CN114976300A - Polymer electrolyte based on polysaccharide material, preparation method of electrolyte and application of electrolyte - Google Patents

Polymer electrolyte based on polysaccharide material, preparation method of electrolyte and application of electrolyte Download PDF

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CN114976300A
CN114976300A CN202210531658.XA CN202210531658A CN114976300A CN 114976300 A CN114976300 A CN 114976300A CN 202210531658 A CN202210531658 A CN 202210531658A CN 114976300 A CN114976300 A CN 114976300A
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polysaccharide
electrolyte
polymer electrolyte
zinc
sodium
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朱玉松
张兴鹏
李紫嫣
王雨琦
姚汪兵
林有芹
宋金保
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Nanjing Tech University
Nanjing Guoxuan Battery Co Ltd
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Nanjing Tech University
Nanjing Guoxuan Battery Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • 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
    • 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
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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

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  • Secondary Cells (AREA)

Abstract

The invention belongs to the field of high molecular materials and energy storage, and particularly relates to preparation of a polysaccharide-based polymer electrolyte and application of the polysaccharide-based polymer electrolyte in an electrochemical energy storage system (including but not limited to batteries (including secondary batteries), fuel cells, super capacitors, flow batteries and the like). The gel polymer electrolyte is composed of a polysaccharide polymer film and electrolyte required by a corresponding battery for holding and absorbing. The invention relates to a preparation method of polysaccharide gel polymer electrolyte, which has simple preparation process, low cost and environment-friendly preparation process. The gel electrolyte not only has the characteristics of good mechanical property and low production cost, but also has the advantages of high ionic conductivity, excellent ion migration number, good cycle performance, high safety performance, high capacity, high power, high energy density and the like in the application of an electrochemical energy storage system. The polysaccharide-based polymer electrolyte can be widely applied to electrochemical energy storage systems.

