TW201546822A - The polymeric gel electrolyte and manufacturing method thereof - Google Patents

Abstract

A polymeric gel electrolyte, which comprises: 45 ~ 70wt% of a thermoplastic polymer, 2 ~ 10wt% of a lithium salt, 10 ~ 35wt% of an organic solvent and 10 ~ 35wt% of a plasticizer, and the polymeric gel electrolyte preferably comprises 5 ~ 20wt% of a ion liquid and 0.1 ~ 5% of a stabilizer. Mixing the thermoplastic polymer, the lithium salt, the organic solvent, the plasticizer, the ion liquid and the stabilizer to obtain the polymeric gel electrolyte.

Description

Colloidal polymer electrolyte and manufacturing method thereof

The present invention relates to an electrolyte, in particular to a colloidal polymer electrolyte, and to a method of producing the colloidal polymer electrolyte.

Electrolytes, which are substances contained in many electrical components, help to establish current channels inside the electrical components, such as conventional batteries, capacitors, and electrochromic components, all of which have electrolytes.

The conventional electrolytes can be classified into conventional liquid electrolytes and conventional solid electrolytes depending on their state. The conventional liquid electrolyte has high ion conductivity and its current conduction effect is quite superior. However, since the conventional liquid electrolyte has fluidity, when the electrical component is used for a long period of time or is pressed by an external force, the leakage of the electrical component is reduced, resulting in leakage of the electrical component, and the electrical component is inoperable; In addition, the conventional liquid electrolyte contains an organic solvent (such as liquid propylene carbonate and ethylene carbonate), and if such an organic solvent is leaked, there is a safety concern, and the above-mentioned electric component using the conventional liquid electrolyte It poses a considerable threat. The conventional solid electrolyte uses a polymer or an inorganic metal oxide instead of the conventional liquid electrolyte to solve the liquid leakage problem of the conventional liquid electrolyte. However, the conventional solid electrolyte has an interface resistance between the electrodes, so that the conventional solid state The ionic conductivity of the electrolyte is not high, resulting in unsatisfactory performance of the electrical component.

In view of this, it is necessary to provide a colloidal polymer electrolyte and the colloidal high In the method for producing a molecular electrolyte, the colloidal polymer electrolyte has a higher ionic conductivity than the solid electrolyte, and the colloidal polymer electrolyte cannot flow freely, thereby avoiding leakage.

The main object of the present invention is to provide a colloidal polymer electrolyte which has a high ionic conductivity and does not cause liquid leakage.

Another object of the present invention is to provide a method for producing a colloidal polymer electrolyte which is used for producing a colloidal polymer electrolyte having a high ionic conductivity and which does not cause liquid leakage.

In order to achieve the foregoing object, the technical means and the effects achievable by the technical method include: a colloidal polymer electrolyte comprising: a thermoplasticity of 45 to 70% by weight. a molecule, 2 to 10% of a lithium salt, 10 to 35% of an organic solvent, and 10 to 35% of a plasticizer; wherein the thermoplastic polymer, the lithium salt, the organic solvent, and the plasticizer are The colloidal polymer electrolyte is obtained by kneading.

In the colloidal polymer electrolyte of the present invention, the colloidal polymer electrolyte further comprises an ionic solution in an amount of 5 to 20% by weight.

In the colloidal polymer electrolyte of the present invention, the colloidal polymer electrolyte further contains a stabilizer in an amount of 0.1 to 5% by weight.

The colloidal polymer electrolyte of the present invention, wherein the thermoplastic polymer is selected from the group consisting of polyvinyl butyral or polyethylene.

In the colloidal polymer electrolyte of the present invention, the thermoplastic polymer is polyvinyl butyral.

In the colloidal polymer electrolyte of the present invention, the thermoplastic polymer is a polyvinyl butyral having a molecular weight of from 50,000 to 112,000 g/mol.

The colloidal polymer electrolyte of the present invention, wherein the lithium salt is selected from the group consisting of lithium perchlorate or lithium dioxalate borate.

The colloidal polymer electrolyte of the present invention, wherein the organic solvent is selected from the group consisting of propylene carbonate, ethylene carbonate, butylene ester, N-methyl-pyrrolidine, dimethyl carbonate or ethyl acetate .

