CN111196888B - Gel polymer electrolyte doped with modified particles and preparation method and application thereof - Google Patents
Gel polymer electrolyte doped with modified particles and preparation method and application thereof Download PDFInfo
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- CN111196888B CN111196888B CN202010009344.4A CN202010009344A CN111196888B CN 111196888 B CN111196888 B CN 111196888B CN 202010009344 A CN202010009344 A CN 202010009344A CN 111196888 B CN111196888 B CN 111196888B
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 40
- 239000002245 particle Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 5
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- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004408 titanium dioxide Substances 0.000 abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 10
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- -1 alkali metal salt Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000011245 gel electrolyte Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 208000008918 voyeurism Diseases 0.000 description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001566 impedance spectroscopy Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
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- 239000002077 nanosphere Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a gel polymer electrolyte doped with modified particles, a preparation method thereof and application thereof in an electrochromic device. The preparation method comprises the following steps: (1) dissolving a polymer matrix and lithium salt in a mixed solution of a plasticizer and a solvent, and continuously stirring at 45-55 ℃; the polymer matrix is one of polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate and polyvinylidene fluoride; (2) adding modified inorganic powder into the solution obtained in the step (1), and continuously stirring for 1-3 hours to form viscous sol; the total mass of the polymer matrix and the lithium salt is 100%, and the adding amount of the modified inorganic powder is 3-25 wt%; the modified inorganic powder is silicon dioxide or titanium dioxide, and the surface of the modified inorganic powder is coated with a PMMA layer; (3) and (3) pouring the sol obtained in the step (2) into a mold, and drying at 55-65 ℃ to obtain the gel polymer electrolyte doped with the modified particles.
Description
Technical Field
The invention relates to the technical field of electrochromism, in particular to a gel polymer electrolyte doped with modified particles and a preparation method and application thereof.
Background
The electrochromic glass is composed of transparent base materials such as glass and the like and a dimming material layer, and can generate reversible regulation on light transmittance and reflectivity under the action of low voltage (2-5V). The electrochromic glass has the intelligent functions of continuously changing colors, adjusting visible light transmittance and realizing continuous adjustment of transparency and opacity; the operation mode is diversified and the control is simple and convenient in use; the functional anti-glare and anti-peeping natural light irradiation device can improve the natural light irradiation intensity, and has anti-glare and anti-peeping functions, so that the device is widely applied to the fields and places such as building doors and windows, automobiles, advertisement decoration and meeting rooms. The Smart Glass (Smart Glass) does not have the defects that the traditional Solar Control Glass (Solar Control Glass) and Low Emissivity (Low Emissivity) cannot dynamically adjust the light transmittance, and is a window material which has a development prospect and integrates intelligence and energy conservation. One of the important elements is the presence of the electrolyte.
Like all electrochemical devices, electrochromic glass devices also require the presence of an electrolyte between the positive and negative electrodes that can transport ions, but separate electrons. Commonly used electrolyte materials include liquid materials with high conductivity, such as salt solutions, and solid electrolyte materials with high safety, such as ionic conductors. With the improvement of safety requirements of electrochromic glass, liquid electrolyte slowly begins to show its disadvantages, such as difficult packaging of small devices and easy leakage to cause safety accidents. As an emerging electrolyte, the polymer electrolyte has been developed from the beginning of the 70 s, and has been revolutionized for several decades, and has played an indispensable role in more and more fields, and the development of the polymer electrolyte can be roughly divided into four stages:
firstly, the method comprises the following steps: in the seventies of the 19 th century, Fenton et al reported for the first time in 1973 that a two-component composite of polyethylene oxide (PEO) and an alkali metal salt was synthesized, and the composite was in a solid state and had a certain ionic conductivity and could be used as an electrolyte of a battery. II, secondly: more new materials and new theories are beginning to be developed, including dynamic permeation models of Ratner, WLF equations, etc. In addition, the application of polymer electrolytes is beginning to advance to the electrochromic and smart window areas. Thirdly, the method comprises the following steps: with the further development of lithium ion batteries and small devices, the conventional PEO-based polymer electrolyte cannot adapt to the fast pace well, so people begin to search for more novel and better-performing materials, including structural modification of the original materials, and the like. Fourthly, the method comprises the following steps: this stage mainly introduces inorganic particles and completes the combination of inorganic-organic composite. It has been found that not only the ionic conductivity of the polymer electrolyte can be improved but also the mechanical properties thereof can be effectively enhanced by introducing inorganic nanoparticles such as silicon oxide, aluminum oxide, etc. Meanwhile, research on ionic liquids has also been slowly started.