Description

Polymer electrolyte based on polysaccharide material, preparation method of electrolyte and application of electrolyte
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a polysaccharide-based gel polymer electrolyte and a preparation method thereof, and also relates to application of the polymer electrolyte in an electrochemical energy storage system.
Background
Since the 90 s of the 20 th century, lithium ion batteries have become the main power source of portable devices such as mobile phones, mobile computers, game machines, cameras, etc. due to the realization of the industrialization process, mainly due to the following characteristics: high energy density, long service life, low self-discharge and no memory effect. In recent years, the rise of electric automobiles such as Tesla and the like also promotes the application of lithium ion batteries, and compared with the traditional fuel oil automobile, the electric automobile greatly solves the problem of non-renewable energy consumption, can relieve the large consumption of petroleum energy in China and also has a great promotion effect on improving the environmental problem. However, with the widespread use of lithium ion batteries, some problems are gradually revealed. The organic electrolyte used by the lithium ion battery has the danger of flammability and explosiveness, and is easy to have major safety accidents in the production and transportation processes, thereby having potential safety hazards. In addition, the discarded lithium batteries can cause environmental pollution if not reasonably recycled and disposed. With the great increase of the energy density of the battery, the safety problem of the lithium ion battery becomes an obstacle to large-scale energy storage.
In recent years, a novel metal secondary battery, namely a water-based battery, is researched and developed, and the research discovery of the water-based battery widens the application and research of a metal secondary battery energy storage device and provides a new direction for a new generation of large-scale energy storage system. Among them, the research of the aqueous zinc ion battery among the aqueous batteries is most drawing attention as the aqueous zinc ion battery because zinc metal in the battery has advantages of high natural abundance, large production amount, low cost, no toxicity, easy use, mature processing technology, high volume energy density, high stability and compatibility in an aqueous electrolyte, and a two-electron redox property providing a high theoretical anode capacity, and thus the aqueous zinc ion battery is considered as a secondary battery having a great development prospect. However, the water-based battery has some defects, such as short circuit in the battery caused by zinc dendrite growth, low mass energy density and volume energy density of the battery, and the like, so that the water-based battery is difficult to be applied on a large scale.
Disclosure of Invention
The invention aims to provide a polysaccharide gel polymer electrolyte for an electrochemical energy storage system, which has the advantages of high ion transference number, good mechanical property, high safety performance, stable chemical property, low production cost, wide electrochemical window, compatibility with common electrode materials and excellent electrochemical performance (low internal resistance, long cycle stability and excellent rate performance).
The preparation method of the polymer electrolyte based on the polysaccharide material comprises the following steps:
(1) dissolving polysaccharide in a solvent to obtain a uniform and clear solution;
(2) the thickness of the polysaccharide polymer film prepared by a casting method, a coating method, a hot pressing method, a freeze drying method, an electrostatic spinning method, a phase conversion method, a dipping method, a foaming method or a Bellcore method is controlled to be 5-500 mu m;
(3) placing the polysaccharide polymer film obtained in the step (2) in a vacuum drying oven, drying at room temperature to 300 ℃, and removing trace solvent;
(4) and (3) soaking the polysaccharide polymer membrane obtained in the step (3) after drying in a liquid electrolyte for 1 minute to 24 hours to obtain the polysaccharide polymer electrolyte.
The dissolving process in the step (1) is to stir and dissolve for 4 to 6 hours at room temperature.
The liquid electrolyte in the step (4) is formed by dissolving zinc salt, lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt and aluminum salt of the electrolyte in carbonate, ether or pure water or is ionic liquid, and the concentration is 0.1mol L-1-50mol L-1.
The zinc salt comprises one or a mixture of zinc sulfate (ZnSO4), zinc acetate ((CH3COO)2Zn), zinc trifluoromethanesulfonate (Zn (CF3SO3)2), zinc chloride (ZnCl) and zinc nitrate (Zn (NO3) 2); the lithium salt comprises one or a mixture of lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium bistrifluoromethanesulfonylimide (LiTFSI) and lithium bistrifluorosulfonylimide (LiFSI); the sodium salt comprises one or a mixture of sodium perchlorate (NaClO4), lithium hexafluorophosphate (NaPF6), sodium bistrifluoromethanesulfonylimide (NaTFSI), sodium sulfate (Na2SO4), sodium acetate (CH3COONa) and sodium bistrifluorosulfonylimide (NaFSI); the potassium salt includes potassium perchlorate (KClO4), potassium hexafluorophosphate (KPF6), potassium tetrafluoroborate (KBF4), potassium hexafluoroarsenate (KAsF6), potassium bistrifluoromethanesulfonylimide (KTFSI), potassium bistrifluoromethylsulfonyl imide (KN (CF) 3 SO 2 ) 2 ) One or a mixture thereof; the calcium salt comprises calcium hexafluorophosphate (Ca (PF) 6 ) 2 ) Calcium chloride (CaCl) 2 ) Calcium sulfate (CaSO) 4 ) Calcium triflate ((CF) 3 SO 3 ) 2 Ca), calcium perchlorate (Ca (ClO) 4 ) 2 ) One or a mixture thereof; the aluminum salt comprises one or more of aluminum trifluoromethanesulfonate (Al (OTf)3), aluminum chloride (AlCl3), aluminum nitrate (Al (NO3)3) and aluminum sulfate (Al2(SO4) 3).
