TWI489672B - A colloidal polymer electrolyte - Google Patents

Description

Colloidal polymer electrolyte

The invention relates to a colloidal electrolyte for a dye-sensitized solar cell (DSC) and a preparation method thereof, which are used for solving a liquid electrolyte-based dye-sensitized solar cell, having a package and a long-term use of an electrolyte. There will be a leak.

In the 1990s, Professor Michael Gratzel of Switzerland developed a new type of nano-TiO ₂ solar cell. In 1992, Michael Gratzel et al. immersed in a nano-sized porous electrode with high specific surface area in immersion in organic compounds such as transition metals and Os. The dye is configured to enhance the electrode performance of the Solar cell, and its energy conversion efficiency can reach 10-12%. Most notably, DSSC's total production cost is lower than that of twinned solar cells, the process is simple and it is easy to form a large area, and it can be prepared into a flexible battery with great potential.

Since a dye-sensitized solar cell mainly composed of a liquid electrolyte is used, there is a problem that the package is not easy to be used and the electrolyte may leak during long-term use, and the package material may be deteriorated by irradiation of UV light, resulting in poor stability.

Generally, solid-state or pseudo-solid DSSCs still have lower photoelectric conversion efficiency than liquid electrolytes. In the study of DSSCs, polyvinylidene fluoride-co-trichloroethylene (PVDF-HFP) and its derivatives have been commonly used in solidified liquid electrolytes. Since the fluorine atom of PVDF-HFP has a small ionic radius and high electrical conductivity, it is expected to improve the ionic conductivity of the solid electrolyte, but its conductivity is still not satisfactory, so it is necessary to develop a solid state with better conductivity. Or a colloidal electrolyte.

The present invention is directed to the problem of preparing a colloidal electrolyte, and it is desired to solve the problem of electrolyte encapsulation and leakage under prolonged use, and proposes a colloidal electrolyte having excellent properties.

The present invention relates to a colloidal polymer electrolyte, which is particularly suitable for a colloidal electrolyte of a Dye-Sensitized Solar Cell (DSSC), (1) an olefin-Malay having a repeating unit of the following general formula (I) The acid anhydride (derivative-containing) copolymer is reacted with an imidazole compound of the general formula (II), and further reacted with an anionic compound selected from the general formula (III), (IV) and HBF ₄ or a mixture thereof.

Or (2) reacting an imidazole compound of the following general formula (II) with an anionic compound selected from the general formula (III), (IV) and HBF ₄ or a mixture thereof, and repeating the unit with the general formula (I) The olefin-maleic anhydride (derivative-containing) copolymer reacts.

Wherein R ₁ and R ₁ are a C ₆ -C ₂₀ alkyl group selected from a H atom, a halogen atom, a halogen-substituted or unsubstituted C ₁ -C ₆ alkyl group, or a halogen-substituted or unsubstituted; R ₃ And R ₄ is a C ₆ -C ₂₀ aromatic group selected from a H atom, a halogen atom, a halogen-substituted or unsubstituted C ₁ -C ₆ alkyl group, or a halogen-substituted or unsubstituted. n is an integer greater than one.

Wherein m is an integer of 0 to 30, Y is a reactive functional group selected from the group consisting of NH ₂ , NHR, and OH, and R is a C ₁ -C ₆ alkyl group.

In general formula (III) RX wherein R is C ₁ - C ₂₀ alkyl, X is halogen, and is selected from the group consisting of F, Cl, Br, I, preferably Br, I, more preferably I.

Wherein n is an integer of 1 to 30, and X ₁ and X ₂ are each halogen, and are selected from the group consisting of F, Cl, Br, and I, preferably Br, I, and more preferably I.

