WO2021119920A1

WO2021119920A1 - All-solid-state pvb-based ion transport material, preparation method therefor and use thereof

Info

Publication number: WO2021119920A1
Application number: PCT/CN2019/125648
Authority: WO
Inventors: 崔明培; 韩金保; 余力; 梁文平; 邝耀庭; 崔锡桥; 崔锡汉; 龙甫强; 苏龙庆
Original assignee: 佛山市钜仕泰粉末冶金有限公司
Priority date: 2019-12-16
Filing date: 2019-12-16
Publication date: 2021-06-24
Also published as: CN113272373A; CN113272373B

Abstract

The present application relates to the technical field of ion transport materials, and particularly to an all-solid-state PVB-based ion transport material, a preparation method therefor and the use thereof. With single-layer graphene, single-wall carbon nanotubes or silver nanowires as a nano-powder, by controlling the content of a Lewis base containing an alkali metal in a conductive slurry and the ratio of the Lewis base to the nano-powder, the present application provides a high-conductivity ion transport material. In addition, the ion transport material is a solid material, and is applied to an electrochromic glue-laminated glass as an ion transport layer. The electrochromic glue-laminated glass is not only convenient to package, so as to solve the problem of difficult packaging of an electrochromic device, but also has a fast discoloration speed; in addition, the difference between the light transmissivity of the glass after being energized and stabilized and the light transmissivity when same is deenergized is greater than or equal to 45%, and the electrochromic effect is good. By means of the ultrasonic dispersion of a mixture of a dispersant, a solvent and the nano-powder using an ultrasonic cell mill with the dispersion time being controlled, the performance of the formed conductive slurry can be ensured and failure is prevented.

Description

An all-solid PVB-based ion transport material and its preparation method and application

Technical field

This application relates to the technical field of ion transport materials, and in particular to an all-solid PVB-based ion transport material and its preparation method and application.

Background technique

With the development of the national economy and modern science and technology, energy conservation and environmental protection have received more and more attention. Building energy consumption accounts for a larger proportion of the ever-increasing total energy consumption in society. my country's building energy consumption has accounted for 27.6% of the total energy consumption of the whole society, and it is increasing year by year. Therefore, building energy efficiency has become a long-term strategic policy for my country's economic development. Laminated safety glass is widely used in the construction industry due to its excellent properties such as safety, sound insulation, heat insulation, and UV resistance. Its excellent heat insulation performance is mainly due to the thermal conductivity of the polymer material in the laminated glass than that of ordinary glass. The coefficient is much lower, and the hindering effect on the heat flow is greater in the heat flow transfer process. At present, the interlayer films in laminated glass are mainly PVB, EVA, TPU, and SGP. However, compared with traditional LOE-E insulating glass, laminated glass made of these interlayer films alone has poor heat insulation performance. Therefore, technicians began to study the interlayer film with excellent thermal insulation properties. Chinese patents 201210106417.7 and 201410353896.1 use EVA as a substrate to prepare a functional thermal insulation EVA film with high shielding of ultraviolet and infrared rays and high transmittance of visible light. Chinese patent 201110312122.0 uses a small amount of organic solvent to dissolve a small amount of PVB, then add an appropriate amount of ITO powder, repeatedly mill it with a ball mill to form a nano-emulsion, and then add it to the PVB resin powder in a certain proportion with a plasticizer, and plasticize it in the extruder. The mold is formed into a film to obtain a heat-insulating PVB film. Although the application of these interlayer films for laminated glass can solve the problem of building energy saving, the optical properties of these laminated glasses are fixed. As a "smart window" with adjustable absorption and reflection and controllable energy in the near-infrared region on the market, it has very attractive application prospects in the construction industry. There is an urgent need for an optical parameter that can generate color and light transmittance under an external electric field. Reversible change of glass, namely electrochromic glass.

Electrochromic materials refer to the material's optical properties (transmittance, reflectance, absorptivity, emissivity, etc.) that produce stable and reversible changes in the visible light wavelength range under the action of an applied current or electric field. It can be widely used in energy, Information, electronics, construction and other aspects. Electrochromic glass is based on glass or acrylic glass, which is successively plated with a transparent conductive layer, an electrochromic layer, an ion transport layer, an ion storage layer and a transparent conductive layer. In the early research, the liquid electrolyte was mainly used as the ion transport layer of the electrochromic device, which would bring great inconvenience to the packaging of the electrochromic device, and it was also not conducive to large-area display. Chinese patent document CN201510591161.7 aims at the problem that electrochromic devices can only use liquid electrolyte as the ion transport layer, which leads to difficulties in encapsulation of electrochromic devices and is not conducive to large-area display. It discloses an ion transport material and its preparation method and application. However, the use of solid ion transport materials as the ion transport layer of electrochromic glass needs to be further improved and optimized in terms of electrical conductivity, discoloration speed and light transmittance.

