TW201317265A - With high conductivity of Polyethylene Glycols copolymer - Google Patents

Abstract

Supercapacitor includes a gel electrolyte is provided. The gel electrolyte is one selected from a group consisting of a Polyethylene Glycols copolymer, a acrylnitrile copolymer and a plasticizer.

Description

Highly conductive polyethylene glycol copolymer

The present invention relates to a colloidal polymer electrolyte for a highly conductive copolymer of a supercapacitor, especially comprising a polyethylene glycol (PEG) copolymer or an acrylonitrile copolymer, which has high conductivity. As a colloidal polymer electrolyte of a supercapacitor.

In general, a polymer electrolyte is a coordination of a positive ion of a polymer and a salt, and is dissociated into a free ion by a positive ion and a negative ion, and a free ion migrates as the polymer moves. The polymer electrolyte can be classified into a solid polymer electrolyte (SPE), a gel-type polymer electrolyte (GPE, GE), and a composite polymer electrolyte (CPE) with an inorganic substance added thereto. . A polymer electrolyte membrane has been prepared by mixing polyoxyethylene (PEO) with a lithium salt for many years. In addition, polydimethylsiloxanes (PDMS) and polystyrene (PS) can also be used as materials for polymer electrolytes.

Lithium ions react with the unpaired electron pair of the polar group on the polymer backbone, and dissociate from the negative ion to form a coordination or a solvent. However, the crystalline polymer tends to reduce the flexibility of the molecular chain, and the solid polymer electrolyte of polyoxyethylene has a significantly poor room temperature conductivity and a softer polydimethyl siloxane conductivity. Also, because the glass transition point is too low, the dimensional stability is poor, and it is not taken seriously.

However, linear polyether polymer materials such as polyoxyethylene (PEO) crystallize at low temperatures (<60 ° C), which leads to a decrease in conductivity and lithium ion conductivity; at high temperatures (>60 ° C), electrolyte membranes are lost due to melting. Mechanical strength. Therefore, a polymer chain having a specific physicochemical property is generally introduced to reduce the crystallinity of the PEO polymer and increase the mechanical strength at a high temperature.

In recent years, the solid polymer electrolyte has insufficient conductivity, and some polar solvents of low molecular weight, also known as plasticizers or plasticizers, are added to the polymer electrolyte to form a colloidal form, and the semi-crystalline polymer electrolyte is converted into an amorphous type. (amorphous), to reduce the energy required to move ions on the polymer chain, increase the mobility of ions, called colloidal polymer electrolyte or colloidal polymer electrolyte. The most common polyacrylonitrile (PAN) colloidal polymer electrolyte series is added to low volatility and high dielectric constant solvents, such as propylene carbonate (PC), diethylene carbonate (DEC). Ethylene carbonate (EC) and polyurethane (PU) are plasticizers to improve conductivity. For example, in the 2007 Ph.D. thesis of Liang Yuhao, it was revealed that the addition of propylene carbonate (PC) plasticizer, polyacrylonitrile (PAN) and polyethylene glycol (PEG) by free radical polymerization to make a copolymer. The colloidal electrolyte only increases the conductivity to the range of 10 ^-5.2 to 10 ^-6 S/cm.

As a result of the job, the inventor, in view of the lack of prior art, thought of and improved the idea of invention, and finally invented the "highly conductive polyethylene glycol copolymer" in this case.

The main purpose of the present invention is to provide a colloidal polymer electrolyte comprising: a polyethylene glycol (PEG) copolymer; a plasticizer and a colloidal copolymer formed from the copolymer, and a lithium salt and the An electrolyte formed by a colloidal copolymer.

Another main object of the present invention is to provide a colloidal polymer electrolyte comprising: an acrylnitrile (AN) copolymer-plasticizer and a colloidal copolymer formed from the copolymer, and a lithium salt and The electrolyte formed by the colloidal copolymer.