The gel polymer electrolyte has unique advantages when being applied to an electrochromic device, and mainly comprises a simple preparation method; the working electrode and the counter electrode can be effectively isolated; compared with liquid electrolyte, the gel electrolyte has lower activity to lithium ions, does not react with the lithium ions, has higher stability in the lithium ions and is not easy to leak; the problem of volume change of the electrode in the circulation process can be better solved; can act as an adhesive for better device assembly.
Chinese patent CN109507840A discloses a preparation method of a gel electrolyte, which mainly comprises an electrolyte solution composed of an ionic-like liquid and a lithium salt, and then hydrophilic silica is doped under the condition of introducing nitrogen, so that the preparation process is complex. Chinese patent CN110212241A discloses a preparation method of a porous gel polymer electrolyte, which comprises a lithium salt and a three-dimensional porous network structure formed by a polymer matrix, wherein the polymer matrix is composed of a polymer and inorganic nanoparticles. But does not address the modification of inorganic nanoparticles. Chinese patent CN110208996A discloses a gel electrolyte applied to an electrochromic device and a preparation method thereof, wherein the gel electrolyte comprises electrolyte, a polymer matrix and hydrophobic nano fumed silica.
Because the surface characteristics of the inorganic nano particles are greatly different from those of the polymer used as the matrix, the intrinsic inorganic nano particles are easy to aggregate and segregate when being compounded with the polymer, so that the performance of the composite material is reduced, and the composite material is denatured in the service process, so that the performance is deteriorated or even disappears. Therefore, the inorganic particle composite concentration used in the prior art is in a low range, and the inorganic-organic composite effect is not fully exerted.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a preparation method of a gel polymer electrolyte doped with modified particles, which adopts inorganic nano particles (modified inorganic powder) with the surface coated with a methyl methacrylate (PMMA) layer, utilizes the good compatibility of PMMA and a polymer matrix to ensure that the modified inorganic powder still has good dispersibility under high concentration, and fully exerts the inorganic-organic composite effect, so that the prepared gel polymer electrolyte has good electrochemical performance and mechanical performance, and can be well applied to electrochromic devices.
A method for preparing a gel polymer electrolyte doped with modified particles comprises the following steps:
(1) dissolving a polymer matrix and lithium salt in a mixed solution of a plasticizer and a solvent, and continuously stirring at 45-55 ℃;
the polymer matrix is one of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polymethyl methacrylate (PMMA) and polyvinylidene fluoride (PVDF);
(2) adding modified inorganic powder into the solution obtained in the step (1), and continuously stirring for 1-3 hours to form viscous sol;
the total mass of the polymer matrix and the lithium salt is 100%, and the adding amount of the modified inorganic powder is 3-25 wt%;
the modified inorganic powder is silicon dioxide or titanium dioxide, and the surface of the modified inorganic powder is coated with a PMMA layer;
(3) and (3) pouring the sol obtained in the step (2) into a mold, and drying at 55-65 ℃ to obtain the gel polymer electrolyte doped with the modified particles.
The invention covers an organic layer on the surface of inorganic powder (such as silicon dioxide or titanium dioxide), makes the inorganic powder well dispersed in a polymer matrix by utilizing better compatibility among organic matters, enhances the electrochemical performance, thermal stability and optical transmittance of the gel polymer, and can be well applied to electrochromic devices.