The solvent carbonate, ether or pure water comprises one or more of ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, ethylene glycol diether, tetrahydrofuran, dioxolane and pure water.
A polymer electrolyte based on a polysaccharide material, prepared by the steps of,
(1) dissolving polysaccharide in a solvent to obtain a uniform and clear solution;
(2) the thickness of the polysaccharide polymer film prepared by a casting method, a coating method, a hot pressing method, a freeze drying method, an electrostatic spinning method, a phase conversion method, a dipping method, a foaming method or a Bellcore method is controlled to be 5-500 mu m;
(3) placing the polysaccharide polymer film obtained in the step (2) in a vacuum drying oven, drying at room temperature to 300 ℃, and removing trace solvent;
(4) and (3) soaking the polysaccharide polymer membrane obtained in the step (3) after drying in a liquid electrolyte for 1 minute to 24 hours to obtain the polysaccharide polymer electrolyte.
The polysaccharide includes but is not limited to chitosan, starch, sodium alginate, zinc alginate, agar, inulin, cellulose acetate, methyl cellulose, sodium carboxymethyl cellulose.
The dissolving process in the step (1) is to stir and dissolve for 4 to 6 hours at room temperature.
The liquid electrolyte in the step (4) is formed by dissolving zinc salt, lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt and aluminum salt of the electrolyte in carbonate, ether or pure water or is ionic liquid, and the concentration is 0.1mol L-1-50mol L-1.
Applications for polymer electrolytes based on polysaccharide materials include, but are not limited to, batteries, fuel cells, supercapacitors, flow batteries.
The prepared polysaccharide-based gel polymer membrane is adopted to be gelled with the electrolyte to form the composite gel polymer electrolyte, and the obtained gel polymer electrolyte has the characteristics of high strength and low production cost, and is high in conductivity, wide in electrochemical window, good in cycle performance and high in safety performance, and can be used for an electrochemical energy storage system with high capacity, high power and high energy density.
The invention relates to a preparation method of polysaccharide gel polymer electrolyte, which has simple preparation process, low cost and environment-friendly preparation process. The prepared polysaccharide gel polymer electrolyte has high conductivity, wide electrochemical window, high ion migration number and good compatibility with electrode materials, can effectively inhibit the growth of metal dendrites, and obviously improves the cycle stability and rate capability of electrochemical energy storage devices such as batteries and the like. The gel polymer electrolyte can be used for electrochemical energy storage devices such as batteries (including secondary batteries), fuel cells, super capacitors, flow batteries and the like with high energy density, large capacity and high safety.
Drawings
FIG. 1a is a scanning electron micrograph of the surface of a zinc alginate polymer film obtained in example 1 of the present invention.
FIG. 1b is a scanning electron micrograph of a cross section of a zinc alginate polymer film obtained in example 1 of the present invention.
FIG. 1c is a scanning electron microscope image of the surface of the sodium alginate polymer film obtained in example 2 of the present invention.
FIG. 1d is a scanning electron microscope image of the cross section of the sodium alginate polymer film obtained in example 2 of the present invention.
FIG. 1e is a scanning electron microscope image of the glass fiber membrane obtained by the comparative example of the present invention.
FIG. 2 is a graph comparing the tensile force-stress curves of the zinc alginate polymer film obtained in example 1 of the present invention and the glass fiber separator used in the comparative example.
FIG. 3 is a graph comparing the tensile force-stress curves of the sodium alginate polymer film obtained in example 2 of the present invention and the glass fiber membrane used in the comparative example.
FIG. 4 is a graph comparing thermogravimetric curves of the zinc alginate polymer film obtained in example 1 of the present invention and the glass fiber separator used in the comparative example.
FIG. 5 is a graph showing a comparison of thermogravimetric curves of the zinc alginate gel polymer electrolyte obtained in example 1 of the present invention and the glass fiber separator used in the comparative example after absorbing the electrolyte.
FIG. 6 is a thermogravimetric comparison graph of sodium alginate polymer film obtained in example 2 of the present invention and glass fiber membrane used in comparative example.
FIG. 7 is a thermogravimetric curve comparison graph of the sodium alginate gel polymer electrolyte obtained in example 2 of the present invention and the glass fiber membrane used in the comparative example after absorbing the electrolyte.
FIG. 8 is a graph comparing Arrhenius equation curves of the zinc alginate gel polymer electrolyte obtained in example 1 of the present invention and the glass fiber separator-liquid electrolyte used in the comparative example.
FIG. 9 is a graph comparing Arrhenius equation curves of sodium alginate gel polymer electrolyte obtained in example 2 of the present invention and glass fiber membrane-liquid electrolyte used in comparative example.
FIG. 10 is a graph comparing the ion migration number test of the zinc alginate gel polymer electrolyte obtained in example 1 of the present invention and the glass fiber separator-liquid electrolyte used in the comparative example.