The above-mentioned polyethylene glycol (PEG) series-containing copolymer may be selected from poly(vinylidene fluoride, PVDF)-hexafluoropropylene (HFP). (PEG-(PVDF-co-PHFP), polyethylene glycol-glycidyl methacrylate (GMA)-methyl methacrylate (MMA) is abbreviated as ((PEG-b-GMA) )-co-MMA), polyvinyl alcohol (PVA)-polyethylene glycol (abbreviated as (PVA-b-PEG), polypropylene-polyethylene glycol-polypropylene (polypropylene glycol) PPG) abbreviated as (PPG-PEG-PPG), polymethyl methacrylate-VAc-polyethylene glycol diacrylate (PEGDA) ((PMMA-PVAc)-co-PEGDA), polyethylene glycol-graft copolymerization-polymethyl acrylate (PEG-g-PMA), polyethylene glycol-graft copolymerization-polymethyl methacrylate ( PEG-g-PMMA) or PP-PEG-PPG diamine, 3-methoxypropyl propyl glycidyl ether ), a cross-linked copolymer of tetraethoxysilane (cros) One of a group of one or a combination of slink copolymers.

The above acrylonitrile-containing copolymer may be selected from the group consisting of polyacrylonitrile-polyethylene glycol-polyacrylonitrile (PAN-PEG-PAN), polyacrylonitrile-polyethylene glycol (PAN-PEG), and polyethylene. One of a group consisting of one of alcohol-polyacrylonitrile-polyethylene glycol (PEG-PAN-PEG), polyacrylonitrile-polyacrylic acid (PAN-PAA) copolymer, or a combination thereof.

The plasticizer is selected from the group consisting of dimethylformamide (DMF), ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC) and γ. One of -butyrolactone (γ-BL).

Regardless of the preparation method of the polyethylene glycol series or the acrylonitrile series in the present invention, a polymer is synthesized from a monomer according to the properties of each copolymer, and thus conventional addition polymerization, condensation polymerization, and ion are generally known. Polymerization, radical polymerization, step-reaction polymerization, and the like can be applied.

Another main object of the present invention is to provide a method for producing a colloidal polymer electrolyte, comprising: providing a polyethylene glycol (PEG)-containing compound; and polymerizing the polyethylene glycol compound with a compound selected from the group consisting of From an acrylic compound, an alkenyl compound, a decane compound or a polyurethane (PU); mixing a plasticizer and a lithium salt to form a colloidal electrolyte.

The above acrylic compound may be selected from the group consisting of glycidyl methacrylate (GMA), methyl methacrylate (MMA), poly(ethylene glycol) diacrylate (PEGDA). , poly methacrylate (PMA), polymethyl methacrylate (PMMA) or polypropylene-polyethylene glycol-polypropylene diamine (PPG-PEG-PPG diamine) or One of the groups that make up the combination. The above alkenyl compound may be selected from polyacrylonitrile (PAN) poly(vinylidene fluoride (PVDF), hexafluoropropylene (HFP), polyvinyl alcohol (PVA), polyacetic acid. One of a group consisting of vinyl acetate (VAc), polypropylene (PPG) or polypropylene propylene glycol diamine or a combination thereof.

The above decane compound may be selected from the group consisting of 3-(trimethoxysilyl)propyl glycidyl ether and a cross-linked copolymer of tetraethoxysilane. One of a group of one or a combination thereof. Or polyurethane (PU).

For example, the preparation of PAN-b-PEG-b-PAN copolymer is prepared by free-radical polymerization using ceric ammonium nitrate (CAN) as a redox radical in a nitric acid solution. The initiator of the polymerization. First, the PEG is reacted with the initiator to generate free radicals at both ends of the PEG chain, and the radicals at both ends are reacted with the acrylonitrile (AN) monomer to finally obtain the PAN-b-PEG-b-PAN product. Based on the polymerization method, radicals are generated at both ends of the PEG chain, and Fourier Transform Infrared Spectroscopy (FT-IR) and ¹ H-NMR are performed by a wave number range of 4000 cm ^-1 to 400 cm ^-1 . Nuclear magnetic resonance spectroscopy for polymer structure analysis, although the final product may have PAN-b-PEG-b-PAN, PEG-b-PAN-b-PEG-b-PAN-b-PEG, PEG-b-PAN, etc. The state appeared, but the final product type was dominated by PAN-b-PEG-b-PAN. Or a sol-gel condensation polymerization method for synthesizing polypropylene-polyethylene glycol-polypropylene diamine, 3-glycidoxypropyltrimethoxydecane, tetraethoxyanthracene Crosslinking copolymer.