In the colloidal polymer electrolyte of the present invention, the plasticizer is a group consisting of diethylene glycol butyl ether and adipic acid.

The colloidal polymer electrolyte of the present invention, wherein the ionic solution is a compound containing a main cyclopropyl group.

A method for producing a colloidal polymer electrolyte for producing a colloidal polymer electrolyte, comprising: providing a thermoplastic polymer; reacting the thermoplastic polymer at 50 to 100 ° C for 5 to 40 minutes to obtain a dry a thermoplastic polymer; the dried thermoplastic polymer is uniformly mixed with a lithium salt, an organic solvent and a plasticizer to obtain a polymer adhesive; the polymer adhesive is rotated at 90 to 120 ° C The gelled polymer electrolyte was obtained by kneading at 40 to 80 rpm for 1 to 10 minutes.

A method for producing a colloidal polymer electrolyte according to the present invention, wherein the polymer adhesive further comprises an ionic solution.

In the method for producing a colloidal polymer electrolyte of the present invention, the polymer adhesive further comprises a stabilizer.

In the method for producing a colloidal polymer electrolyte according to the present invention, the thermoplastic polymer is reacted at 60 ° C for 30 minutes to obtain the dried thermoplastic polymer.

In the method for producing a colloidal polymer electrolyte according to the present invention, the polymer adhesive is kneaded at 110 ° C for 2 minutes at a number of revolutions of 65 rpm to obtain the colloidal polymer electrolyte.

A method for producing a colloidal polymer electrolyte of the present invention, further comprising: The colloidal polymer electrolyte is extruded at a temperature of 100 to 140 ° C and a pressure of 0.5 to 1 MPa to obtain a colloidal polymer electrolyte membrane.

In the method for producing a colloidal polymer electrolyte according to the present invention, the colloidal polymer electrolyte membrane has a thickness of 100 to 500 μm.

In the method for producing a colloidal polymer electrolyte of the present invention, the colloidal polymer electrolyte membrane is coated with a protective film to obtain a flexible colloidal polymer electrolyte membrane.

In the method for producing a colloidal polymer electrolyte according to the present invention, the thermoplastic polymer is selected from the group consisting of polyvinyl butyral or polyethylene.

A method for producing a colloidal polymer electrolyte according to the present invention, wherein the thermoplastic polymer is polyvinyl butyral.

In the method for producing a colloidal polymer electrolyte according to the present invention, the thermoplastic polymer is a polyvinyl butyral having a molecular weight of from 50,000 to 112,000 g/mol.

In the method for producing a colloidal polymer electrolyte according to the present invention, the lithium salt is selected from the group consisting of lithium chlorate or lithium bis(oxalate) borate.

The method for producing a colloidal polymer electrolyte according to the present invention, wherein the organic solvent is selected from the group consisting of propylene carbonate, ethylene carbonate, butylene ester, N-methyl-pyrrolidine, dimethyl carbonate or ethyl acetate. Group.

In the method for producing a colloidal polymer electrolyte according to the present invention, the plasticizer is a group consisting of diethylene glycol butyl ether and adipic acid.

A method for producing a colloidal polymer electrolyte according to the present invention, wherein the ionic solution is a compound containing a main cyclopropyl group.

The colloidal polymer electrolyte of the present invention has a specific ratio of a specific component to each component therein, and uniformly disperses the components by kneading, so that the colloidal polymer electrolyte has high cohesive mechanical properties and has a low Fluidity, and the ionic conductivity of the colloidal polymer electrolyte is also significantly improved compared with the solid electrolyte, thereby achieving high ion conductivity and no leakage. efficacy.

The method for producing a colloidal polymer electrolyte of the present invention is to uniformly disperse a specific component and a component of a specific ratio by kneading, thereby achieving the effect of producing a colloidal polymer electrolyte having high ion conductivity and causing no liquid leakage.

The above and other objects, features and advantages of the present invention will become more <RTIgt; The method comprises a thermoplastic polymer of 45 to 70% by weight, a lithium salt of 2 to 10%, an organic solvent of 10 to 35%, and a plasticizer of 10 to 35%, which is high in colloidal state. The molecular electrolyte preferably further comprises from 5 to 20% by weight of the ion solution, and from 0.1 to 5% by weight of the stabilizer.

