIG. 2(c).

The triboelectric generator according to the present invention generates an output by repeating the process shown in FIGS. 2(a) to 2(e).

On the other hand, when the negatively charged body according to the present invention is used, it can be applied to a triboelectric generator to achieve excellent effects.

That is, when the negatively charged object according to the present invention is applied to a generator, the charging characteristics can be greatly improved by using the principle of generation, separation, and accumulation of electric charges by friction. In addition, by introducing the concept of a charge pump, which is a system that integrates a charge generator, a charge separator, and a charge accumulator, to overcome the intrinsic limit of the output current of the material itself, a triboelectric generator with a high output value can be implemented. .

Accordingly, the output value of the triboelectric generator according to the present invention may be between 16 μA and 70 μA.

In addition, in the triboelectric generator, the negatively charged body according to the present invention may be applied in a thin film structure between the upper electrode and the lower electrode. In this case, the thickness of the thin film may be, for example, 0.1 μm to 1000 μm, 1 μm to 800 μm, or 50 μm to 600 μm. If the thickness of the thin film is less than 0.1㎛, there is a problem that the function as a generator is not implemented because the resistance between the upper and lower electrodes disappears. Therefore, there is a problem in that the output is reduced.

The present invention will be described in more detail through the following examples and comparative examples. However, the examples are provided to illustrate the present invention and do not limit the scope of the present invention only to these examples.

Example 1

Step (1)

First, through aluminum oxide treatment, the radical inhibitors present in each monomer styrene and 4-(chloromethyl)styrene were removed. Thereafter, the ratio of the monomer (styrene: 4- (chloromethyl) styrene) was maintained at 9:1 and dissolved in 1,4-dioxane. Next, under an argon atmosphere, 4 mol% of azobisisobutyronitrile was added and stirred at 90°C. The molecular weight of the copolymer was controlled by adjusting the reaction time to 12, 24, and 72 hours, respectively. After the reaction was completed, the resulting mixture was precipitated in methanol and hexane to remove unreacted monomers. Finally, by vacuum drying, Poly(styrene-co-chloromethylstyrene) polymer intermediate A was obtained.

Step (2)

The polymer intermediate A obtained in step (1) was dissolved in N,N-dimethylformamide (DMF), an excess of sodium azide was added thereto, and the mixture was stirred for 12 hours. After the reaction was completed, it was purified by precipitation in methanol and hexane, and vacuum-dried to obtain a Poly(styrene-co-axidomethylstyrene) polymer intermediate B.

Step (3)

The polymer intermediate B having the substituted azide and fullerene (C ₆₀ ) were dissolved in chlorobenzene, followed by stirring at 60° C. for 12 hours. In order to remove unreacted fullerene, precipitation was repeated several times in hexane and filtered _{to synthesize a Poly(styrene-co-NC 60} methylstyrene) polymer.

Comparative Example 1

A commercially available polytetrafluoroethylene (PTFE) film was used to form a negatively charged body.

Experimental Example 1: Measurement of properties of negatively charged objects

After maximizing the amount of electrons on the surface of the negatively charged object prepared according to Example 1 and Comparative Example 1 using corona discharge to check the charge collection and retention ability, 30N using a pushing device on the upper part of the triboelectric generator, A load was applied under the condition of 3 Hz, and the charge density was measured using an electrometer. The charge amount retention characteristics over time were confirmed.

The measurement results of the charge trapping ability of the negatively charged object prepared as described above are shown in FIGS. 3A (Comparative Example 1) and 3B (Example 1), respectively.

Referring to FIGS. 3A and 3B , it can be seen that the charge trapping ability of the negatively charged body prepared according to Example 1 is higher than that of the negatively charged body manufactured according to Comparative Example 1 over time.

Therefore, when the negatively charged object according to the present invention is applied to a triboelectric generator, it can be confirmed that the charge collection ability is remarkably increased, thereby having excellent charge generation efficiency.

Although preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, and can be easily changed by those of ordinary skill in the art from the embodiments of the present invention to equivalents. It includes all changes to the extent recognized as such.