The lithium battery electrolyte membrane is prepared by mixing dimethylformamide (DMF) and lithium perchlorate (LiClO ₄ ) with the above-mentioned copolymer, and the plasticizer has (a) low melting point (-61 ° C): At low temperature (-20 ° C), there is no crystallization, and the ability to plasticize the polymer copolymer at a low temperature is maintained, so that the colloidal electrolyte maintains high conductivity characteristics.

(b) High boiling point (153 ° C): Plasticizers are not easily vaporized in the usual temperature range, which can improve the temperature range of lithium ion batteries and reduce the safety of lithium batteries.

(c) High dielectric constant (36): Various lithium salts are more likely to be dissociated from the polymer electrolyte, and associated with the polymer chain, such as association, de-association and transport.

(d) High lithium ion association ability: dimethylformamide (DMF) compared to propylene carbonate (PC), diethyl carbonate (DEC) plasticizer, dimethylformamide and lithium The ions have a high association ability, which makes the electrolyte membrane have better lithium ion conductivity and conductivity value.

In the design of lithium-ion batteries, the world's major battery manufacturers, in addition to considering safety, still hope to achieve the goals of small size, light weight, high energy density, low cost and environmentally friendly properties. In addition to affecting the lithium ion conduction rate, the electrolyte membrane of a lithium ion battery also relates to lithium ion battery characteristics such as cycle life, use potential, low temperature discharge, charging time, and safety characteristics. The key material of the electrolyte membrane battery for lithium ion batteries.

When the ion conduction mechanism between the electrolyte membrane of the lithium ion battery and the electrode interface is improved and improved, the irreversible charge and discharge (during the cycle), the dendritic lithium formation, and the avoidance of piercing the separator can be reduced. The short circuit within the contact of the negative electrode effectively improves the cycle performance and reduces the risk factors of combustion and explosion.

In the future, for the application of electric vehicles, industrial machinery and fixed-type storage systems, lithium-ion batteries will be developed towards medium and large-scale technologies and products. Due to its high energy density, high power density and long life, lithium-ion batteries have become a key factor in the development of 3C products, electric vehicles and energy storage systems. The competitive advantages of lithium-ion batteries have become obvious.

Four indicators, such as high energy, high power, high safety and long service life, will be the key to the development of medium and large lithium-ion battery technology in the future. The cost reduction will be the key to the commercialization of medium and large lithium batteries. The subject, and the important direction to solve the cost problem, may focus on the development of key materials for the 20% cost lithium battery electrolyte membrane.

The above described objects, features, and advantages of the present invention will become more apparent and understood.

A polyacrylonitrile-polyethylene glycol-polyacrylonitrile (PAN-PEG-PAN) copolymer prepared according to the examples, having a structural formula as shown in the first figure, wherein xyz is a natural number greater than 1, and additionally doped A lithium salt such as lithium perchlorate to form a colloidal polymer electrolyte, which provides an electrolyte and a separator. As shown in the second figure, polyacrylonitrile-polyethylene glycol-polyacrylonitrile (PAN-PEG-PAN) Fourier transform infrared spectroscopy can confirm PAN300-b-PEG1K-b-PAN300 with PEG 1K series as an example. Copolymers such as PAN30-b-PEG1K-b-PAN30, PAN50-b-PEG1K-b-PAN50 and PAN150-b-PEG1K-b-PAN150 have a cyano (CN) wave number position (2243 cm ^-1 ) and an ether group (COC) Asymmetric stretching vibration wave position (1254 cm ^-1 ), ether-based symmetric stretching vibration wave position (1077 cm ^-1 ). Hydrogen nuclear magnetic resonance spectroscopy ( ¹ H-NMR) using PAN30-b-PEG1K-b-PAN30 as an example confirms that the group represented by the chemical shift position of 3.3-3.6 ppm is the ether group of the PEG segment (CH _{2 ).} CH ₂ O), the chemical shift position of 2.0-2.3 ppm represents the CH group of the PAN segment, and the chemical shift position of 3.0-3.2 ppm represents the CH ₂ group of the PAN segment.