The invention further relates to a method for preparing a colloidal polymer electrolyte, which comprises reacting an olefin-maleic anhydride (derivative-containing) copolymer with an imidazole compound to form a plurality of pendant pendant groups containing imidazole, and using the imidazole in the pendant side group. The N moiety in the functional group is reacted with an anionic compound of RX or HBF ₄ or a general formula (IV) or a mixture thereof to form a bond to form a colloidal electrolyte having one and/or more than one anion, wherein Preferably, the bis-anion of the general formula (IV) is used to crosslink the colloidal electrolyte to form a network structure.

Another colloidal polymer electrolyte of the present invention is prepared by reacting an imidazole compound with an anionic compound and reacting with an olefin-maleic anhydride (derivative-containing) copolymer to form a plurality of imidazole pendant pendant groups having an anion or A colloidal electrolyte of a crosslinked structure. The N-site of the imidazole functional group is reacted with an anionic compound of RX or HBF ₄ or a general formula (IV) or a mixture thereof to form an imidazole-based compound having an anionic terminal, which is compatible with an olefin-maleic anhydride. (containing a derivative) a functional group reacted with a copolymer to form a colloidal electrolyte having one and/or more than one anion, wherein preferably comprising a general anion of formula (IV) The colloidal electrolyte crosslinks to form a network structure.

The anionic compound of the formula (III) of the present invention may, for example, be a halogenated methane, an halogenated ethane, a halogenated propane or the like, or a C ₁ - C ₂₀ halogenane, preferably an iodoalkane.

The dianion compound of the formula (IV) of the present invention may, for example, be selected from the group consisting of dihaloethane, dihalopropane, dihalobutane, dihalopentane, dihalohexane, dihaloheptane, dihalooctane, A dihalohalane, a dihalodecane, or a mixture thereof, etc., is a C ₂ -C ₃₂ dihaloalkane, preferably a diiodane.

The imidazole-based compound of the formula (II) of the present invention has a reactive functional group reactive with a carboxyl group, for example, selected from the group consisting of NH ₂ , NHR, and OH, wherein R is a C ₁ -C ₆ alkyl group. The obtained electrolyte utilizes an anion thereof as a conductive group, and utilizes its colloidal state to solve the problem that the current liquid electrolyte is not easily packaged and leaked. The resulting electrolyte film has good electrical conductivity and energy conversion efficiency of DSSC.

Photosensitizing the dye due to the illumination after the jump to the excited state, shall electrolyte supplying electrons it back to the ground state to reach the battery cycle, commonly used electrolyte is I ₃ ^- a liquid electrolyte, due to package easily, prone to leakage of the problem, the present invention In one embodiment, an olefin-maleic anhydride (derivative-containing) copolymer is reacted with aminopropylimidazole to form a pendant pendant group having a plurality of guanidinopropyl imidazoles, and N in the imidazole functional group contained in the pendant pendant group is used. The iodoalkane reacts to form a bond, wherein the diiodoalin is included, and the electrolyte can be crosslinked to have a network structure, and the electron film is supplied to the dye film by iodide ions in the network structure, and charge transfer is performed to complete the DSSC working cycle. . The formation of the mesh structure has the advantages of improving the conductive path, increasing the structural stability, and the service life, which is a feature not currently available in other colloidal electrolytes.

The colloidal polymer electrolyte of the present invention may further contain nano particles such as nano-sized TiO ₂ , nano carbon spheres or carbon tubes, TiN, AlN nanoparticles and graphite as fillers to enhance the properties of the colloidal electrolyte. It can improve the photoelectric conversion efficiency of DSSCs.

The colloidal polymer electrolyte of the present invention may further contain a stabilizer such as iodine (LiI), 4-tert-butylpyridine (TBP), or N-butylbenzimidazole (N- Butyl benzimidazole (NBB), and 1-methylbenzimida (NMBI) are equal to the above-mentioned colloidal polymer electrolyte (PGE) to form a composite polymer electrolyte, which acts mainly to stabilize iodine in the electrolyte due to 4- Laid - butylpyridine may be the upper surface of the TiO ₂ film is not fully coordinated with Ti on the pyridine ring by N, hinder the conduction band electrons in the surface of the TiO ₂ thin film electrolyte I ^3- composite, can significantly improve the sun The open circuit voltage, fill factor and photoelectric conversion efficiency of the battery.