Claims (14)

It comprises a repeating unit represented by the following formula (1) as a main chain,
_{A C 60} fullerene-containing group represented by the following Chemical Formula 2 is included as a side chain bonded to the main chain,
A negatively charged body comprising a polymer group or a methyl group at one end of the main chain:
<Formula 1>

<Formula 2>

In Formulas 1 and 2,
A ₁ and A ₂ are each independently selected from a methylene group, an ethylene group, a propylene group, and a phenylene group; and
Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group , and a C ₆ -C ₂₀ aryl group; _{and a C 1} -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and C substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group. ₆ -C ₂₀ aryl group; substituted with one or more of, a methylene group, an ethylene group, a propylene group, and a phenylene group,
At least one hydrogen included in A ₁ and A ₂ is substituted with a group represented by Formula 2,
0≤n1≤1, 0≤n2≤1, the sum of n1 and n2 is 1,
m1 is selected from an integer of 1 to 5,000,
L ₁ is a methylene group, an ethylene group, a propylene group, and a phenylene group; and
Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, C ₁ -C ₂₀ alkyl group, and C ₁ -C ₂₀ alkoxy It is selected from a methylene group, an ethylene group, a propylene group, and a phenylene group substituted with one or more of the groups,
a1 is selected from an integer of 0 to 10,
* denotes a binding site with the main chain. delete According to claim 1,
The repeating unit represented by the formula (1) is a negatively charged body represented by the following formula (1-1):
<Formula 1-1>

In Formula 1-1,
For the description of n1, n2 and m1, refer to the bar defined in claim 1,
wherein R ₁₁ to R ₁₈ are a binding site with the side chain represented by Formula 2, hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydra a zino group, a hydrazono group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and a C ₆ -C ₂₀ aryl group; and
_{C 1} -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group -C ₂₀ aryl group; is selected from
However, _{at least one of R 11} to R ₁₈ is a binding site with the side chain represented by Formula 2 above. delete According to claim 1,
Wherein L ₁ is a group represented by any one selected from the following Chemical Formulas 3-1 to 3-4, a negatively charged body:

In Formulas 3-1 to 3-4,
Z ₁ and Z ₂ are each independently, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, C ₁ -C ₂₀ alkyl group, and a C ₁ -C ₂₀ alkoxy group,
d4 is an integer from 0 to 4,
* and *' are binding sites with neighboring atoms. According to claim 1,
The polymer group has a weight average molecular weight (Mw) of 10 kDa to 100 kDa. According to claim 1,
wherein the polymer group is a homopolymer or copolymer. According to claim 1,
wherein the polymer group is selected from polydimethyl siloxane (PDMS), polyimide groups, and combinations thereof. According to claim 1,
A negatively charged body represented by the following formulas A to B:
<Formula A>

<Formula B>

<Formula 4>

In Formulas A to B,
0≤n11≤1, 0≤n12≤1, the sum of n11 and n12 is 1,
P ₁ is selected from the group represented by Formulas B-1 to B-8,
d1 is selected from an integer of 1 to 10,
x is an integer selected from 1 to 50,
R ₂₁ to R ₂₆ are a group represented by Formula 4, hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazo no group, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and a C ₆ -C ₂₀ aryl group; and
_{C 1} -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group -C ₂₀ aryl group; is selected from
c3 is an integer selected from 0 to 3,
c4 is an integer selected from 0 to 4,
L ₃₁ is *-C(R ₃₂ )(R ₃₃ )-*', *-Si(R ₃₂ )(R ₃₃ )-*', *-N(R ₃₂ )-*', *-O-*' , and *-S-*',
a31 is an integer selected from 0 to 5;
R ₃₁ to R ₃₃ are hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, an azide group (-N ₃ ), C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group, -B(Q ₁₁ )(Q ₁₂ ), -N(Q ₁₁ )(Q ₁₂ ), -C (Q ₁₁ )(Q ₁₂ )(Q ₁₃ ), —Si(Q ₁₁ )(Q ₁₂ )(Q ₁₃ ), and —Ge(Q ₁₁ )(Q ₁₂ )(Q ₁₃ ); and
_{C 1} -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group -C ₂₀ aryl group; is selected from
The Q ₁₁ to Q ₁₃ are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group, a hydrazono group, a a zide group (-N ₃ ), a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, and a C ₆ -C ₂₀ aryl group; and
_{C 1} -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, and C ₆ substituted with one or more selected from deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, and a nitro group -C ₂₀ aryl group; is selected from
* and *' are binding sites with neighboring atoms. A triboelectric generator comprising the negatively charged body of any one of claims 1, 3, and 5 to 9. 11. The method of claim 10,
The triboelectric generator has an output value of 16 μA to 70 μA. 11. The method of claim 10,
A triboelectric generator satisfying the following conditions 1 and 2:
<Condition 1>
Q ₁ ≥ 4 × Q ₀
<Condition 2>
Q ₂ ≥ 0.5 × Q ₁
Among the conditions 1 and 2, Q ₀ is the charge amount of the triboelectric generator before charge injection, Q ₁ is the initial charge amount of the triboelectric generator after charge injection, and Q ₂ is the charge amount of the triboelectric generator 2 hours after charge injection. 11. The method of claim 10,
The negatively charged body is a triboelectric generator in the form of a thin film. 14. The method of claim 13,
The thickness of the thin film is 0.1㎛ to 1000㎛ triboelectric generator.

Images