In order to understand the difference and performance between the colloidal polymer electrolyte (GE) prepared by (PAN-PEG-PAN) and the conventional liquid electrolyte (LE), the following comparisons were made by electrochemical tests.

The third graph (a) and the third graph (b) respectively show a conventional liquid electrolyte and the colloidal polymer electrolyte of the present invention, which are based on cyclic voltammetry at low speed (10 mVs ^-1 ) to high speed (2000 mVs ^-1 ). A capacitance plot of its capacitance value relative to its potential value in different states. As shown in the third (a) and third (b), both the liquid electrolyte (LE) and the colloidal polymer electrolyte (GE) have good capacitance storage capacity, from 500 mV s ^-1 to high speed. The capacitor curve can still be maintained, with only a slight deflection, and the colloidal polymer electrolyte (GE) shows better storage capacity than the liquid electrolyte (LE).

The fourth panel shows a schematic representation of the conductivity of the PEG 6K series of copolymers relative to lithium perchlorate (g) / PEG-b-PAN (g). It can be seen from the figure that the copolymer of PEG 6K series has a higher conductivity value when LiClO ₄ (g)/polymer(g)=4, and when PEG 6K-b-PAN 30 has relative The highest conductivity value, while 30 represents the reaction molar ratio of AN to PEG is 30 times. According to other experimental data of the present invention (not shown), the PEG 6K series of copolymers have higher conductivity values than other series of copolymers, and it is speculated that ethylene oxide (EO) is a copolymer. Shorter segments (eg PEG 1K series), the ability to transfer lithium ions is low; and when the ethylene oxide segment is longer (eg PEG 10K series), the ability to transfer lithium ions is lower due to the PEG segment Caused by recrystallization.

The fifth graph shows the specific capacitance values of the liquid electrolyte (LE) and the colloidal polymer electrolyte (GE) versus the discharge current, respectively. In the figure, the liquid electrolyte is 1 mole of lithium perchlorate dissolved in dimethylformamide, each carbon material electrode has an area of 1 square centimeter, and each capacitor is charged to 2.1V at a current of 1 mA before discharge. Voltage value. In the charge and discharge test, the capacitance decreases as the discharge current increases, which is caused by the resistance of the electrolyte ions or the internal electron transfer of the electrodes. At high discharge rates, the liquid electrolyte and the colloidal polymer electrolyte can obviously maintain the performance of high electric capacity, and the capacitor of the colloidal polymer electrolyte is better than the liquid electrolyte. The fifth figure shows the capacitance of the colloidal polymer electrolyte (GE) and the liquid electrolyte (LE). The capacitance obtained by the low current rate is equivalent, and the capacitance of GE at high current rate is higher than that of LE. The difference in the internal resistance of the capacitor. The internal resistance mainly includes the electrolyte resistance, the contact resistance between the electrode and the electrolyte, and the resistance generated by the movement of ions in the carbon hole.

The sixth graph shows a graph of the specific energy of the liquid electrolyte (LE) and the colloidal polymer electrolyte (GE) versus specific power, respectively. In the figure, the energy density of the capacitor of the colloidal polymer electrolyte (GE) is greater than that of the liquid (LE). For example, at a high power of 10,000 W kg ^-1 , the energy density of a capacitor of a colloidal polymer electrolyte (10.8 Wh kg ^-1 ) is significantly greater than that of a liquid (LE).