Application content

This application aims at the existing electrochromic glass with solid ion transport material as the ion transport layer, and its conductivity, discoloration speed and light transmittance still need to be further improved and optimized, and provides an all-solid PVB-based ion transport Materials, as well as the preparation method and application of the all-solid PVB-based ion transport material.

In order to achieve the above-mentioned purpose, this application adopts the following technical solutions.

The first aspect of the application provides an all-solid PVB-based ion transport material. The all-solid PVB-based ion transport material is made by uniformly mixing conductive paste and PVB resin in any ratio; the conductive paste is made of nanopowders. Body fluid and B liquid, the nano powder liquid is composed of a solvent, nano powder dispersed in the solvent and a dispersant, the B liquid is composed of a plasticizer and an alkali metal-containing Lewis base, and the quality of the nano powder liquid is 2.7-3.2% of the mass of B liquid;

The mass percentage of Lewis base in the B solution is 17-20%;

The mass of the dispersant in the nano powder liquid is 20-120% of the mass of the nano powder;

The nano powder is selected from at least one of single-layer graphene, single-wall carbon nanotubes, and nano silver wires.

Preferably, the sheet diameter of the single-layer graphene is 0.5-5 μm, and the single-layer rate is ≥80%; the purity of the single-walled carbon nanotube is ≥95%, the diameter is 1-2 nm, and the length is 5-30 μm; The average diameter of the nano silver wires is less than or equal to 20 nm, and the length is more than or equal to 30 μm.

Preferably, the Lewis base is selected from at least one of LiI, LiAsF ₆ , LiPF ₆ , LiClO ₄ , LiN(SO ₃ CF ₃ ) ₂ , LiBF ₄ , and LiCF ₃ SO ₃ .

Preferably, the plasticizer is selected from at least one of polyethylene glycol 300 (PEG-300), ethylene glycol, anhydrous ethylene carbonate, anhydrous propylene carbonate, and triethylene glycol diisocaprylate .

Preferably, the mass of the plasticizer is 20-45% of the mass of the PVB resin.

Preferably, the solvent is N,N-dimethylformamide (DMF) or N-methylpyrrolidone (NMP) or absolute ethanol.

Preferably, the dispersant is polyvinylpyrrolidone (PVP), Dispersago-9311 or EFKA4310.

In another aspect of the present application, a method for preparing the above-mentioned all-solid PVB-based ion transport material is provided, which includes the following steps:

S1. First mix the dispersant and the solvent uniformly, then add nano powder to the mixture and disperse the nano powder in the solvent to obtain a nano powder liquid; dissolve the Lewis base in the plasticizer to obtain liquid B;

S2, the nano powder liquid and the B liquid are mixed uniformly to obtain a conductive paste;

S3. The conductive paste is mixed with PVB resin and stirred evenly, and after plasticization, an all-solid PVB-based ion transport material is obtained.

Preferably, in step S1, the mixture of dispersant, solvent and nano-powder is ultrasonically dispersed for 5-60 minutes with an ultrasonic cell pulverizer.

In another aspect of the present application, there is provided an electrochromic laminated glass, which is composed of an upper laminated glass, an ion transport adhesive film, and a lower laminated glass laminated in sequence; the ion transport adhesive film is made of any of the above-mentioned all solid PVB-based ion transport material is formed; the upper laminated glass is composed of tempered glass and an ITO coating and a molybdenum oxide coating sequentially plated on the tempered glass; the lower laminated glass is composed of tempered glass and an ITO coating and trioxide sequentially plated on the tempered glass Composition of tungsten coating.