In detail, the thermoplastic polymer may be selected from the group consisting of polyvinyl butyral (PVB) or polyethylene (PE), which provides a path for ion conduction, in this embodiment, The thermoplastic polymer is polyvinyl butyral.

The lithium salt may be selected from the group consisting of Lithium perchlorate or Lithium bis (oxalate) boronate (LiBOB), which can dissociate lithium ions, the lithium The ions move between the thermoplastic polymers to conduct electricity. In the present embodiment, the lithium salt is lithium perchlorate.

The organic solvent is particularly a high-boiling organic solvent, and may be selected from the group consisting of Propylene carbonate (PC), Ethylene carbonate (EC), and Gamma-butyrolactone (γ-BL). a group consisting of N-methyl-pyrrolidine (NMP), dimethyl carbonate (DMC) or ethyl acetate (Ethyl acetate, EA for short). The organic solvent is capable of transferring lithium ions therein. It can also help dissociate lithium ions from the lithium salt.

The plasticizer is selected from the group consisting of diethylene glycol butyl ether and adipic acid, and the addition of the plasticizer can increase the transmittance of the colloidal polymer electrolyte, and the transmittance can be increased. The applicability of the colloidal polymer electrolyte can be applied to, for example, an electrochromic device (ECD), and the addition of a plasticizer can also adjust the viscosity of the colloidal polymer electrolyte, in this embodiment. The plasticizer is a mixture of diethylene glycol monobutyl ether and Adipic acid mixture (D-600).

The ionic solution is a compound containing a main cyclopropyl group. In the present embodiment, the ionic solution is [Pmim][ClO4]. The ionic solution provides other conductive ions different from lithium ions to increase the ion concentration of the colloidal polymer electrolyte, and the ionic solution also enhances the environmental stability of the lithium ion.

The stabilizer has the functions of anti-oxidation or anti-UV, and can eliminate or slow the self-addition reaction or oxidation of the unsaturated bond in the thermoplastic polymer at a certain temperature, thereby preventing the structure and properties of the thermoplastic polymer from occurring. Variety. The stabilizer may be a compound such as carbon black, zinc oxide, titanium oxide, benzophenone, benzotriazole, salicylate, triazine, substituted acrylonitrile, organonickel chelate or hindered amine. When the thermoplastic polymer is irradiated to ultraviolet light for a long period of time, it is easily hardened due to internal bond breakage, and the colloidal polymer electrolyte composed is easily broken. Therefore, the addition of the stabilizer can slow down the thermoplasticity. The molecules are decomposed to prolong the service life of the composed colloidal polymer electrolyte. In the present embodiment, the PVB stabilizer of Changchun Chemical Model AO-60 was selected.

After the thermoplastic polymer, the lithium salt and the organic solvent are mixed, the thermoplastic polymer is swelled by the organic solvent to form a polymer network, and the high-mass power of the main chain or the side chain of the thermoplastic polymer An atom (for example, oxygen) or a hydroxyl group (ie, OH ^- ) has an unpaired electron, and therefore, lithium ions (Li ⁺ ) dissociated from the lithium salt form a temporary coordinate bond with the thermoplastic polymer. The knot is passed in the polymer network. The presence of the organic solvent provides another means of conducting lithium ions such that lithium ions can move in the colloidal polymer electrolyte described above by the organic solvent.

When the thermoplastic polymer, the lithium salt, the organic solvent, the plasticizer, and the ionic solution are mixed, the gelation reaction (Gelation) greatly reduces the fluidity, and on the other hand, the colloidal polymer electrolyte remains The shape change can be caused by an external force, and therefore, it also has cohesive mechanical properties and processability for facilitating deformation.

The following is a method for producing the colloidal polymer electrolyte of the present invention: first, the thermoplastic polymer is dehydrated to obtain a dried thermoplastic polymer, and then the dried thermoplastic polymer and the lithium salt, The organic solvent and the plasticizer are uniformly mixed to obtain a polymer adhesive, and then the polymer adhesive is kneaded to obtain the colloidal polymer electrolyte. The colloidal polymer electrolyte comprises 45 to 70% by weight of the thermoplastic polymer, 2 to 10% of the lithium salt, 10 to 35% of the organic solvent, and 10 to 35% of the plasticizer. And the colloidal polymer electrolyte preferably further comprises 5 to 20% by weight of the ionic solution and 0.1 to 5% by weight of the stabilizer, and the ionic solution and the dried thermoplastic are high. The molecule, the lithium salt, the organic solvent, the plasticizer, and the stabilizer are mixed to obtain the polymer adhesive, and the polymer adhesive is further kneaded. Mixing means uniformly dispersing two or more kinds of heterogeneous components at a specific temperature, stirring speed and stirring time to improve the physical and mechanical properties of the colloid.