In order to investigate the resistance composition of the supercapacitor, the following analysis is performed by AC impedance. The seventh figure shows the Nyquist impedance plot of liquid electrolyte (LE) and colloidal polymer electrolyte (GE); the horizontal axis represents the real part of the impedance and the vertical axis represents the imaginary part of the impedance. And the range of its frequency is from 10mHz to 100kHz when the potential is 0V. As for its high frequency range, it is shown in the figure. As can be seen from the seventh figure, the electrolytes using GE and LE as capacitors have good capacitance behavior, but the capacitors of colloidal polymer electrolyte (GE) have lower resistance. For example, the resistance at a frequency of 1 kHz: GE is 0.94 Ω, and LE is 0.37 Ω. To investigate its resistance composition, observe the measurement of the impedance of the high frequency region. In the figure in the seventh figure, the starting point (R _i ) of the GE curve is smaller than LE, indicating the difference between the resistances of the electrolyte. The ion conductivity of GE is higher than that of LE because GE has PEO and PAN polymer chains. PEO has an oxy group to provide lithium ions to jump on the bond, and PAN also contributes to the transfer of the electrolyte, and the PEO-co-PAN polymer has a higher solubility for the lithium salt than the solution phase, so the GE R _{i is} smaller than the LE . The semicircle is the contact between the capacitor electrode and the electrolyte interface, and the semicircle of GE is larger than that of the LE, which is caused by the contact resistance (R _c ) between the carbon material and the GE electrolyte; and there is a significant difference between GE and LE in the semicircle. The transition from the end point to the straight rise, which is the mass transfer resistance (EDR) between the carbon particles, and the GE as the electrolyte, the EDR is significantly lower, the difference is that the GE can penetrate the electrode particles, making it a lower The EDR value, and the resistance of the ions in the pores is also relatively small, which is also caused by the difference in ion concentration outside the carbon particles. The resistance values of LE and GE are listed in Table 1, where R _p is the resistance of the carbon material pore and R _t is the total resistance of the capacitor.

Example:

Example 1 Synthesis of Polyacrylonitrile-Polyethylene Glycol-Polyacrylonitrile Copolymer (PAN- b -PEG- b- PAN triblock copolymer)

2.94 g of ceric ammonium nitrate (CAN) was dissolved in 180 ml of nitric acid (HNO ₃ ) to prepare a starter solution.

8.537 g of polyethylene glycol (PEG) was dissolved in 160 mL of distilled water in a three-necked reaction flask to prepare a solution. Turn on nitrogen (N ₂ ) and adjust the flow rate to a bubble of 2 seconds. Turn on the magnet stirrer and adjust the agitation speed to 500 rpm to completely dissolve the PEG and equilibrate with the 40 °C oil bath temperature. Fill the nitrogen for at least 30 minutes to drive off the oxygen in the reactor.

8.537 g of acrylnitrile monomer was added to the reactor to equilibrate with the oil bath temperature. The 180-ml nitric acid ammonium nitrate (CAN) nitric acid solution was poured slowly into the three-necked reaction flask. After 6 hours of reaction, the reaction was completed and the temperature was lowered. The product was placed in a vacuum condenser, and the concentrated product was poured into water from 500 ml, and stirred for 1 hour, and allowed to stand for 5 hours. After drying by suction filtration, the dried product was poured into 500 ml of acetone, stirred for 1 hour, and allowed to stand for 5 hours.

The mixture was dried under reduced pressure and filtered twice to remove excess small molecules and polyethylene glycol. The product was finally dried under a vacuum oven at 80 ° C for 48 hours. Polymer structure analysis was carried out by IR spectroscopy and ¹ H-NMR spectroscopy.

Example 2 Synthesis of Polyacrylonitrile-Polyethylene Glycol Copolymer (PAN- b- MPEG copolymer)

1.894 g of ammonium cerium nitrate (CAN) was dissolved in 115 ml of nitric acid to prepare a starter solution.

In a three-necked reaction flask, 6.909 g of poly(ethylene glycol monomethyl ether, PEGME) was dissolved in 104 mL of distilled water to prepare a solution. Turn on the magnet stirrer and adjust the agitation speed to 500 rpm to completely dissolve the PEG and equilibrate with the 40 °C oil bath temperature. Fill the nitrogen for at least 30 minutes to drive off the oxygen in the reactor.

5.499 g of acrylonitrile monomer was added to the reactor to equilibrate with the oil bath temperature. Slowly pour 115 ml of ammonium nitrate solution of ammonium cerium nitrate (CAN) into the three-necked reaction flask. After 6 hours of reaction, the reaction was completed and cooled. The product was placed in a vacuum condenser, and the concentrated product was poured into water from 500 ml, and stirred for 1 hour, and allowed to stand for 5 hours. After drying by suction filtration, the dried product was poured into 500 ml of acetone, stirred for 1 hour, and allowed to stand for 5 hours.