Compared with the prior art, the beneficial effects of this application are:

This application uses single-layer graphene, single-wall carbon nanotubes or nano-silver wires as nano-powders, and by controlling the content of Lewis bases containing alkali metals in the conductive paste and the ratio of Lewis bases to nano-powders, it provides a An ion transport material with high conductivity. At the same time, the ion transport material is a solid material. It is applied to electrochromic laminated glass as an ion transport layer, which is not only convenient for packaging, but also solves the problem of difficult packaging of electrochromic devices, and the electrochromic clip The plastic glass has a fast discoloration speed, and the difference between the transmittance of the glass after the power is stable and when the power is off is greater than or equal to 45%, and the electrochromic effect is good. In this application, an ultrasonic cell pulverizer is used to ultrasonically disperse the mixture of dispersant, solvent and nano powder and control the dispersion time, which can guarantee the performance of the formed conductive slurry and prevent failure.

Detailed ways

In order to fully understand the technical content of the present application, the technical solution of the present application will be further introduced and illustrated below in conjunction with specific embodiments.

Example 1

This embodiment provides an all-solid PVB-based ion transport material and a preparation method of the ion transport material, and also provides an electrochromic laminated glass using the ion transport material.

Preparation method of all solid-state PVB-based ion transport materials:

(1) Accurately measure 150ml NMP in a 300ml Erlenmeyer flask, add 60mg PVP to it, stir evenly with a glass rod until all PVP is dissolved, and then add 150mg of monolayer graphene (sheet diameter 0.5-5μm, thickness 0.45nm, Single layer rate 80%), stir evenly, and disperse for 30 minutes with a 1KW ultrasonic cell pulverizer to obtain a nano-powder liquid.

Weigh 1200 g of anhydrous propylene carbonate in a beaker, add 250 g of LiAsF _{6 to it} , and heat at 80° C. and stir until all is dissolved to obtain liquid B.

(2) Take 40 grams of nano powder liquid and mix all B liquid uniformly to obtain conductive paste.

(3) Accurately weigh 4000g PVB resin powder and place it in the blender, then add the conductive paste to the blender containing PVB resin powder and stir evenly, take it out, seal and plasticize for more than 24 hours to obtain a solid PVB The base ion transport material is then extruded through a single screw to obtain an ion transport film, and the film thickness is controlled to be 0.3mm.

Preparation of electrochromic laminated glass:

Using the ion transport film prepared in this embodiment as the ion transport layer in the electrochromic laminated glass, the electrochromic laminated glass is produced. The pre-laminated structure of the electrochromic laminated glass is composed of the upper laminated glass, the ion transport film, The lower laminated glass is composed of 5mm toughened glass, 50nm thick ITO coating and 300nm thick molybdenum oxide coating successively plated on the glass, and the lower laminated glass is composed of 5mm toughened glass and successively plated on the glass. It is composed of 50nm thick ITO coating and 300nm thick tungsten trioxide coating. The pre-stacked structure was placed in a laminating furnace at -0.08MPa and 135°C for 35 minutes to prepare electrochromic laminated glass.

Performance Testing:

A conductivity tester was used to test the conductivity of the ion transport adhesive film prepared in this embodiment. And to test the time required for the color change of the electrochromic laminated glass when it is energized, use a light transmittance tester to test the light transmittance of the electrochromic laminated glass under power and power failure.

The conductivity of the ion transport adhesive film prepared in this example is 1.25 ms/cm. The time required for the electrochromic laminated glass to change color to a stable color after being energized is 16S, and the light transmittance of the glass when the color is stable 2%, the light transmittance of the glass after power off is 68%.

Example 2

Preparation method of all solid-state PVB-based ion transport materials:

(1) Accurately measure 150ml DMF in a 300ml Erlenmeyer flask, add 180mg PVP to it, stir evenly with a glass rod until all PVP is dissolved, and then add 300mg single-walled carbon nanotubes (purity greater than 95%, diameter 1- 2nm, length 5-30μm), stir evenly, and disperse for 45min with a 1KW ultrasonic cell pulverizer to obtain a nano-powder liquid.

Weigh 1000 g of anhydrous propylene carbonate in a beaker, add 250 g of LiClO _{4 to it} , and heat at 80° C. and stir until all is dissolved to obtain liquid B.

(2) Take 40 g of the nano powder liquid and mix all the liquid B uniformly to obtain a conductive paste.

(3) Accurately weigh 4000g PVB resin powder and place it in the blender, then add the conductive paste to the blender containing PVB resin powder and stir evenly, take it out, seal and plasticize for more than 24 hours to obtain a solid PVB The base ion transport material is then extruded through a single screw to obtain an ion transport film, and the film thickness is controlled to 0.5mm.

The electrochromic laminated glass was produced in the manner described in Example 1.