In the step (1), the polymer matrix is easily soluble in a solvent, and the lithium salt is easily soluble in a plasticizer. Too low a concentration of the polymer matrix results in no film formation, and too high a concentration results in a gel sheet that is too stiff and has a low degree of bonding to the electrode sheet. The increase of the lithium salt concentration is favorable for increasing the number of carrier ions, and the increase of the ionic conductivity is not favorable for forming microcrystals after the lithium salt concentration exceeds a certain concentration. Increasing the plasticizer concentration also increases the ionic conductivity of the overall gel film, but too much concentration reduces the mechanical strength of the system. Therefore, in all aspects, preferably, in the step (1), the mass ratio of the polymer matrix, the lithium salt, the plasticizer and the solvent is 8-10: 1-5: 15-25: 60-80.
Preferably, in the step (2), the modified inorganic powder is added in an amount of 10wt% to 15wt% based on 100% by mass of the total mass of the polymer matrix and the lithium salt, and the ionic conductivity of the obtained gel polymer electrolyte is the maximum.
Preferably, in the step (2), the particle size of the modified inorganic powder is 100 to 200 nm.
The lithium salt may be LiPF6、LiAsF6、LiBF4、LiClO4、LiCF3SO3、LiN(CF3SO2)2Preferably LiClO4. Lithium perchlorate is one of the mainstream lithium salts used in current commercial electrolyte, has relatively stable property, is not sensitive to water, and is easily soluble in propylene carbonate.
The plasticizer can be one of Propylene Carbonate (PC), Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC). The plasticizer is generally required to be in a liquid state at normal temperature, and has the advantages of good thermal stability, high boiling point, low melting point, large dielectric constant, low viscosity, good electrochemical stability, low volatility, no toxicity and good compatibility with a system. The plasticizer is preferably propylene carbonate, depending on various factors.
The solvent may be acetone.
Preferably, the preparation method of the modified inorganic powder comprises the following steps:
(A) ultrasonically dispersing inorganic powder in an ethanol water solution, then dropwise adding a silane coupling agent, continuously stirring for 6-10 hours at 55-65 ℃, centrifuging, and drying to obtain an intermediate product;
the inorganic powder is silicon dioxide or titanium dioxide, and the particle size is 15-20 nm;
(B) and (B) ultrasonically dispersing the intermediate product obtained in the step (A) in deionized water, then adding an initiator and a polymer monomer, continuously stirring for 4-8 hours at 75-85 ℃ in a nitrogen atmosphere, centrifuging, and drying to obtain the modified inorganic powder.
Introducing a silane coupling agent on the surface of the inorganic powder, and performing hydrolysis reaction by using hydroxyl on the surface of the inorganic powder, thereby realizing grafting of the silane coupling agent. Polymerizing a layer of organic matter on the surface of the inorganic powder grafted with the silane coupling agent, and utilizing an initiator to break and reconnect double bonds on the silane coupling agent and the polymer monomer so as to successfully complete polymerization.
The silane coupling agent can be KH-570 or A-171, preferably KH-570. KH-570 is an organic functional group silane coupling agent, and can improve the mechanical and electrical properties of the glass fiber reinforced and inorganic filler-containing thermosetting resin, and is beneficial to improving the adhesive property of organic materials and inorganic materials.
Preferably, in the step (A), the volume ratio of the ethanol to the water in the ethanol aqueous solution is 2-4: 1.
Preferably, in the step (A), the ratio of the inorganic powder, the ethanol aqueous solution and the silane coupling agent is 1-2 g, 200mL and 2-4 g;
in the step (B), the ratio of the intermediate product, the deionized water, the initiator and the polymer monomer is 0.5-2 g/100 mL/0.01-1 g/1-6 g.