The reduced pressure was concentrated and filtered and dried twice to remove excess small molecules and polyethylene glycol. The product was finally dried under a vacuum oven at 80 ° C for 48 hours. Polymer structure analysis was carried out by IR spectroscopy and ¹ H-NMR spectroscopy.

Example 3 Colloidal polymer electrolyte

Weighed 0.1g of Polyacrylonitrile - polyethylene glycol - polyacrylonitrile copolymer (PAN- b -PEG- b -PAN) with 0.4g of lithium perchlorate salts, 10g of dimethylformamide was added XI The amine (DMF) uniformly dissolves lithium perchlorate (LiClO ₄ ) and the polymer. The solution was sealed and placed in an oven at 80 ° C until completely homogeneously dissolved. The solution was poured into an aluminum pan, and the aluminum pan was placed in an oven at 80 ° C to naturally evaporate to obtain a colloidal polymer electrolyte membrane.

Example 4 Synthesis of polypropylene-polyethylene glycol-polypropylene diamine, 3-glycidoxypropyltrimethoxydecane, tetraethoxy ruthenium crosslinked copolymer (PPG-PEG-PPG diamine, 3 - (Trimethoxysilyl) propyl glycidyl ether, tetraethoxysilane) colloidal polymer electrolyte

A tetraethoxysilane (TEOS), 3-glydicyloxypropyl trimethoxy-silane (GLYMO) reaction solution was preliminarily placed in the reaction flask to have a reaction molar ratio of 1: 4, and 2 M hydrochloric acid was added at room temperature to carry out a sol-gel condensation polymerization reaction for 60 minutes.

Prepare H ₂ N-PPG ₄₀ -PEG ₅ -PPG ₄₀ -NH ₂ triblock copolymer (D2000), acetonitrile reaction solution in another reaction flask, and add lithium perchlorate (LiClO ₄ ) to make the mixed solution suitable. The concentration ratio of the oxygen atom to the lithium atom, such as [O] / [Li] = 8, is stirred for another 60 minutes until the mixture is homogeneous.

The two solutions of the above two steps were uniformly mixed at room temperature and reacted for 24 hours. 10 g of dimethylformamide (DMF) was added to a 1 g mixed solution and poured into a Teflon tray, and naturally volatilized at room temperature for 24 hours to form a film. The electrolyte membrane was placed in a 95 ° C vacuum oven for 24 hours to drive off the residual solvent to obtain a transparent electrolyte membrane.

Example 5 Synthesis of Electrolyte Containing Polyvinyl Alcohol-Polyethylene Glycol (PVA-b-PEG)

A solution of borane (BH ₃ ) / tetrahydrofuran (THF) was prepared, and 10 mmol of borane was weighed and dissolved in 10 ml of tetrahydrofuran.

Poly (vinyl alcohol (PVA) / polyethylene glycol methyl ether (PEGME) / dimehtyl sulfoxide (DMSO) reaction solution of different molecular weights and different molecular weights are pre-configured in a three-neck reaction flask. Set up the reaction tube, condenser tube and other reaction devices, adjust the oil bath temperature to 50 ° C, turn on the magnet stirrer, adjust the stirring speed to 500 rpm, so that PVA / PEGME is completely dissolved in DMSO and the oil bath temperature is balanced. Fill the nitrogen for at least 60 minutes to drive off the oxygen in the reactor.

A borane/tetrahydrofuran solution was added to the feed tube so that the reaction molar ratio was 1:1:2 than BH ₃ /PVA/PEGME, and the flow rate was adjusted slowly into the three-neck reaction flask. After the reaction temperature was raised from 50 ° C to 100 ° C for 24 hours, the reaction was terminated, cooled, and exposed to the atmosphere.

The product was concentrated under reduced pressure, and the concentrated product was slowly poured into 500 ml of diethyl ether. After stirring for 1 hour, it was allowed to stand for 5 hours. The steps of dissolving in diethyl ether in three portions were repeated under reduced pressure to remove excess small molecules and PEGME. The final product was dried in a vacuum oven at 80 ° C for 48 hours.