Performance Testing:

A conductivity tester was used to test the conductivity of the ion transport adhesive film prepared in this embodiment. And to test the time required for the color change of the electrochromic laminated glass when it is energized, use a light transmittance tester to test the light transmittance of the electrochromic laminated glass when the power is on and when the power is off.

The conductivity of the ion transport adhesive film prepared in this example is 1.16ms/cm, and the time required for the electrochromic laminated glass to change color to a stable color after being energized is 21S, and the light transmittance of the glass when the color is stable 3%, the light transmittance of the glass after power off is 65%.

Example 3

Preparation method of all solid-state PVB-based ion transport materials:

(1) Weigh 5g of dispersant EFKA4310 and 470g of absolute ethanol and stir evenly, add 25g of nano silver wires (average diameter less than 20nm, length greater than 30μm) into the mixture, stir evenly, and disperse for 45min with a 1KW ultrasonic cell pulverizer to obtain Nano powder body fluid.

Weigh 1200 g of triethylene glycol diisocaprylate in a beaker, add 250 g of LiClO _{4 to it} , and heat at 80° C. and stir until all is dissolved to obtain liquid B.

(2) Take 40 g of nano powder liquid and mix all B liquid uniformly to obtain conductive paste.

Performance Testing:

The conductivity of the ion transport adhesive film prepared in this example is 0.87ms/cm, and the time required for the electrochromic laminated glass to change color until the color is stable after being energized is 27S, and the light transmittance of the glass when the color is stable and unchanged 3%, the light transmittance of the glass after power off is 58%.

Example 4

Preparation method of all solid-state PVB-based ion transport materials:

(1) Accurately measure 150ml NMP in a 300ml Erlenmeyer flask, add 180mg Dispersago-9311 to it, stir evenly with a glass rod until all PVP is dissolved, and then add 150mg of single-layer graphene (sheet diameter 0.5-5μm, thickness 0.45nm, single layer rate 80%), stir evenly and then disperse for 30 minutes with a 1KW ultrasonic cell pulverizer to obtain a nano-powder liquid.

Weigh 1100g polyethylene glycol 300 in a beaker, add 250g LiPF6 to it, heat at 80°C and stir until all is dissolved to obtain liquid B.

(3) Accurately weigh 5500g of PVB resin powder and place it in the blender, then add the conductive paste to the blender containing PVB resin powder and stir evenly, take it out, seal and plasticize it for more than 24 hours to obtain a solid PVB The base ion transport material is then extruded through a single screw to obtain an ion transport film, and the film thickness is controlled to be 0.3mm.

Performance Testing:

The conductivity of the ion transport adhesive film prepared in this example is 0.81ms/cm, and the time required for the electrochromic laminated glass to change color until the color is stable after being energized is 29S, and the light transmittance of the glass when the color is stable and unchanged 1%, the light transmittance of the glass after power off is 55%.

Example 5

Preparation method of all solid-state PVB-based ion transport materials:

Weigh 1200 g of ethylene glycol in a beaker, add 250 g of LiBF _{4 to it} , and heat at 80° C. and stir until all is dissolved to obtain liquid B.

(3) Accurately weigh 2700g PVB resin powder and place it in the blender, then add the conductive paste to the blender containing PVB resin powder and stir evenly, take it out, seal and plasticize it for more than 24 hours to obtain all solid PVB The base ion transport material is then extruded through a single screw to obtain an ion transport film, and the film thickness is controlled to be 0.3mm.

Performance Testing:

The conductivity of the ion transport adhesive film prepared in this example is 0.96ms/cm, and the time required for the electrochromic laminated glass to change color to stable and unchanged after being energized is 24S, and when the color is stable, the light transmittance of the glass is 1%, the light transmittance of the glass after power off is 60%.

Example 6

Preparation method of all solid-state PVB-based ion transport materials:

Weigh 1200 g of anhydrous ethylene carbonate in a beaker, add 250 g of LiCF ₃ SO _{3 to it} , and heat at 80° C. and stir until all is dissolved to obtain liquid B.

Performance Testing:

The conductivity of the ion transport adhesive film prepared in this example is 0.91ms/cm, and the time required for the electrochromic laminated glass to change color to a stable color after being energized is 26S, and the light transmittance of the glass when the color is stable 2%, the light transmittance of the glass after power failure is 59%.