Preferably, in the step (1), the polymer matrix is polyvinylidene fluoride-hexafluoropropylene;
in the step (B), the polymer monomer is methyl methacrylate. On one hand, the polymer PMMA of methyl methacrylate can be blended and modified with PVDF-HFP, the PMMA has higher liquid absorption rate, lithium salt has higher activity in the PMMA, and meanwhile, the PMMA is also an amorphous polymer, the chain segment movement is favorable for the transmission of the lithium salt, and the polymer has better compatibility with the PVDF-HFP.
The initiator may be potassium persulfate.
In the step (3), preferably, the mold is made of polytetrafluoroethylene, so that the gel polymer electrolyte gel sheet can be stripped more conveniently and more easily. The drying temperature range is considered to allow sufficient volatilization of the solvent while retaining the plasticizer as much as possible.
The invention also provides the gel polymer electrolyte doped with the modified particles prepared by the preparation method.
The invention also provides application of the gel polymer electrolyte doped with the modified particles in an electrochromic device.
Compared with the prior art, the invention has the main advantages that: on one hand, PMMA and polymer matrix PVDF-HFP have the effect of blending modification, and the polymer blending can inhibit crystallization, improve the segment motion capability, improve the conductivity and improve the mechanical property; on the other hand, the good compatibility of PMMA and PVDF-HFP improves the dispersion effect of the modified inorganic powder in the polymer matrix and the doping effect of the modified inorganic powder, and the good electrochemical performance and the good mechanical performance of the prepared composite gel polymer electrolyte are achieved under the combined action of the PMMA and the PVDF-HFP.
Drawings
FIG. 1 is an SEM photograph of the unmodified silica of comparative example 1, in which the magnification of the large figure is 1 ten thousand times and the magnification of the insert figure at the upper right corner is 5 ten thousand times;
FIG. 2 shows SiO as modified silica in comparative example 22SEM photograph of PMMA-1 with a magnification of 1 ten thousand times for the big picture and a magnification of 5 ten thousand times for the inset in the upper right corner;
FIG. 3 shows a modified silica SiO in example 12SEM photograph of PMMA-2, with a magnification of 1 ten thousand times for the large image and a magnification of 5 ten thousand times for the inset in the upper right corner;
FIG. 4 shows the unmodified silica in comparative example 1, the modified silica SiO in comparative example 22PMMA-1, modified silica SiO in example 12-infrared spectra of PMMA-2, MMA and KH-570;
fig. 5 is a graph comparing ionic conductivities of the gel polymer electrolytes of comparative examples 1 and 2 and example 1.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Comparative example 1
Dissolving dried polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and lithium perchlorate in a mixed solution of PC and acetone according to a ratio, and magnetically stirring at 50 ℃. The mass ratio of polyvinylidene fluoride-hexafluoropropylene to lithium perchlorate to PC to acetone is 9:3:20: 68.
Adding unmodified silica with different concentrations into the solution, wherein the mass sum of the polyvinylidene fluoride-hexafluoropropylene and the lithium perchlorate is 100%, and the content of the doped unmodified silica is 1%, 2%, 3%, 4%, 5%, 7%, 10% and 15% in sequence, and continuously stirring for 2h to form viscous sol. And then pouring the sol into a polytetrafluoroethylene mold, and putting the polytetrafluoroethylene mold into an oven to dry for 12 hours at the temperature of 60 ℃ to obtain the gel polymer electrolyte.
Comparative example 2
Dissolving dried polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and lithium perchlorate in a mixed solution of PC and acetone according to a ratio, and magnetically stirring at 50 ℃. The mass ratio of polyvinylidene fluoride-hexafluoropropylene to lithium perchlorate to PC to acetone is 9:3:20: 68.
Adding modified silicon dioxide SiO with different concentrations into the solution2-PMMA-1, modified silicon dioxide SiO doped with 100% of the sum of the mass of polyvinylidene fluoride-hexafluoropropylene and lithium perchlorate2The content of PMMA-1 was, in order, 1%, 2%, 3%, 4%, 5%, 7%, 10%, 15%, stirring was continued for 2h to form a viscous sol. And then pouring the sol into a polytetrafluoroethylene mold, and putting the polytetrafluoroethylene mold into an oven to dry for 12 hours at the temperature of 60 ℃ to obtain the gel polymer electrolyte.