The ionic liquid electrolyte, the double ion electrolyte, and the mutually compatible electrolyte may also be mixed in the electrolyte. The dual ionic liquid electrolyte, the mutually compatible electrolyte and the stabilizer are described in Chinese Patent No. 97149632.

For example, in the colloidal polymer electrolyte (PGE) of the present invention, a substance comprising: lithium iodide, an ionic liquid of an iodine molecule, and a mutually compatible electrolytic layer: 1-propyl-2,3-dimethylimidazolium iodide ( 1-propyl-2,3-dimethylimidazolium iodide, PDMII), 1-propyl-3-methylimidazolium iodide (PMII), 1-ethyl-3-methylimidazolium iodide (1-propyl-3-methylimidazolium iodide, PMII) 1-ethyl-3-methylimidazolium iodide, EMII), 1,3-dimethylimidazolium iodide (DMII), 1-allyl-3-methylimidazolium iodide (1-allyl-3) -methylimidazolium iodide, AMII) solution, concentration 0.01 g ~ 1 g / 1 g PGE, other electrolyte solvents selected from: ethanol, acetonitrile, methoxy acetonitrile, propionitrile, 3-methoxypropyl (MPN), Ethyl carbonate, propyl carbonate, ethylene carbonate or 2-ethyl-4-methylimidazole is dissolved in the electrolyte of the present invention after dissolving the above electrolyte to prepare a composite colloidal polymer electrolyte.

The present invention further provides a dye-sensitized solar cell having a structure as shown in FIG. 1, the dye-sensitized solar cell 10 comprising: a working electrode 20; an auxiliary electrode 40 on the opposite side of the working electrode; An electrolyte component 30 comprising the colloidal polymer electrolyte of the present invention, the working electrode 20 comprising an electrode substrate 21 and an oxide semiconductor porous film 22 formed on the electrode substrate 21, wherein the electrode substrate 21 further comprises a transparent The material of the substrate 21a is, for example, glass, a transparent plastic substrate, a ceramic abrasive plate, or a flexible transparent plastic film, and the conductive layer 21b contains tin-doped indium oxide (ITO), tin dioxide (tin). Tin oxide, SnO ₂ ), fluorine-doped tin oxide (FTO) or a combination thereof. The oxide semiconductor porous film 22 includes titanium oxide (TiO ₂ ), tin dioxide (SnO ₂ , tungsten oxide (WO ₃ ), zinc oxide (ZnO), niobium oxide (Nb ₂ O ₅ ), or a combination thereof, preferably. It is titanium dioxide (TiO ₂ ).

The oxide semiconductor porous film 22 functions to adsorb a photosensitizing dye, and the dye sensitizer may optionally contain a Ruthenium-complex as a dye, for example, N3 dye (Ru(NCS) ₂ ), N719. Dyes (RuL ₂ (NCS) ₂ : 2TBA), N749 (black dye), C101, and the like. Or selected from other organic dyes (anthraquinone dyes classified as organometallic complex dyes), including black rice, thorns, bauhinia, yellow thorns, organic dyes D149 (D), Mercurochrome (M), Eosin Y (E ), Rose bengal (R), Coumarin 343 (C), porphyrin, phthalocyanine or coumarin, or a mixture thereof, in combination with two or more dye sensitizers Improve efficiency.

The auxiliary electrode 40 includes a film on a non-conductor substrate and a conductive film formed thereon, such as platinum, carbon, graphite, graphene, or the like, on an ITO, FTO or the like.

Property determination

1. The photoelectric characteristics of the battery were measured under a solar light simulator (Newport, Oriel class A, 91160A) under 100% (AM 1.5, 100 mW/cm ² ) illumination, and the photoelectric conversion efficiency % was measured.