In detail, the thermoplastic polymer is kept at a temperature of 50 to 100 ° C for 5 to 40 minutes, and the moisture of the thermoplastic polymer is evaporated to remove the moisture in the thermoplastic polymer to obtain the dried thermoplastic polymer. In the present embodiment, the thermoplastic polymer was dried by holding at 60 ° C for 30 minutes.

The polymer adhesive is kneaded at 90-120 ° C for 1 to 10 minutes, and the various contained components are uniformly dispersed to improve the physical and mechanical properties of the colloid, and the colloidal polymer electrolysis is obtained. In the present embodiment, the thermoplastic polymer, the lithium salt, the organic solvent, the plasticizer, and the ionic solution were sufficiently uniformly dispersed by kneading at 110 ° C for 4 minutes at a rotational speed of 40 to 80 rpm.

Preferably, the obtained colloidal polymer electrolyte is further extruded at a pressure of 0.5 to 1 MPa at 100 to 140 ° C to obtain a colloidal polymer electrolyte membrane, and the thickness of the colloidal polymer electrolyte membrane is preferably 100~ 500 μm. In addition, the colloidal polymer electrolyte membrane can be coated by a protective film to obtain a flexible colloidal polymer electrolyte membrane, which is insulated from the outside by moisture and oxygen. The polymer electrolyte membrane can be properly preserved and the service life of the flexible colloidal polymer electrolyte membrane is increased.

In order to prove that the colloidal polymer electrolyte of the present invention has a high ionic conductivity, the composition of each component is fixed by the above-mentioned manufacturing method (hereinafter all in weight percentage): thermoplastic polymer 50%, the lithium salt 8%, the organic solvent 17%, the plasticizer 17%, the ionic solution 8% and the stabilizer 1%, and the glue prepared by different components and parameters (such as the proportion of each component of the organic solvent) The state of the polymer electrolyte (groups A1 to A4, respectively) is tested for ionic conductivity. In this case, the ITO conductive glass is used as an electrode substrate by using an alternating current impedance analysis method, and the colloidal polymer electrolyte is sandwiched by the electrode substrate. And connected to an AC impedance analyzer for measurement, the results are shown in Table 1.

By adjusting the molecular weight of the thermoplastic polymer and the type and ratio of the organic solvent, the colloidal polymer electrolyte having different ionic conductivity can be obtained. This experiment proves that the groups A1 to A4 have high ionic conductivity, among which Group A1 has the best ionic conductivity. Therefore, it can be known from the ionic conductivity test that the ionic polymer electrolyte obtained by the present invention has an ionic conductivity of about 10 ^-5 to 10 ^-4 S/cm, which is a significant improvement over the ionic conductivity of the solid electrolyte. .

In summary, the colloidal polymer electrolyte of the present invention is a cohesive mechanical property of the colloidal polymer electrolyte due to a specific ratio between the specific component and each component thereof and uniform dispersion of the components by kneading. High and low fluidity, and the ionic conductivity of the colloidal polymer electrolyte is also significantly improved compared with the solid electrolyte. Therefore, the colloidal polymer electrolyte of the present invention can achieve high ion conductivity without causing leakage. The effect.

While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.