Modified silicon dioxide SiO2The preparation method of PMMA-1 is as follows:
(A) dispersing 1.5g of unmodified silicon dioxide in 200mL of ethanol, performing ultrasonic treatment for 30min, then dropwise adding 3g of silane coupling agent KH-570, magnetically stirring at 60 ℃ for 8h, centrifuging the stirred solution for 3 times by using deionized water, and then performing vacuum drying at 50 ℃ for 12h to obtain an intermediate product;
(B) dispersing 1g of the intermediate product obtained in the step (A) in 100mL of deionized water, performing ultrasonic treatment for 30min, adding 0.05g of potassium persulfate and 3g of Methyl Methacrylate (MMA), performing magnetic stirring for 6h at 80 ℃ in a nitrogen atmosphere, centrifuging the stirred solution for 3 times by using deionized water, and performing vacuum drying at 50 ℃ for 12h to obtain modified silicon dioxide SiO2-PMMA-1。
Example 1
Dissolving dried polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and lithium perchlorate in a mixed solution of PC and acetone according to a ratio, and magnetically stirring at 50 ℃. The mass ratio of polyvinylidene fluoride-hexafluoropropylene to lithium perchlorate to PC to acetone is 9:3:20: 68.
Adding modified silicon dioxide SiO with different concentrations into the solution2-PMMA-2, modified silicon dioxide SiO doped with 100% of the sum of the mass of polyvinylidene fluoride-hexafluoropropylene and lithium perchlorate2The content of PMMA-2 was, in order, 1%, 2%, 3%, 4%, 5%, 7%, 10%, 15%, stirring was continued for 2h to form a viscous sol. And then pouring the sol into a polytetrafluoroethylene mold, and putting the polytetrafluoroethylene mold into an oven to dry for 12 hours at the temperature of 60 ℃ to obtain the gel polymer electrolyte.
Modified silicon dioxide SiO2Preparation method of PMMA-2 and modified silica SiO in comparative example 22The preparation of PMMA-1 was identical, except that in step (A), ethanol was replaced with an aqueous solution of ethanol (150mL of ethanol, 50mL of deionized water) in a volume ratio of 3: 1.
Comparative examples 1 and 2 are different from example 1 in the inorganic powder. As shown in FIGS. 1 to 3, FIG. 1 shows that inorganic powders are piled together, the particle size is about 15 to 20nm as shown in the large figure, FIG. 2 shows that the modification is not successful, the morphology is similar to that of FIG. 1, and FIG. 3 shows that the nanospheres are successfully preparedThe result shows that PMMA is successfully grafted on the silicon dioxide pellets, and the particle size is measured to be 100-200 nm. FIG. 4 shows the SiO that was successfully modified2The PMMA-2 pellets not only retain the antisymmetric stretching vibration peak of the original Si-O-Si of the silica, but also show the peaks which are not existed in the silica and are only above MMA and KH-570, such as>C ═ O stretching vibration peak, C — H stretching vibration peak. FIGS. 3 and 4 in combination demonstrate the successful preparation of PMMA-coated silica pellets, SiO2-PMMA-2。
In order to measure the ionic conductivity of the gel polymer electrolyte, the prepared gel polymer electrolyte is cut into stainless steel wafers, the blocking electrodes of the stainless steel wafers/the gel polymer electrolyte/the stainless steel wafers are externally connected to an electrochemical workstation, and the impedance spectrum of the electrochemical workstation is measured.