2. Determination of the conductivity of the electrolyte

The present invention utilizes an electrolyte measurement module to measure electrical conductivity. The electrolyte is sandwiched between the two electrodes and fixed by a clamp. The working electrode and the reference electrode are connected to both sides of the electrode, the fixed amplitude is 10 mV, the scanning frequency is 1 M Hz to 1000 Hz, and the impedance value of the film is measured at a temperature of 30 ° C. The impedance data is substituted into the equation to obtain the ion conductivity value.

σ: conductivity (S/cm)

d: film thickness (cm)

R: film resistance value (Ω)

A: electrode area (cm ² )

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.

Preparation of colloidal polymer electrolyte Synthesis Example 1

Copoly-ethylene/maleic anhydride (co-PE/MA) and 1-3-aminopropylimidazole (AI) (functional molar ratio of about 1 :1) Mixing in a deionized water solution, adding a few drops of tin laurate (T-12), and reacting with a magnet for about 24 hours to form a semi-finished product having a plurality of pendant molecules of amidoxime-imidazole, referred to as PE/MA. -AI, and then reacted with about 1:1 (imidazole: iodine) molar ratio of Diiodo pentane (DIP) for about 30 minutes to form a bond to obtain a colloidal polymer electrolyte, referred to as PE/MA- AI/DIP, uniformed into a flatware, dried to form a film, and tested for properties.

Synthesis Example 2

Copoly-styrene/maleic anhydride (co-PS/MA) and 1-(3-Aminopropyl)imidazole (AI) (functional molybdenum ratio) 1:1) Mixing in deionized water solution, adding a few drops of tin laurate (T-12), and stirring with a magnet for about 24 hours to form a semi-finished product with a plurality of pendant amine groups of amidoxime-imidazole, referred to as PS/ MA-AI is further reacted with Diiodo pentane (DIP) of about 1:1.2 (imidazole: iodine) for about 30 minutes to form a bond to obtain a colloidal polymer electrolyte, abbreviated as PS/MA. -AI/DIP, homogenize it into a flatware, dry it into a film, and conduct a property test.

Synthesis Example 3

Copoly-propylene/maleic anhydride anhydride (co-PP/MA) and 1-(3-Hydroylpropyl)imidazole (HI) (functional molybdenum ratio) 1:1) mixed in a deionized water solution, and stirred with a magnet for about 24 hours to form a semi-finished product having a plurality of pendant pendant groups of ester propyl imidazole, abbreviated as PP/MA-HI, and then about 1:1.1 (imidazole: Iodine) Mobi is reacted with Diiodo decane (DID) for about 30 minutes to form a bond to obtain a colloidal polymer electrolyte, abbreviated as PP/MA-HI/DID-1, which is uniformed into the plate. The vessel is dried and made into a film for property testing.

Synthesis Example 4

1-(3-Hydroylpropyl)imidazole (HI) is reacted with about 1:1 (imidazole: iodine) molar ratio of Diiodo decane (DID) for about 30 minutes. Forming a semi-finished product of a bond, and then mixing with a propylene-maleic anhydride anhydride (co-PP/MA) (functional molar ratio of about 1:1) in a deionized aqueous solution to a magnet Stirring for about 24 hours to form a colloidal polymer electrolyte containing a plurality of ester propyl groups containing anionic imidazole pendant side groups, abbreviated as PP/MA-HI/DID-2, which is uniformly mixed into a flatware vessel, and dried. Form a film and conduct a property test.

Synthesis Example 5

Copoly-styrene/maleic anhydride (co-PS/MA) and 1-(3-Aminopropyl)imidazole (AI) (functional molybdenum ratio) 1:1) Mixing in deionized water solution, adding a few drops of tin laurate (T-12), and stirring with a magnet for about 24 hours to form a semi-finished product with a plurality of pendant amine groups of amidoxime-imidazole, referred to as PS/ MA-AI is further reacted with about 1:1.2 (imidazole: iodine) molar ratio of iodide Methane (Iodide Methane, IM/Diiodo pentane, DIP) for about 30 minutes to form a bond. The colloidal polymer electrolyte, referred to as PS/MA-AI/(IM/DIP), is evenly distributed into a flatware vessel, dried to form a film, and tested for properties.

