CN113299987B - Preparation method of solid polymer electrolyte of zinc ion battery - Google Patents
Preparation method of solid polymer electrolyte of zinc ion battery Download PDFInfo
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- 239000007787 solid Substances 0.000 title claims abstract description 37
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 36
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 19
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 14
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 125000004386 diacrylate group Chemical group 0.000 claims description 8
- 244000028419 Styrax benzoin Species 0.000 claims description 7
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 7
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 7
- 229960002130 benzoin Drugs 0.000 claims description 7
- 235000019382 gum benzoic Nutrition 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000007605 air drying Methods 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 3
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 28
- 239000011701 zinc Substances 0.000 description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 230000001678 irradiating effect Effects 0.000 description 6
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
- C08F299/028—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight photopolymerisable compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method of a solid polymer electrolyte of a zinc ion battery, which comprises the following steps: the method comprises the following steps: heating and melting PEGDA; step two: adding a photoinitiator into PEGDA; step three: placing the liquid obtained in the step two under a xenon lamp for irradiation; step four: sequentially adding zinc acetate dihydrate and PAN into an NMP solvent, and heating and stirring the mixed solution in a water bath to form a light yellow liquid; step five: slowly pouring the light yellow liquid obtained in the step four into the PEGDA liquid obtained in the step three, and continuously heating and stirring in a water bath; step six: and D, transferring the mixed liquid obtained in the fifth step into a culture dish, and drying and forming in a forced air drying oven to obtain the solid polymer electrolyte membrane. The zinc ion solid polymer electrolyte prepared by the method can improve the interface contact capability, and the higher ionic conductivity can reduce the polarization and improve the cycling stability of the battery.
Description
Technical Field
The invention belongs to the field of new energy materials and electrochemistry, relates to a preparation method of a solid polymer electrolyte, and particularly relates to a preparation method of a polyacrylonitrile-polyethylene glycol diacrylate-based solid polymer electrolyte.
Background
Among rechargeable secondary batteries that have been commercialized at present, lithium ion batteries LIBs are considered as the most potential energy storage and conversion technology in hybrid/electric vehicles and portable electronic devices due to their relatively high energy density and long cycle stability. However, in the lithium ion battery, lithium dendrites are formed due to irregular deposition of metal lithium during charging and discharging, and the lithium dendrites may penetrate through a separator to cause short circuit along with the growth of the lithium dendrites, so that safety problems such as fire and explosion are easily caused due to local high current density heat generation and a flammable environment of an organic electrolyte system. In addition to the above safety issues, the application of lithium ion battery technology also faces the problem of high cost due to the shortage of lithium metal resources. There is therefore a pressing need for alternative high safety, low cost rechargeable secondary battery technologies. While the water-based zinc ion battery is undoubtedly an attractive choice among many candidate batteries, in recent years, with the research on water-based zinc ion batteries, the research on water-based zinc ion batteries is intense, and the discovery still has some troublesome problems, such as dendritic growth of metal zinc negative electrode, MnO of zinc ion battery2Dissolution of the positive electrode, and the like.
Solid polymer electrolytes generally have higher mechanical strength than liquid electrolytes and therefore can act as a physical barrier, retaining Zn2+The growth of dendritic crystals is inhibited while the conductivity is ensured, and the problem of dissolution of the anode of the water-based battery is fundamentally solved; compared with the all-solid electrolyte, the polymer solid electrolyte has the advantages of easy processing, close contact with the electrode and the like. But the conductivity of the zinc ion solid state polymer electrolyte is low due to the strong interaction of divalent zinc ions. Therefore, the invention of high room temperature conductivity, which can improve the contact between the positive and negative electrode interfaces and can be applied to the solid state polymerization of the zinc ion battery is urgently neededA substance electrolyte.
Disclosure of Invention
The invention aims to provide a preparation method of a solid polymer electrolyte of a zinc ion battery, which aims to solve the problems of low room-temperature conductivity, nonuniform deposition of a metal zinc cathode, dissolution of an active material of a positive electrode and the like of the conventional zinc ion solid polymer electrolyte.