Then, using the formula
Calculating the ionic conductivity of the product, wherein:
σ is the ionic conductivity (S · cm)-1)；
d is the thickness (cm) of the gel polymer electrolyte membrane, which can be measured by a vernier caliper, and is specifically 0.20 mm;
Rbthe resistance is the bulk resistance (omega) of the polymer, and can be directly read through impedance spectroscopy;
a is the effective contact area of the gel polymer electrolyte, here the area of the stainless steel disc, which is 1.618cm in diameter.
As shown in fig. 5, after the successfully modified silica is doped, the maximum doping amount of the silica can be increased, and at the same time, the ion conductivity of the gel polymer electrolyte is increased more, and no subsequent severe slip-down phenomenon occurs. Therefore, the gel polymer electrolyte doped with the successfully modified silicon dioxide is a good electrolyte material suitable for electrochromic devices. Moreover, when the ethanol is replaced by the ethanol aqueous solution with the volume ratio of 1:3 when preparing the modified silica, the maximum doping amount of the silica and the ions of the gel polymer electrolyte can be further improvedElectrical conductivity. Example 1 doping of modified powder SiO2PMMA-2 with an ionic conductivity of 2.22X 10 at room temperature at a doping level of 10wt%-3S/cm, which is significantly higher than comparative examples 1 and 2.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (6)
1. A preparation method of a gel polymer electrolyte doped with modified particles is characterized by comprising the following steps:
(1) dissolving a polymer matrix and lithium salt in a mixed solution of a plasticizer and a solvent, and continuously stirring at 45-55 ℃;
the polymer matrix is one of polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate and polyvinylidene fluoride;
(2) adding modified inorganic powder into the solution obtained in the step (1), and continuously stirring for 1-3 hours to form viscous sol;
the total mass of the polymer matrix and the lithium salt is 100%, and the adding amount of the modified inorganic powder is 10-25 wt%;
the modified inorganic powder is silicon dioxide, and the surface of the modified inorganic powder is coated with a PMMA layer; the particle size of the modified inorganic powder is 100-200 nm;
the preparation method of the modified inorganic powder comprises the following steps:
(A) ultrasonically dispersing inorganic powder into an ethanol water solution with the volume ratio of ethanol to water being 2-4: 1, then dropwise adding a silane coupling agent, continuously stirring for 6-10 hours at 55-65 ℃, centrifuging, and drying to obtain an intermediate product; the ratio of the inorganic powder to the ethanol aqueous solution to the silane coupling agent is 1-2 g to 200mL to 2-4 g;
the inorganic powder is silicon dioxide, and the particle size is 15-20 nm;
(B) ultrasonically dispersing the intermediate product obtained in the step (A) in deionized water, then adding an initiator and a polymer monomer, continuously stirring for 4-8 hours at 75-85 ℃ in a nitrogen atmosphere, centrifuging, and drying to obtain the modified inorganic powder; the ratio of the intermediate product to the deionized water to the initiator to the polymer monomer is 0.5-2 g to 100mL to 0.01-1 g to 1-6 g;
(3) and (3) pouring the sol obtained in the step (2) into a mold, and drying at 55-65 ℃ to obtain the gel polymer electrolyte doped with the modified particles.
2. The method for preparing the gel polymer electrolyte doped with the modified particles according to claim 1, wherein in the step (1), the mass ratio of the polymer matrix, the lithium salt, the plasticizer and the solvent is 8-10: 1-5: 15-25: 60-80.
3. The method for preparing gel polymer electrolyte doped with modified particles as claimed in claim 1, wherein in the step (2), the modified inorganic powder is added in an amount of 10wt% to 15wt% based on 100% of the total mass of the polymer matrix and the lithium salt.
4. The method for preparing gel polymer electrolyte of doped modified particle according to claim 1, wherein in the step (1), the polymer matrix is polyvinylidene fluoride-hexafluoropropylene;
in the step (B), the polymer monomer is methyl methacrylate.
5. The gel polymer electrolyte doped with modified particles prepared by the preparation method according to any one of claims 1 to 4.
6. Use of the modified particle doped gel polymer electrolyte of claim 5 in an electrochromic device.
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