Synthesis Example 6

Copoly-ethylene/maleic anhydride (co-PE/MA) and 1-3-aminopropylimidazole (AI) (functional molar ratio of about 1 :1) Mixing in a deionized water solution, adding a few drops of tin laurate (T-12), and reacting with a magnet for about 24 hours to form a semi-finished product having a plurality of pendant molecules of amidoxime-imidazole, referred to as PE/MA. -AI, and reacted with about 1:1 (imidazole: HBF ₄ ) molar ratio of HBF ₄ (abbreviation, BF) for about 30 minutes to form a bond to obtain a colloidal polymer electrolyte, referred to as PE/MA-AI/BF. , it is evenly poured into a flatware, dried to form a film, and tested for properties.

Synthesis Example 7

Copoly-ethylene/maleic anhydride (co-PE/MA) and 1-3-aminopropylimidazole (AI) (functional molar ratio of about 1 :1) Mixing in a deionized water solution, adding a few drops of tin laurate (T-12), and reacting with a magnet for about 24 hours to form a semi-finished product having a plurality of pendant molecules of amidoxime-imidazole, referred to as PE/MA. -AI, and reacted with about 1 : 1 (imidazole: methyl iodide) molar ratio of Iodide Methane (IM) for about 30 minutes to form a bond to obtain a colloidal polymer electrolyte, referred to as PE/MA- AI/IM, homogenize it into a flatware, dry it into a film, and conduct a property test.

Synthesis Example 8

Copoly-ethylene/maleic anhydride (co-PE/MA) and 1-3-aminopropylimidazole (AI) (functional molar ratio of about 1 :1) Mixing in a deionized water solution, adding a few drops of tin laurate (T-12), and reacting with a magnet for about 24 hours to form a semi-finished product having a plurality of pendant molecules of amidoxime-imidazole, referred to as PE/MA. -AI, and reacted with about 1:1 (imidazole: iodane) molar ratio of diiodo propane (DIPp) for about 30 minutes to form a bond to obtain colloidal polymer electrolysis. Quality, referred to as PE/MA-AI/DIPp, it is evenly distributed into a flatware, dried to form a film, and tested for properties.

Synthesis Example 9

Copoly-ethylene/maleic anhydride (co-PE/MA) and 1-3-aminopropylimidazole (AI) (functional molar ratio of about 1 :1) Mixing in a deionized water solution, adding a few drops of tin laurate (T-12), and reacting with a magnet for about 24 hours to form a semi-finished product having a plurality of pendant molecules of amidoxime-imidazole, referred to as PE/MA. -AI, adding 0.5M 4-tert-butylpyridine (TBP) and a small amount of carbon nanotubes to mix uniformly, and then reacting with about 1:1 (imidazole: iodine) molar ratio of Diiodo pentane (DIP) After 30 minutes, a bond was formed to obtain a colloidal polymer electrolyte, abbreviated as PE/MA-AI/DIP/TBP, which was uniformly introduced into a flatware vessel, dried to form a film, and tested for properties.

Synthesis Example 10

Copoly-ethylene/maleic anhydride (co-PE/MA) and 1-3-aminopropylimidazole (AI) (functional molar ratio of about 1 :1) Mixing in a deionized water solution, adding a few drops of tin laurate (T-12), and reacting with a magnet for about 24 hours to form a semi-finished product having a plurality of pendant molecules of amidoxime-imidazole, referred to as PE/MA. -AI, adding 0.5M 4-tetrabutylpyridine (TBP), and a small amount of carbon nanotubes (CNT) mixed uniformly, and then with about 1:1 (imidazole: iodine) molar ratio of pentanediiodide (Diiodo) Pentane, DIP) reacts for about 30 minutes to form a bond to obtain a colloidal polymer electrolyte, abbreviated as PE/MA-AI/DIP/TBP/CNT-1, which is uniformly mixed into a plate vessel and dried to form a film. Nature test.