Example 7

Preparation method of all solid-state PVB-based ion transport materials:

(1) Accurately measure 150ml NMP in a 300ml Erlenmeyer flask, add 60mg PVP to it, stir evenly with a glass rod until all PVP is dissolved, and then add 150mg of monolayer graphene (sheet diameter 0.5-5μm, thickness 0.45nm, Single layer rate 80%), stir evenly and disperse for 30 minutes with a 1KW ultrasonic cell pulverizer to obtain nano powder liquid.

Weigh 1200 g of anhydrous propylene carbonate in a beaker, add 250 g of LiN(SO ₃ CF ₃ ) _{2 to it} , and heat at 80° C. and stir until all is dissolved to obtain liquid B.

Performance Testing:

The conductivity of the ion transport adhesive film prepared in this example is 0.82ms/cm, and the time required for the electrochromic laminated glass to change color to a stable color after being energized is 29S, and the light transmittance of the glass when the color is stable 1%, the light transmittance of the glass after power off is 55%.

Example 8

Preparation method of all solid-state PVB-based ion transport materials:

Weigh 1200 g of anhydrous propylene carbonate in a beaker, add 250 g of LiCF ₃ SO _{3 to it} , and heat at 80° C. and stir until all is dissolved to obtain liquid B.

Performance Testing:

The conductivity of the ion transport adhesive film prepared in this example is 0.79ms/cm. The time required for the electrochromic laminated glass to change color to stable and unchanged color is 30S when the color is stable and the light transmittance of the glass is stable and unchanged. 3%, the light transmittance of the glass after power off is 52%.

Example 9

Preparation method of all solid-state PVB-based ion transport materials:

Weigh 1200 g of anhydrous propylene carbonate in a beaker, add 250 g of LiI to it, and heat at 80° C. and stir until all is dissolved to obtain liquid B.

Performance Testing:

A conductivity tester was used to test the conductivity of the ion transport adhesive film prepared in this embodiment. And to test the time required for the color change of the electrochromic laminated glass when it is energized, the light transmittance of the electrochromic laminated glass under the power-on and power-off conditions was tested with a light transmittance tester.

The conductivity of the ion transport adhesive film prepared in this example is 0.78ms/cm. The time required for the electrochromic laminated glass to change color to stable and unchanged after being energized is 30S, and when the color is stable, the light transmittance of the glass is 3%, the light transmittance of the glass after power off is 51%.

Comparative example 1

This comparative example provides an all-solid PVB-based ion transport material and a preparation method of the ion transport material. Preparation method of all solid-state PVB-based ion transport materials:

(1) Accurately measure 150ml of NMP in a 300ml conical flask, add 60mg of PVP to it, stir evenly with a glass rod until all PVP is dissolved, and then add 150mg of monolayer graphene (sheet diameter 0.5-5μm, thickness 0.45nm, single The layer rate is 80%), the mixture is evenly stirred and then transferred to a pin-type sand mill for dispersion for 1 hour to obtain a nano-powder liquid.

(3) Accurately weigh 4000g PVB resin powder and place it in the blender, then add the conductive paste to the blender containing PVB resin powder and stir evenly, take it out, seal and plasticize for more than 24 hours to obtain a solid state The PVB-based ion transport material is then extruded through a single screw to obtain an ion transport film, and the film thickness is controlled to 0.3mm.

A conductivity tester was used to test the conductivity of the ion transport adhesive film prepared in this comparative example, and the conductivity was 0.02 ms/cm. After the ion transport film is placed at room temperature (25-32°C) for a week, crystals precipitate in the ion transport film, making the ion transport film turbid, and small particle spots can be observed in the film.

Comparative example 2

Preparation method of all solid-state PVB-based ion transport materials:

(1) Accurately measure 150ml NMP in a 300ml Erlenmeyer flask, add 60mg PVP to it, stir evenly with a glass rod until all PVP is dissolved, and then add 150mg of monolayer graphene (sheet diameter 0.5-5μm, thickness 0.45nm, Single layer rate 80%), stir evenly, and disperse for 90 minutes with a 1KW ultrasonic cell pulverizer to obtain a nano-powder liquid.

A conductivity tester was used to test the conductivity of the ion transport adhesive film prepared in this comparative example, and the conductivity was 0.11 ms/cm.