Weighing about 0.1g of polyvinyl alcohol-polyethylene glycol (PVA-b-PEG) copolymer and 0.4g of lithium perchlorate, adding 10g of dimethylformamide (DMF) to dissolve lithium salt evenly Copolymer. After sealing, it was placed in an oven at 80 ° C until it was completely dissolved.

The solution was poured into an aluminum pan, and the aluminum pan was placed in an oven at 80 ° C to volatilize to a suitable DMF content to obtain a colloidal polymer electrolyte membrane.

Other embodiments

A colloidal polymer electrolyte comprising: a polyethylene glycol (PEG); an acrylonitrile (AN) monomer and a polyethylene glycol form a copolymer; a plasticizer and the copolymer form a colloidal state The copolymer, and a lithium salt, form an electrolyte with the colloidal copolymer.

2. A compound comprising: a copolymer of polyacrylonitrile; and a plasticizer.

3. A colloidal polymer electrolyte comprising: a polyethylene glycol copolymer; a colloidal copolymer formed with a plasticizer and a lithium salt and the colloidal copolymer; Electrolyte.

4. A colloidal polymer electrolyte comprising: an acrylonitrile (AN) copolymer-plasticizer and a colloidal copolymer formed from the copolymer, and a lithium salt formed with the colloidal copolymer Electrolyte.

5. The colloidal polymer electrolyte according to the above embodiment, wherein the polyethylene glycol (PEG) copolymer may be selected from the group consisting of polyethylene glycol-polyvinylidene fluoride-polyhexafluoropropylene (PEG-( PVDF-co-PHFP), polyethylene glycol-glycidyl methacrylate-methyl methacrylate ((PEG-b-GMA)-co-MMA), polyvinyl alcohol-polyethylene glycol (PVA-b -PEG), polypropylene-polyethylene glycol-polypropylene (PPG-PEG-PPG), polymethyl methacrylate-polyvinyl acetate-polyethylene glycol diacrylate ((PMMA-PVAc)-co- PEGDA), polyethylene glycol-graft copolymerization-polymethyl acrylate (PEG-g-PMA), polyethylene glycol-graft copolymerization-polymethyl methacrylate (PEG-g-PMMA) or polypropylene- Polyethylene glycol-PPG diamine, 3-(Trimethoxysilyl)propyl glycidyl ether, tetraethoxysilane One of a group of cross-linked copolymers or a combination thereof.

6. The colloidal polymer electrolyte according to the above embodiment, wherein the copolymer of acrylonitrile is selected from the group consisting of polyacrylonitrile-polyethylene glycol-polyacrylonitrile (PAN-PEG-PAN), polyacrylonitrile-poly Ethylene glycol (PAN-PEG), polyethylene glycol-polyacrylonitrile-polyethylene glycol (PEG-PAN-PEG), polyacrylonitrile-polyacrylic acid (PAN-PAA) copolymer, or a combination thereof Form one of a group.

7. The colloidal polymer electrolyte according to the above embodiment, wherein the lithium salt is lithium perchlorate (LiClO ₄ ).

8. The colloidal polymer electrolyte according to the above embodiment, wherein the plasticizer is selected from the group consisting of dimethylformamide (DMF), ethylene carbonate (EC), propylene carbonate (PC), and dimethyl carbonate. One of a base ester (DMC) and γ-butyrolactone (γ-BL).

9. A compound comprising: a copolymer of polyacrylonitrile (AN); and a plasticizer.

10. A compound comprising: a polyethylene glycol (PEG) copolymer; and a plasticizer.

A method for producing a colloidal polymer electrolyte, comprising: providing a polyethylene glycol (PEG)-containing compound; and polymerizing the polyethylene glycol compound with a compound selected from the group consisting of an acrylic compound and an alkenyl group A compound, a decane compound or a polyurethane (PU); a plasticizer and a lithium salt are mixed to form a colloidal electrolyte.

In summary, the present invention provides a highly conductive polyethylene glycol copolymer colloidal polymer electrolyte suitable for use in a supercapacitor having high conductivity (>10 ^-2 S cm ^-1 ), low impedance, With high energy density, high power work density and wide operating potential window, this colloidal copolymer is made into a film-like electrolyte, which is suitable for supercapacitors, so it is indeed progressive and novel.