Synthesis Example 11

Copoly-ethylene/maleic anhydride (co-PE/MA) and 1-3-aminopropylimidazole (1-(3-Aminopropyl)imidazole, AI) (the functional group molar ratio is about 1:1) is mixed in a deionized water solution, and a few drops of tin laurate (T-12) are added, and the magnet is stirred to react about 24 times. Hours, forming a semi-finished product with a plurality of pendant amine groups of amidoxime propyl imide, referred to as PE/MA-AI, adding 0.1 M lithium iodide, 0.05 M iodine molecular solution, 0.5 M 4-tetrabutyl pyridine (TBP), and A small amount of carbon nanotubes (CNT) are uniformly mixed, and then reacted with about 1:1 (imidazole: iodine) molar ratio of Diiodo pentane (DIP) for about 30 minutes to form a bond to obtain a colloidal polymer. The electrolyte, referred to as PE/MA-AI/DIP/TBP/CNT-2, is evenly distributed into a flatware vessel, dried to form a film, and tested for properties.

Comparative example 1

The electrolyte was prepared by dissolving LiPF ₆ in a solvent of (ethyl carbonate/propyl carbonate) into a 1 M LiPF ₆ ion solution.

Comparative example 2

The colloidal polymer electrolyte (PGE) was changed to Poly(methyl methacrylate-co-methacrylate acid)/poly(ethylene glycol)[P(MMA-co-MAA)/PEG], and KI/I ₂ trimethoxypropionitrile was added. A solution of (3-methoxypropionitrile, MPN) was prepared as a colloidal polymer electrolyte of GEL:I(KI/I ₂ )=10:1.

The dye sensitizer can be selected by using N719 钌 organometallic complex (Ruthenium-complex) as a dye.

The titanium dioxide photoelectrode and the counter electrode of the platinum-plated film were placed in a colloidal electrolytic film, sandwiched by a 60 μm spacer package, and the electrodes were heated and bonded at 100 °C.

Or the counter electrode of the titanium dioxide photoelectrode and the platinum-plated film is sandwiched by a 60 μm spacer package, and the two electrodes are heated and bonded at 100 ° C and left with two holes for pouring the colloidal electrolyte precursor. mixture. The vacuum pump is used to infiltrate the colloidal polymer electrolyte mixed solution, heated to form a network polymer electrolyte, and the solvent is removed, and the two holes are sealed with epoxy resin to form a battery.

The photoelectric characteristics of the battery were measured under a solar light simulator under 100% (AM 1.5, 100 mW/cm ² ) illumination, and the photoelectric conversion efficiency % was measured as shown in Table 1.

Conductivity test

The synthesized colloidal polymer electrolyte was made into a film, and the conductivity test was carried out in a colloidal state. The conductivity values are shown in Table 1.

Industrial availability

The colloidal polymer electrolyte of the invention exhibits excellent conductivity value, about 6~9×10 ^-3 S/cm, which is higher than that of a general colloidal or solid electrolyte, and the photoelectricity of the dye-sensitized solar cell The conversion efficiency is about 5% or more, and the photoelectric conversion efficiency of the dye-sensitized solar cell composed of the conventional ionic liquid is equivalent to or more excellent.

The colloidal polymer electrolyte material of the present invention should have excellent electronic conductivity, easy to be packaged, and free from leakage, and can improve the disadvantages of the first two points, and therefore, can provide High-efficiency dye-sensitized solar cells and their applications in various solar cells.

While the present invention has been described above in terms of several preferred embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. The scope of the present invention is defined by the scope of the appended claims.