In another embodiment, compared to Comparative Example 2, the time for ultrasonic dispersion of the mixture of NMP, PVP and single-layer graphene with a 1KW ultrasonic cell pulverizer when preparing the nanopowder liquid was changed from 90 min to 60 min. Comparative example 2 is exactly the same. A conductivity tester was used to test the conductivity of the prepared ion transport film, and the conductivity was 0.69 ms/cm.

Comparative example 3

Weigh 1600 g of anhydrous propylene carbonate in a beaker, add 750 g of LiClO _{4 to it} , and heat at 80° C. and stir until all is dissolved to obtain liquid B.

A conductivity tester was used to test the conductivity of the ion transport adhesive film prepared in this comparative example, and the conductivity was 0.05 ms/cm. After the ion transport film is placed at room temperature (25-32°C) for a week, crystals precipitate in the ion transport film, making the ion transport film turbid, and small particle spots can be observed in the film.

Comparative example 4

Preparation method of all solid-state PVB-based ion transport materials:

Weigh 1200 g of anhydrous propylene carbonate in a beaker, add 360 g of LiAsF _{6 to it} , and heat at 80° C. and stir until all is dissolved to obtain liquid B.

A conductivity tester was used to test the conductivity of the ion transport adhesive film prepared in this comparative example, and the conductivity was 0.03 ms/cm. After the ion transport film is placed at room temperature (25-32°C) for a week, crystals precipitate in the ion transport film, making the ion transport film turbid, and small particle spots can be observed in the film.

Comparative example 5

Preparation method of all solid-state PVB-based ion transport materials:

Weigh 1000 g of anhydrous propylene carbonate in a beaker, add 280 g of LiClO _{4 to it} , and heat at 80° C. and stir until all is dissolved to obtain liquid B.

Comparative example 6

Preparation method of all solid-state PVB-based ion transport materials:

(1) Accurately measure 150ml NMP in a 300ml Erlenmeyer flask, add 60mg PVP to it, stir evenly with a glass rod until all PVP is dissolved, and then add 150mg of multilayer graphene (sheet diameter 0.5-5μm, thickness 1.0nm, 2-5 layers of graphene accounted for 80%), stirred evenly, and dispersed with a 1KW ultrasonic cell pulverizer for 30 minutes to obtain a nano-powder liquid.

Performance Testing:

The conductivity of the ion transport adhesive film prepared in this example is 0.37ms/cm, the time required for the electrochromic laminated glass to change color when energized is 93S, the light transmittance is 12% when the power is stable, and the light transmittance is 43 after the power is off. %.

Comparative example 7

This embodiment provides an all-solid PVB-based ion transport material and a preparation method of the ion transport material.

Preparation method of all solid-state PVB-based ion transport materials:

(1) Weigh 5g of dispersant EFKA4310 and 470g of absolute ethanol and stir evenly, add 25g of nano silver balls (5-25nm in diameter) to the mixed solution, stir evenly, and disperse for 45 minutes with a 1KW ultrasonic cell pulverizer to obtain a nano powder liquid.

A conductivity tester was used to test the conductivity of the ion transport adhesive film prepared in this comparative example, and the conductivity was 0.01 ms/cm.

In Comparative Example 1, a rod-pin sand mill was used to disperse the mixture of NMP, PVP and single-layer graphene to prepare a nano-powder liquid. The conductivity of the prepared ion transport film was only 0.02ms/cm. The reason may be The use of rod-pin sand mills for dispersion treatment will damage the sheet structure of the single-layer graphene, resulting in the failure of the conductive paste, which not only affects the conductivity of the film, but also causes crystals to precipitate in the film.

In Comparative Example 2, due to the longer time for ultrasonic dispersion of the mixture of NMP, PVP and single-layer graphene, the conductivity of the prepared ion transport film is 0.11ms/cm, which may be due to the longer dispersion time. The lamellar structure of graphene can also cause a certain degree of damage, resulting in a decrease in electrical conductivity.

In Comparative Examples 3-5, due to the high content of Lewis base in the conductive paste, the electrical conductivity of the prepared adhesive film was significantly reduced, which were 0.05 ms/cm, 0.03 ms/cm, and 0.05 ms/cm, respectively. The possible reason is that the increase of the concentration of Lewis base will lead to the increase of the effective carrier number and the increase of the ion conductivity, but when the concentration increases to a certain level, it will hinder _{the dissociation of LiClO 4} and LiAsF ₆ into free ions Li+ and ClO _4- , AsF ₆ -form a neutral ion pair, and Li+, ClO ₄ -, AsF ₆ -easily form excessive physical cross-links with PVB side chains and restrict ion transport.