The purpose of the invention is realized by the following technical scheme:
a process for preparing the solid polymer electrolyte of Zn-ion battery from the mixture of PEGDA and PAN includes ultraviolet initiated polymerization, Zn (OAc)2·2H2O is used as a zinc source to provide zinc ions, and comprises the following steps:
the method comprises the following steps: heating and melting polyethylene glycol diacrylate (PEGDA);
step two: adding the photoinitiator into PEGDA, wherein: the photoinitiator is benzoin dimethyl ether (DMPA), and the addition amount of the photoinitiator is 1-3% of the mass of the polyethylene glycol diacrylate;
step three: and (3) irradiating the liquid obtained in the second step under a xenon lamp, wherein the PEGDA is partially polymerized under the irradiation of a photoinitiator and ultraviolet light, wherein: the constant-temperature irradiation time of the xenon lamp is 5-10 min;
step four: adding zinc acetate dihydrate (Zn (OAc)2·2H2O) and Polyacrylonitrile (PAN) are sequentially added into 10ml of N-methylpyrrolidone (NMP) solvent, and the mixed solution is placed into a water bath kettle to be heated and stirred to form light yellow liquid, wherein: zn2+CN = 0.9-1.1: 1 (mol ratio), water bath heating temperature is 80-100 ℃, and time is 40-50 min;
step five: slowly pouring the light yellow liquid obtained in the fourth step into the PEGDA liquid obtained in the third step, and continuously heating and stirring in a water bath, wherein: the mass ratio of the PEGDA to the PAN is 1.3-1.6: 1, heating in a water bath at the temperature of 80-100 ℃ for 5-10 min;
step six: transferring the mixed liquid obtained in the fifth step into a culture dish, drying and forming in a forced air drying oven, and obtaining the solid polymer electrolyte membrane, wherein: the drying temperature is 130-150 ℃, and the drying time is 40-60 min.
Polyacrylonitrile (PAN) is a polymer with good stability, strong heat resistance and good flame retardancy, is a solid polymer electrolyte polymer matrix which is widely researched, but has poor mechanical properties, and has a strong polar-CN group contained on a macromolecular chain, and has poor interface compatibility with a metal electrode; polyethylene glycol diacrylate (PEGDA) is a hydrogel with good biocompatibility, high ionic conductivity, and 2 carbon-carbon double bonds at the molecular chain end, and can be rapidly polymerized in the presence of a photoinitiator and ultraviolet light. Thus, on the one hand, the-CN groups are destroyed during the reaction and on the other hand, uv light initiated polymerized PEGDA is blended with PAN to obtain a high ionic conductivity, high mechanical strength solid polymer electrolyte.
Compared with the prior art, the invention has the following advantages:
1. the method has simple synthetic route, and the prepared zinc ion solid polymer electrolyte has high ionic conductivity (5.6 multiplied by 10)-4 S cm-1) Certain flexibility and good mechanical strength.
2. The zinc ion solid polymer electrolyte prepared by the method can improve the interface contact capability, and the higher ionic conductivity can reduce the polarization and improve the cycling stability of the battery.
Drawings
FIG. 1 is a graph of the AC impedance of a solid polymer electrolyte;
FIG. 2 is a graph showing the cycle performance obtained by assembling a symmetric cell with a zinc sheet and a solid polymer electrolyte;
FIG. 3 shows the morphology of the zinc metal deposited on the pole piece after cycling of the symmetric cell, (a) 5 μm and (b) 10 μm.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
The method comprises the following steps: heating 0.3g polyethylene glycol acrylate (PEGDA) at 80 deg.C to melt to obtain colorless transparent viscous liquid;
step two: adding benzoin dimethyl ether (DMPA) photoinitiator with the mass fraction of 2% into PEGDA, and continuously stirring for 5min at 80 ℃ to form uniform colorless transparent viscous liquid;
step three: placing the liquid obtained in the step two under a xenon lamp with the power of 1.125W, irradiating for 10min at the constant temperature of 60 ℃, and partially polymerizing PEGDA under the irradiation of a photoinitiator and ultraviolet light to obtain colorless transparent viscous liquid for later use;
step four: 0.83g of Zn (OAc)2·2H2Sequentially adding O and 0.2g Polyacrylonitrile (PAN) into 10ml of N-methylpyrrolidone (NMP) solvent, and heating and stirring the mixed solution in a water bath kettle at the temperature of 80 ℃ for 50min to form light yellow liquid;
step five: slowly pouring the light yellow liquid obtained in the step four into the PEGDA liquid obtained in the step three, and heating the light yellow liquid in water bath at the temperature of 80 ℃ for 10 min;
step six: and (4) transferring the mixed liquid obtained in the fifth step into a culture dish, and drying in a forced air drying oven at 140 ℃ for 55min for forming to obtain the solid polymer electrolyte membrane.