10‧‧‧Dye-sensitized solar cells

20‧‧‧Working electrode

21‧‧‧Electrode substrate

21a‧‧‧Transparent substrate

21b‧‧‧ Conductive layer

22‧‧‧Oxide semiconductor porous film

30‧‧‧ Electrolytes

40‧‧‧Auxiliary electrode

Fig. 1 is a schematic view showing the structure of a dye-sensitized solar cell of the present invention.

10‧‧‧Dye-sensitized solar cells

20‧‧‧Working electrode

21‧‧‧Electrode substrate

21a‧‧‧Transparent substrate

21b‧‧‧ Conductive layer

22‧‧‧Oxide semiconductor porous film

30‧‧‧ Electrolytes

40‧‧‧Auxiliary electrode

Claims (10)

A colloidal polymer electrolyte obtained by reacting an olefin-maleic anhydride (derivative-containing) copolymer of the following general formula (I) with an imidazole compound of the general formula (II), and further selected from the general formula ( The reaction of an anionic compound of III), (IV) and HBF ₄ or a mixture thereof, Wherein R ₁ and R ₂ are a C ₆ -C ₂₀ alkyl group selected from a H atom, a halogen atom, a halogen-substituted or unsubstituted C ₁ -C ₆ alkyl group, or a halogen-substituted or unsubstituted; R ₃ And R ₄ is a C ₆ -C ₂₀ alkyl group selected from a H atom, a halogen atom, a halogen-substituted or unsubstituted C ₁ -C ₆ alkyl group, or a halogen-substituted or unsubstituted; n is an integer greater than 1 ; Wherein m is a 0 to 30 integer, Y is a reactive functional group selected from the group consisting of NH ₂ , NHR, and OH groups, and R is a C ₁ -C ₆ alkyl group; and general formula (III) RX wherein R is C ₁ -C ₂₀ alkyl, X is halogen, selected from F, Cl, Br, I; Wherein n is an integer from 1 to 30, and X ₁ and X ₂ are each a halogen selected from the group consisting of F, Cl, Br, and I. A colloidal polymer electrolyte obtained by reacting an imidazole compound of the following general formula (II) with an anionic compound selected from the general formula (III), (IV) and HBF ₄ or a mixture thereof, and then having a weight with the general formula (I) a unit of olefin-maleic anhydride (containing a derivative) copolymer, Wherein R ₁ and R ₂ are a C ₆ -C ₂₀ alkyl group selected from a H atom, a halogen atom, a halogen-substituted or unsubstituted C ₁ -C ₆ alkyl group, or a halogen-substituted or unsubstituted; R ₃ And R ₄ is a C ₆ -C ₂₀ alkyl group selected from a H atom, a halogen atom, a halogen-substituted or unsubstituted C ₁ -C ₆ alkyl group, or a halogen-substituted or unsubstituted; n is an integer greater than 1 ; Wherein m is a 0 to 30 integer, Y is a reactive functional group selected from the group consisting of NH ₂ , NHR, and OH groups, and R is a C ₁ -C ₆ alkyl group; and general formula (III) RX wherein R is C ₁ -C ₂₀ alkyl, X is halogen, selected from F, Cl, Br, I; Wherein n is an integer from 1 to 30, and X ₁ and X ₂ are each halogen, and are selected from the group consisting of F, Cl, Br, and I. The colloidal polymer electrolyte according to claim 1 or 2, further comprising nano particles such as nano-sized TiO ₂ , carbon spheres, carbon tubes, TiN, AlN and graphite as a filler to form a colloidal high. Molecular electrolyte complexes improve the photoelectric conversion efficiency of DSSCs. The colloidal polymer electrolyte according to claim 1 or 2, further comprising a stabilizer, which may be selected from the group consisting of 4-tert-butylpyridine, iodine (LiI), 4-tert-butylpyridine, and N-butyl. Mixture of benzimidazole, 1-methylbenzimidazole or the like. The colloidal polymer electrolyte according to claim 1 or 2, wherein the colloidal polymer electrolyte further comprises a mixed ionic liquid electrolyte, a diionic electrolyte, and other mutually compatible electrolytes to form a colloidal polymer electrolyte complex. , selected from the group consisting of: iodine molecule / lithium iodide, 1-propyl-2,3-dimethylimidazolium iodide, 1-propyl-3-methylimidazolium iodide, 