Therefore, even though the present invention has been described in detail by the above-described embodiments, it can be modified by those skilled in the art, and is not intended to be protected as claimed.

First: chemical structure of polyacrylonitrile-polyethylene glycol-polyacrylonitrile copolymer; xyz is a natural number greater than 1.

Second: Fourier transform infrared spectroscopy (FT-IR)

Third (a) and third (b): respectively showing a conventional liquid electrolyte (LE) and a colloidal polymer electrolyte (GE) according to the concept of the present invention, the capacitance of the colloidal polymer electrolyte (GE) according to cyclic voltammetry in different states a capacitance plot of the value relative to its potential value;

Figure 4: shows a schematic diagram of the conductivity of a PEG 6K series copolymer relative to lithium perchlorate (g) / PAN-b-PEG-b-PAN (g);

Fig. 5 is a graph showing the specific capacitance values of the liquid electrolyte (LE) and the colloidal polymer electrolyte (GE) with respect to the discharge current;

Figure 6: A graph showing the specific energy of a liquid electrolyte (LE) and a colloidal polymer electrolyte (GE) versus a specific power;

Figure 7: Nyquist impedance diagrams of liquid electrolyte (LE) and colloidal polymer electrolyte (GE), respectively.

Claims (10)

A colloidal polymer electrolyte comprising: an acrylonitrile copolymer-plasticizer and a colloidal copolymer formed from the copolymer, and an electrolyte formed by a lithium salt and the colloidal copolymer. The colloidal polymer electrolyte according to claim 1, wherein the acrylonitrile copolymer may be selected from the group consisting of polyacrylonitrile-polyethylene glycol-polyacrylonitrile (PAN-PEG-PAN), polyacrylonitrile- One or a combination of polyethylene glycol (PAN-PEG), polyethylene glycol-polyacrylonitrile-polyethylene glycol (PEG-PAN-PEG), polyacrylonitrile-polyacrylic acid (PAN-PAA) copolymer One of the group consisting of one. The colloidal polymer electrolyte according to claim 1, wherein the plasticizer is selected from the group consisting of dimethylformamide (DMF), ethylene carbonate (EC), propylene carbonate (PC), and carbonic acid. One of dimethyl ester (DMC) and γ-butyrolactone (γ-BL). The colloidal polymer electrolyte according to claim 1, wherein the lithium salt is lithium perchlorate (LiClO ₄ ). A colloidal polymer electrolyte comprising: a polyethylene glycol (PEG) copolymer; a colloidal copolymer formed with a plasticizer, and a lithium salt and the colloidal copolymer Electrolyte. The compound of claim 5, which further comprises lithium perchlorate (LiClO ₄ ). The colloidal polymer electrolyte according to claim 5, wherein the plasticizer is selected from the group consisting of dimethylformamide (DMF), ethylene carbonate (EC), propylene carbonate (PC), and carbonic acid. One of dimethyl ester (DMC) and γ-butyrolactone (γ-BL). The colloidal polymer electrolyte according to claim 5, wherein the polyethylene glycol copolymer, the polyethylene glycol (PEG) copolymer, may be selected from the group consisting of polyethylene glycol-polyethylene Fluoroethylene-polyhexafluoropropylene (PEG-(PVDF-co-PHFP), polyethylene glycol-glycidyl methacrylate-methyl methacrylate ((PEG-b-GMA)-co-MMA), poly Vinyl alcohol-polyethylene glycol (PVA-b-PEG), polypropylene-polyethylene glycol-polypropylene (PPG-PEG-PPG), polymethyl methacrylate-polyvinyl acetate-polyethylene glycol Acrylate ((PMMA-PVAc)-co-PEGDA), polyethylene glycol-graft copolymerization-polymethyl acrylate (PEG-g-PMA), polyethylene glycol-graft copolymerization-polymethyl methacrylate (PEG-g-PMMA) or PP-PEG-PPG diamine, 3-methoxypropyl propyl glycidyl One of a group consisting of ether, one of a cross-linked copolymer of tetraethoxysilane, or a combination thereof. A compound comprising: a copolymer of polyacrylonitrile (AN); and a plasticizer. A compound comprising: a polyethylene glycol (PEG) copolymer; and a plasticizer.