Example 2
The method comprises the following steps: heating 0.3g polyethylene glycol acrylate (PEGDA) at 80 deg.C to melt to obtain colorless transparent viscous liquid;
step two: adding benzoin dimethyl ether (DMPA) photoinitiator with the mass fraction of 2% into PEGDA, and continuously stirring for 5min at 80 ℃ to form uniform colorless transparent viscous liquid;
step three: placing the liquid obtained in the step two under a xenon lamp with the power of 1.125W, and irradiating for 8min at the constant temperature of 60 ℃, wherein the PEGDA is partially polymerized under the irradiation of a photoinitiator and ultraviolet light and is still colorless transparent viscous liquid for later use;
step four: 0.83g of Zn (OAc)2·2H2Sequentially adding O and 0.2g Polyacrylonitrile (PAN) into 10ml of N-methylpyrrolidone (NMP) solvent, and heating and stirring the mixed solution in a water bath kettle at the temperature of 80 ℃ for 50min to form light yellow liquid;
step five: slowly pouring the light yellow liquid obtained in the step four into the PEGDA liquid obtained in the step three, and heating the light yellow liquid in water bath at the temperature of 80 ℃ for 10 min;
step six: and (4) transferring the mixed liquid obtained in the fifth step into a culture dish, and drying in a forced air drying oven at 140 ℃ for 55min for forming to obtain the solid polymer electrolyte membrane.
Preparation and performance test of PAN-PEGDA solid polymer electrolyte membrane: cutting the dried and formed solid polymer electrolyte membrane into a wafer with the diameter of 12mm, wherein a small amount of zinc acetate can be separated out on the surface in the drying and forming process to further improve the resistance of the electrolyte membrane, so that 8 mu L of deionized water is dripped at the interface when the battery is assembled to remove the influence of the surface zinc acetate on the impedance. The electrochemical alternating current impedance test uses a PARST electrochemical test system, and the test frequency is 1 MHz-1 Hz; a Neware battery test system is used for constant current charge and discharge test, and the constant current charge and discharge adopts 0.1 mA cm-2The current density of (1).
FIG. 1 is a AC impedance spectrum of a PAN-PEGDA solid polymer electrolyte membrane prepared in this example, which had a thickness of about 250 μm and an impedance of 22. omega. and a calculated conductivity of about 5.6X 10-4 S cm-1。
FIG. 2 is a diagram of a symmetrical cell assembled by PAN-PEGDA solid polymer electrolyte membranes prepared in the present example at 0.1 mA cm-2The constant current charging and discharging curve of the current density test shows that the voltage polarization is small and stable, and the symmetrical battery can stably circulate for 140 hours.
Fig. 3 is an SEM photograph of metal zinc deposited on a pole piece after 100 times of constant current charging and discharging of the symmetrical battery assembled from the PAN-PEGDA solid polymer electrolyte membrane prepared in this example, and it can be seen from the figure that the deposited metal zinc is uniformly distributed.
Example 3
The method comprises the following steps: heating 0.3g polyethylene glycol acrylate (PEGDA) at 80 deg.C to melt to obtain colorless transparent viscous liquid;
step two: adding benzoin dimethyl ether (DMPA) photoinitiator with the mass fraction of 2% into PEGDA, and continuously stirring for 5min at 80 ℃ to form uniform colorless transparent viscous liquid;
step three: placing the liquid obtained in the step two under a xenon lamp with the power of 1.125W, and irradiating for 5min at the constant temperature of 60 ℃, wherein the PEGDA is partially polymerized under the irradiation of a photoinitiator and ultraviolet light and is still colorless transparent viscous liquid for later use;
step four: 0.83g of Zn (OAc)2·2H2Sequentially adding O and 0.2g Polyacrylonitrile (PAN) into 10ml of N-methylpyrrolidone (NMP) solvent, and heating and stirring the mixed solution in a water bath kettle at the temperature of 80 ℃ for 50min to form light yellow liquid;
step five: slowly pouring the light yellow liquid obtained in the step four into the PEGDA liquid obtained in the step three, and heating the light yellow liquid in water bath at the temperature of 80 ℃ for 10 min;
step six: and (4) transferring the mixed liquid obtained in the fifth step into a culture dish, and drying in a forced air drying oven at 140 ℃ for 55min for forming to obtain the solid polymer electrolyte membrane.