1-ethyl-3-methylimidazolium iodide, A solution of 1,3-dimethylimidazolium iodide, 1-allyl-3-methylimidazolium iodide. A method for preparing a colloidal polymer electrolyte, which comprises reacting a copolymer of an olefin-maleic anhydride and/or a derivative thereof with an imidazole compound to form a plurality of pendant pendant groups containing imidazole, and using the imidazole in the pendant side group The N moiety in the functional group is reacted with an anionic compound of RX or HBF ₄ or a general formula (IV) or a mixture thereof to form a bond to form a colloidal electrolyte having a functional group reactive with a carboxyl group, the anion The compound comprises at least the general dianion compound of the formula (IV), wherein R (wherein R is a C ₁ -C ₂₀ alkyl group, X is a halogen, selected from the group consisting of F, Cl, Br, I; Wherein n is an integer from 1 to 30, and X ₁ and X ₂ are each halogen, and are selected from the group consisting of F, Cl, Br, and I. The invention relates to a method for preparing a colloidal polymer electrolyte, which comprises reacting an imidazole compound with an anionic compound, and reacting with a copolymer of olefin-maleic anhydride and/or a derivative thereof to form a plurality of imidazole pendant pendant groups having an anion or a colloidal electrolyte having a crosslinkable structure having a functional group reactive with a carboxyl group of a copolymer of olefin-maleic anhydride and/or a derivative thereof, using an N site in the imidazole functional group and RX or HBF ₄ or The anionic compound of the general formula (IV) or a mixture thereof is reacted to form an imidazole compound having an anionic tail which contains at least the general anion compound of the formula (IV), and the general formula (III) RX wherein R is C ₁ ~ C ₂₀ alkyl, X is halogen, selected from F, Cl, Br, I; Wherein n is an integer from 1 to 30, and X ₁ and X ₂ are each halogen, and are selected from the group consisting of F, Cl, Br, and I. A dye-sensitized solar cell comprising: a working electrode; an auxiliary electrode on an opposite side of the working electrode; and an electrolyte component comprising an electrode substrate and an oxide semiconductor formed on the electrode substrate a porous film for adsorbing a dye, characterized in that the electrolyte component comprises a colloidal polymer electrolyte according to any one of claims 1 to 5, or a gel according to any one of claims 6 to 7. The electrolyte obtained by the method for preparing a polymer electrolyte. The dye-sensitized solar cell of claim 8, wherein the electrode substrate comprises a transparent substrate and a conductive layer, and the transparent substrate is selected from the group consisting of glass, a transparent plastic substrate, a ceramic abrasive plate, or a flexible transparent substrate. a plastic film; the conductive layer comprising tin-doped indium oxide (ITO), tin oxide (SnO ₂ ), fluorine-doped tin oxide (FTO) Or a combination of the above; the auxiliary electrode comprises a non-conductor substrate and a conductive film formed thereon, the conductive film being selected from the group consisting of platinum, carbon, graphite, and graphene materials on ITO, FTO substrates. The dye-sensitized solar cell of claim 8, wherein the oxide semiconductor porous film is selected from the group consisting of titanium dioxide (TiO ₂ ), tin dioxide (SnO ₂ , tungsten oxide (WO ₃ ), zinc oxide (ZnO) , cerium oxide (Nb ₂ O ₅ ), or a combination thereof; wherein the dye sensitizer is selected from the group consisting of: N3 dye (Ru(NCS) ₂ ), N719 dye (RuL ₂ (NCS) ₂ : 2TBA), N749 dye (black dye), etc., or other organic dyes selected from the group consisting of: black rice, thorns, bauhinia, thorns, porphyrin, phthalocyanine, coumarin, or The combination of these, etc.