In Comparative Examples 6-7, due to the addition of unsuitable nano-powders, the conductivity of the prepared film was significantly reduced, respectively 0.37ms/cm and 0.01ms/cm. When nano-silver balls were used for the nano-powders, The prepared adhesive film is almost insulated, and the conductivity of the prepared ion transport adhesive film is significantly reduced to 0.37ms/cm by using multilayer graphene as nanopowder. It is used in the production of electrochromic laminated glass and electrochromic clip After energized, the color of plastic glass needs 93 S to be stable and inconvenient. The discoloration speed is slow, and the minimum light transmittance can only reach 12%. After power off, the light transmittance is 43%, and the shielding effect of the glass is poor after power on.

The above only uses examples to further illustrate the technical content of this application for easier understanding by readers, but it does not mean that the implementation of this application is limited to this. Any technical extension or re-creation made in accordance with this application is subject to Protection of this application.

Summary of the invention

technical problem

The solution to the problem

The beneficial effects of the invention

Claims

An all-solid PVB-based ion transport material, which is characterized in that it is made by uniformly mixing conductive slurry and PVB resin in any proportion; the conductive slurry is composed of nano powder liquid and B liquid, and the nano powder liquid is made of a solvent. And nano powder dispersed in a solvent and a dispersant, the B liquid is composed of a plasticizer and an alkali metal-containing Lewis base, and the mass of the nano powder liquid is 2.7-3.2% of the mass of the B liquid;

The mass percentage of Lewis base in the B solution is 17-20%;

The mass of the dispersant in the nano powder liquid is 20-120% of the mass of the nano powder;

The nano powder is selected from at least one of single-layer graphene, single-wall carbon nanotubes, and nano silver wires.
The all-solid PVB-based ion transport material according to claim 1, wherein the sheet diameter of the single-layer graphene is 0.5-5 μm, and the single-layer rate is ≥80%; the purity of the single-walled carbon nanotubes is ≥ 95%, the diameter is 1-2 nm, and the length is 5-30 μm; the average diameter of the nano silver wire is less than or equal to 20 nm, and the length is more than or equal to 30 μm.
The all-solid PVB-based ion transport material according to claim 1, wherein the Lewis base is selected from LiI, LiAsF 6 , LiPF 6 , LiClO 4 , LiN(SO 3 CF 3 ) 2 , LiBF 4 , LiCF 3 At least one of SO 3.
The all-solid PVB-based ion transport material according to claim 1, wherein the plasticizer is selected from polyethylene glycol 300, ethylene glycol, anhydrous ethylene carbonate, anhydrous propylene carbonate, triethylene glycol At least one of alcohol diisocaprylate.
The all-solid PVB-based ion transport material according to claim 4, wherein the mass of the plasticizer is 20-45% of the mass of the PVB resin.
The all-solid PVB-based ion transport material according to claim 1, wherein the solvent is DMF or NMP or absolute ethanol.
The all-solid PVB-based ion transport material according to claim 1, wherein the dispersant is PVP, Dispersago-9311 or EFKA4310.
A method for preparing an all-solid PVB-based ion transport material according to claim 1, characterized in that it comprises the following steps:

S1. First mix the dispersant and the solvent uniformly, and then add nano powder to the mixture to disperse the nano powder in the solvent to obtain a nano powder liquid; dissolve the Lewis base in the plasticizer to obtain liquid B;

S2, the nano powder liquid and the B liquid are mixed uniformly to obtain a conductive paste;

S3. The conductive paste is mixed with PVB resin and stirred evenly, and after plasticization, an all-solid PVB-based ion transport material is obtained.
The method for preparing an all-solid PVB-based ion transport material according to claim 8, characterized in that, in step S1, the mixture of dispersant, solvent and nano-powder is ultrasonically dispersed for 5-60 minutes with an ultrasonic cell pulverizer.
An electrochromic laminated glass, which is characterized in that it is composed of an upper laminated glass, an ion transport adhesive film, and a lower laminated glass that are sequentially stacked; the ion transport adhesive film is composed of any one of claims 1-7. A solid PVB-based ion transport material is formed; the upper laminated glass is composed of tempered glass and an ITO coating and a molybdenum oxide coating successively plated on the tempered glass; the lower laminated glass is composed of tempered glass and an ITO coating successively plated on the tempered glass. Composition of tungsten oxide coating.