Example 4
The method comprises the following steps: heating 0.3g polyethylene glycol acrylate (PEGDA) at 80 deg.C to melt to obtain colorless transparent viscous liquid;
step two: adding benzoin dimethyl ether (DMPA) photoinitiator with the mass fraction of 2% into PEGDA, and continuously stirring for 5min at 80 ℃ to form uniform colorless transparent viscous liquid;
step three: placing the liquid obtained in the step two under a xenon lamp with the power of 1.125W, and irradiating for 5min at the constant temperature of 60 ℃, wherein the PEGDA is partially polymerized under the irradiation of a photoinitiator and ultraviolet light and is still colorless transparent viscous liquid for later use;
step four: 0.91g of Zn (OAc)2·2H2Sequentially adding O and 0.2g Polyacrylonitrile (PAN) into 10ml of N-methylpyrrolidone (NMP) solvent, and heating and stirring the mixed solution in a water bath kettle at the temperature of 80 ℃ for 50min to form light yellow liquid;
step five: slowly pouring the light yellow liquid obtained in the step four into the PEGDA liquid obtained in the step three, and heating the light yellow liquid in water bath at the temperature of 80 ℃ for 10 min;
step six: and (5) transferring the mixed liquid obtained in the fifth step into a culture dish, and drying in a forced air drying oven at 140 ℃ for 55min for forming to obtain the solid polymer electrolyte membrane.
Example 5
The method comprises the following steps: heating 0.3g polyethylene glycol acrylate (PEGDA) at 80 deg.C to melt to obtain colorless transparent viscous liquid;
step two: adding benzoin dimethyl ether (DMPA) photoinitiator with the mass fraction of 2% into PEGDA, and continuously stirring for 5min at 80 ℃ to form uniform colorless transparent viscous liquid;
step three: placing the liquid obtained in the step two under a xenon lamp with the power of 1.125W, and irradiating for 5min at the constant temperature of 60 ℃, wherein the PEGDA is partially polymerized under the irradiation of a photoinitiator and ultraviolet light and is still colorless transparent viscous liquid for later use;
step four: 0.75 g of Zn (OAc)2·2H2Sequentially adding O and 0.2g Polyacrylonitrile (PAN) into 10ml of N-methylpyrrolidone (NMP) solvent, and heating and stirring the mixed solution in a water bath kettle at the temperature of 80 ℃ for 50min to form light yellow liquid;
step five: slowly pouring the light yellow liquid obtained in the step four into the PEGDA liquid obtained in the step three, and heating the light yellow liquid in water bath at the temperature of 80 ℃ for 10 min;
step six: and (4) transferring the mixed liquid obtained in the fifth step into a culture dish, and drying in a forced air drying oven at 140 ℃ for 55min for forming to obtain the solid polymer electrolyte membrane.
Claims (6)
1. A preparation method of a solid polymer electrolyte of a zinc ion battery is characterized by comprising the following steps:
the method comprises the following steps: heating and melting polyethylene glycol diacrylate;
step two: adding a photoinitiator into the polyethylene glycol diacrylate, and controlling the adding amount of the photoinitiator to be 1-3% of the mass of the polyethylene glycol diacrylate;
step three: placing the liquid obtained in the step two under a xenon lamp for irradiation;
step four: zinc acetate dihydrate and polyacrylonitrile are sequentially addedAdding into N-methylpyrrolidone solvent, heating and stirring the mixed solution in a water bath to form a light yellow liquid, and controlling Zn2+The molar ratio of the carbon source to CN is 0.9-1.1: 1;
step five: slowly pouring the faint yellow liquid obtained in the fourth step into the liquid obtained in the third step, heating and stirring in a continuous water bath, and controlling the mass ratio of the polyethylene glycol diacrylate to the polyacrylonitrile to be 1.3-1.6: 1;
step six: and D, transferring the mixed liquid obtained in the fifth step into a culture dish, and drying and forming in a drying oven to obtain the solid polymer electrolyte membrane.