Claims (25)

A colloidal polymer electrolyte comprising: 45 to 70% by weight of a thermoplastic polymer, 2 to 10% of a lithium salt, 10 to 35% of an organic solvent, and 10 to 35% of a plastic And a thermoplastic polymer, the lithium salt, the organic solvent, and the plasticizer are kneaded to obtain the colloidal polymer electrolyte. The colloidal polymer electrolyte according to claim 1, wherein the colloidal polymer electrolyte further comprises an ionic solution in an amount of 5 to 20% by weight. The colloidal polymer electrolyte according to claim 1, wherein the colloidal polymer electrolyte further comprises a stabilizer in an amount of 0.1 to 5% by weight. The colloidal polymer electrolyte according to claim 1, wherein the thermoplastic polymer is selected from the group consisting of polyvinyl butyral or polyethylene. The colloidal polymer electrolyte according to claim 1, wherein the thermoplastic polymer is polyvinyl butyral. The colloidal polymer electrolyte according to claim 1, wherein the thermoplastic polymer is a polyvinyl butyral having a molecular weight of from 50,000 to 112,000 g/mol. The colloidal polymer electrolyte according to claim 1, wherein the lithium salt is selected from the group consisting of lithium perchlorate or lithium dioxalate borate. The colloidal polymer electrolyte according to claim 1, wherein the organic solvent is selected from the group consisting of propylene carbonate, ethylene carbonate, butyrate, N-methyl-pyrrolidine, and carbonic acid. A group consisting of methyl ester or ethyl acetate. The colloidal polymer electrolyte according to claim 1, wherein the plasticizer is a group consisting of diethylene glycol butyl ether and adipic acid. The colloidal polymer electrolyte according to claim 2, wherein the ion The solution is a compound containing a primary cyclopropyl group. A method for producing a colloidal polymer electrolyte for producing a colloidal polymer electrolyte, comprising: providing a thermoplastic polymer; reacting the thermoplastic polymer at 50 to 100 ° C for 5 to 40 minutes to obtain a dry a thermoplastic polymer; the dried thermoplastic polymer is uniformly mixed with a lithium salt, an organic solvent and a plasticizer to obtain a polymer adhesive; the polymer adhesive is rotated at 90 to 120 ° C The gelled polymer electrolyte was obtained by kneading at 40 to 80 rpm for 1 to 10 minutes. The method for producing a colloidal polymer electrolyte according to claim 11, wherein the polymer adhesive further comprises an ionic solution. The method for producing a colloidal polymer electrolyte according to claim 11, wherein the polymer adhesive further comprises a stabilizer. The method for producing a colloidal polymer electrolyte according to claim 11, wherein the thermoplastic polymer is reacted at 60 ° C for 30 minutes to obtain the dried thermoplastic polymer. The method for producing a colloidal polymer electrolyte according to claim 11, wherein the polymer adhesive is kneaded at 110 ° C for 2 minutes at a rotation speed of 65 rpm to obtain the colloidal state. Polymer electrolyte. The method for producing a colloidal polymer electrolyte according to claim 11, wherein the colloidal polymer electrolyte is extruded at a temperature of 100 to 140 ° C and a pressure of 0.5 to 1 MPa. Forming to obtain a colloidal polymer electrolyte membrane. The method for producing a colloidal polymer electrolyte according to claim 16, wherein the colloidal polymer electrolyte membrane has a thickness of 100 to 500 μm. The method for producing a colloidal polymer electrolyte according to claim 16, wherein the colloidal polymer electrolyte membrane is coated with a protective film to obtain a flexible colloidal polymer electrolyte membrane. The method for producing a colloidal polymer electrolyte according to claim 11, wherein the thermoplastic polymer is selected from the group consisting of polyvinyl butyral or polyethylene. The method for producing a colloidal polymer electrolyte according to claim 11, wherein the thermoplastic polymer is polyvinyl butyral. The method for producing a colloidal polymer electrolyte according to claim 11, wherein the thermoplastic polymer is a polyvinyl butyral having a molecular weight of from 50,000 to 112,000 g/mol. The method for producing a colloidal polymer electrolyte according to claim 11, wherein the lithium salt is selected from the group consisting of lithium chlorate or lithium bis(oxalate) borate. The method for producing a colloidal polymer electrolyte according to claim 11, wherein the organic solvent is selected from the group consisting of propylene carbonate, ethylene carbonate, butyrate, N-methyl-pyrrolidine, a group consisting of dimethyl carbonate or ethyl acetate. The method for producing a colloidal polymer electrolyte according to claim 11, wherein the plasticizer is a group consisting of diethylene glycol butyl ether and adipic acid. The method for producing a colloidal polymer electrolyte according to claim 12, wherein the ionic solution is a compound containing a main cyclopropyl group.