2. The method for preparing a solid polymer electrolyte of a zinc ion battery according to claim 1, wherein in the second step, the photoinitiator is benzoin dimethyl ether.
3. The preparation method of the solid polymer electrolyte of the zinc ion battery according to claim 1, wherein in the third step, the constant temperature irradiation time of a xenon lamp is 5-10 min.
4. The method for preparing the solid polymer electrolyte of the zinc-ion battery according to claim 1, wherein in the fourth step, the water bath heating temperature is 80-100 ℃ and the time is 40-50 min.
5. The method for preparing the solid polymer electrolyte of the zinc-ion battery according to claim 1, wherein in the fifth step, the water bath heating temperature is 80-100 ℃ and the time is 5-10 min.
6. The method for preparing the solid polymer electrolyte of the zinc-ion battery according to claim 1, wherein in the sixth step, the drying temperature is 130-150 ℃ and the drying time is 40-60 min.
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| CN202110572585.4A CN113299987B (en) | 2021-05-25 | 2021-05-25 | Preparation method of solid polymer electrolyte of zinc ion battery |
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010048933A (en) * | 1999-11-30 | 2001-06-15 | 박호군 | An electrolyte of uv-curing polymer blend, its fabricating method and its application to lithium polymer battery |
| CN101127408A (en) * | 2007-08-23 | 2008-02-20 | 广州市天赐高新材料科技有限公司 | Micro joint gel state lithium ion battery polymer electrolyte film and its making method |
| KR20130118756A (en) * | 2012-04-20 | 2013-10-30 | 한국에너지기술연구원 | Anode active materials and manufacturing method thereof, and anode and lithium battery using the same |
| JP2014026818A (en) * | 2012-07-26 | 2014-02-06 | Sumitomo Chemical Co Ltd | Molten salt battery |
| WO2014157125A1 (en) * | 2013-03-29 | 2014-10-02 | 住友化学株式会社 | Sodium secondary battery |
| CN105489932A (en) * | 2015-12-09 | 2016-04-13 | 哈尔滨理工大学 | Method for preparing polymer electrolyte film for lithium-ion battery by ultraviolet crosslinking assay |
| CN106207242A (en) * | 2014-11-19 | 2016-12-07 | 苏州宝时得电动工具有限公司 | Aqueous electrolyte and battery |
| WO2017020860A1 (en) * | 2015-08-05 | 2017-02-09 | 苏州宝时得电动工具有限公司 | Battery, battery set and uninterruptable power source |
| CN107403968A (en) * | 2016-05-20 | 2017-11-28 | 苏州宝时得电动工具有限公司 | Aqoue seconary battery |
| KR20180000195A (en) * | 2016-06-22 | 2018-01-02 | 울산과학기술원 | Composite electolyte, method for manufacturing the same, and rechargeable battery comprising the same |
| WO2020167017A1 (en) * | 2019-02-15 | 2020-08-20 | 주식회사 유뱃 | Electrochemical device and method for manufacturing same |
| WO2020192678A1 (en) * | 2019-03-25 | 2020-10-01 | Ford Cheer International Limited | Metal-organic-framework (mof) coated composite separators for electrochemical devices and applications of same |
| CN112151859A (en) * | 2020-09-30 | 2020-12-29 | 香港科技大学 | Composite solid electrolyte with two surfaces and preparation method thereof |
| CN112310490A (en) * | 2019-07-31 | 2021-02-02 | 南京林业大学 | Preparation method of gel electrolyte for double-cross-linked-water-system metal ion energy storage device |
| CN112436188A (en) * | 2020-12-26 | 2021-03-02 | 哈尔滨工业大学 | Polymer-based solid electrolyte with high room temperature ionic conductivity and preparation method and application thereof |
| CN112490499A (en) * | 2020-11-19 | 2021-03-12 | 惠州锂威新能源科技有限公司 | Preparation method of polymer solid electrolyte membrane |
| CN112768836A (en) * | 2021-01-12 | 2021-05-07 | 东华大学 | Zinc ion selective transmission diaphragm and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7135254B2 (en) * | 2001-01-31 | 2006-11-14 | Korea Institute Of Science And Technologies | Multi-layered, UV-cured polymer electrolyte and lithium secondary battery comprising the same |
| US11302911B2 (en) * | 2019-05-13 | 2022-04-12 | Global Graphene Group, Inc. | Particulates of polymer electrolyte-protected anode active material particles for lithium-ion batteries |
-
2021
- 2021-05-25 CN CN202110572585.4A patent/CN113299987B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010048933A (en) * | 1999-11-30 | 2001-06-15 | 박호군 | An electrolyte of uv-curing polymer blend, its fabricating method and its application to lithium polymer battery |
| CN101127408A (en) * | 2007-08-23 | 2008-02-20 | 广州市天赐高新材料科技有限公司 | Micro joint gel state lithium ion battery polymer electrolyte film and its making method |
| KR20130118756A (en) * | 2012-04-20 | 2013-10-30 | 한국에너지기술연구원 | Anode active materials and manufacturing method thereof, and anode and lithium battery using the same |
| JP2014026818A (en) * | 2012-07-26 | 2014-02-06 | Sumitomo Chemical Co Ltd | Molten salt battery |
| WO2014157125A1 (en) * | 2013-03-29 | 2014-10-02 | 住友化学株式会社 | Sodium secondary battery |
| CN106207242A (en) * | 2014-11-19 | 2016-12-07 | 苏州宝时得电动工具有限公司 | Aqueous electrolyte and battery |
| WO2017020860A1 (en) * | 2015-08-05 | 2017-02-09 | 苏州宝时得电动工具有限公司 | Battery, battery set and uninterruptable power source |
| CN105489932A (en) * | 2015-12-09 | 2016-04-13 | 哈尔滨理工大学 | Method for preparing polymer electrolyte film for lithium-ion battery by ultraviolet crosslinking assay |
| CN107403968A (en) * | 2016-05-20 | 2017-11-28 | 苏州宝时得电动工具有限公司 | Aqoue seconary battery |
| KR20180000195A (en) * | 2016-06-22 | 2018-01-02 | 울산과학기술원 | Composite electolyte, method for manufacturing the same, and rechargeable battery comprising the same |
| WO2020167017A1 (en) * | 2019-02-15 | 2020-08-20 | 주식회사 유뱃 | Electrochemical device and method for manufacturing same |
| WO2020192678A1 (en) * | 2019-03-25 | 2020-10-01 | Ford Cheer International Limited | Metal-organic-framework (mof) coated composite separators for electrochemical devices and applications of same |
| CN112310490A (en) * | 2019-07-31 | 2021-02-02 | 南京林业大学 | Preparation method of gel electrolyte for double-cross-linked-water-system metal ion energy storage device |
| CN112151859A (en) * | 2020-09-30 | 2020-12-29 | 香港科技大学 | Composite solid electrolyte with two surfaces and preparation method thereof |
| CN112490499A (en) * | 2020-11-19 | 2021-03-12 | 惠州锂威新能源科技有限公司 | Preparation method of polymer solid electrolyte membrane |
| CN112436188A (en) * | 2020-12-26 | 2021-03-02 | 哈尔滨工业大学 | Polymer-based solid electrolyte with high room temperature ionic conductivity and preparation method and application thereof |
| CN112768836A (en) * | 2021-01-12 | 2021-05-07 | 东华大学 | Zinc ion selective transmission diaphragm and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Electrochemical properties of gel polymer electrolyte based on poly(acrylonitrile)-poly(ethylene glycol diacrylate) blend;Byung-Won Cho等;《Korean J. Chem. Eng》;20071130;第24卷(第6期);第1037-1041页 * |
| 新型全固态聚合物电解质PEG475-DMAA的制备及其电化学性能研究;邢雅兰等;《轻工学报》;20181029(第05期);第75-82页 * |
| 金属离子交联型丙烯酸酯乳液的研究进展;严文斌等;《涂料工业》;20110701(第07期);第72-75页 * |
| 锂离子电池用固态电解质的研究现状与展望;闫雅婧;《无机盐工业》;20200708(第07期);第28-31页 * |
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