FIG. 11 is a graph comparing the ion mobility test of the sodium alginate gel polymer electrolyte obtained in example 2 of the present invention and the glass fiber separator-liquid electrolyte used in the comparative example.
Fig. 12 is a graph comparing rate performance of zinc alginate gel polymer electrolyte obtained in example 1 of the present invention and glass fiber separator used in comparative example through Zn | gel film or separator | CVO battery system.
Figure 13 is a graph comparing the rate performance of the sodium alginate gel polymer electrolyte obtained in example 2 of the present invention and the glass fiber separator used in the comparative example through a Zn | gel film or separator | NVP @ rGO battery system.
Fig. 14 is a graph comparing the cycle performance of the zinc alginate gel polymer electrolyte obtained in example 1 of the present invention and the glass fiber separator used in the comparative example at a current density of 3C by a Zn | gel film or separator | CVO battery system.
Figure 15 is a graph comparing the cycling performance of the sodium alginate gel polymer electrolyte obtained in example 2 of the present invention and the glass fiber separator used in the comparative example through a Zn | gel film or separator | NVP @ rGO battery system at a current density of 3C.
Detailed Description
Example 1
As shown in fig. 1 to 13
(1) 0.4g of sodium alginate powder was dissolved in 40ml of ultrapure water, and the mixture was stirred for 4 hours with a magnetic stirrer set at 500 revolutions. The stirred solution was allowed to stand for 6 h.
(2) The solution after standing was poured into a glass petri dish and heated on a heating plate at 45 ℃ for 6 h. Then putting the membrane into ultrapure water for soaking and washing, and finally putting the membrane into a vacuum drying oven at 60 ℃ for drying for 8 hours to finally obtain the sodium alginate membrane.
(3) Soaking in 3M ZnSO 4 And (3) carrying out a displacement reaction in the solution, standing overnight, washing the surface with ultrapure water, and drying to finally obtain the zinc alginate polymer film.
(4) The electrolyte membrane thus obtained was cut into a suitable size, placed in a vacuum drying oven, dried at 80 ℃ for 24 hours to remove trace amounts of water, cooled to room temperature under vacuum, and transferred into a glove box for storage. Soaking the zinc alginate hydrogel polymer electrolyte in 1M ZnSO4 electrolyte for 12 hours to obtain the zinc alginate hydrogel polymer electrolyte (ZA).
(5) Zinc metal as negative electrode, calcium vanadate (Ca) 0.25 V 2 O 5 ) The water-based zinc ion battery is assembled by the positive electrode and the zinc alginate gel polymer electrolyte.
Example 2
(1) 0.4g of sodium alginate powder was dissolved in 40ml of ultrapure water, and the mixture was stirred for 4 hours with a magnetic stirrer set at 500 revolutions. The stirred solution was allowed to stand for 6 h.
(2) Pouring the water solution into a storage container of a freeze dryer, and freeze-drying at the temperature of-60 ℃ and the vacuum degree of 10Pa in a cold trap.
(3) And (3) heating and rolling the dried product at 80 ℃ for 30 times to obtain a polymer film with the thickness of 35 mu m.
(4) The obtained polymer film was cut into a suitable size, placed in a vacuum drying oven, dried at 80 ℃ for 24 hours to remove trace water, cooled to room temperature under vacuum, and transferred into a glove box for storage. Soaking in 0.5mol L -1 (CH 3 COO) 2 Zn+CH 3 And (4) adding the COONa electrolyte for 12 hours to obtain the sodium alginate gel polymer electrolyte.
(5) The zinc ion battery is assembled by taking metal zinc as a negative electrode, taking sodium vanadium phosphate (NVP @ rGO) as a positive electrode and taking sodium alginate gel polymer electrolyte.
Example 3
(1) Cellulose acetate and acetone were mixed at 1/400 and stirred at room temperature for 6 hours to give a clear and homogeneous solution.
(2) Pouring the solution into an electrostatic spinning storage container, and setting the injection speed to be 0.08mmmin -1 The positive voltage is set to 15KV, the negative voltage is set to 0.5KV, and the left-right translation distance is 20 mm.
(3) And (3) putting the electrostatic spinning product into a vacuum drying oven at 80 ℃ and drying for 12h to obtain a polymer film with the thickness of 35 mu m.
(4) The prepared polymer film is cut into a proper size, placed in a vacuum drying oven, dried for 24 hours at 80 ℃ to remove trace solution, cooled to room temperature in a vacuum state, and transferred into a glove box for storage. It was immersed in 1mol L of -1 LiPF 6 The cellulose acetate gel polymer electrolyte is obtained after 12 hours in the electrolyte (purchased from Zhang Home harbor Thailand Huarong New Material Co., Ltd.).
(5) Metallic lithium as a negative electrode, lithium iron phosphate (LiFePO) 4 ) As the anode, the cellulose acetate gel polymer electrolyte is assembled into the lithium ion battery.
Comparative example 1
After slicing a commercial glass fiber septum (Whatman, GF/A) into 19mm discs, the discs were dried in a vacuum oven at 80 ℃ for 24 hours. Before electrochemical test, the glass fiber diaphragm is soaked in 1mol l -1 ZnSO 4 And the electrolyte is immersed for 12 hours.
Scanning electron microscope, thermogravimetry, liquid absorption rate and tensile stress characterization are carried out on the zinc alginate and sodium alginate polymer films obtained by the methods of the embodiment 1 and the embodiment 2 and the glass fiber diaphragm in the comparative example; TG, conductivity, ion migration number and charge and discharge tests are carried out on the glass fiber diaphragm soaked by the gel polymer electrolyte and the electrolyte.
The liquid absorption rate is calculated according to the formula (1) after the zinc alginate film, the sodium alginate film and the glass fiber diaphragm are soaked in the electrolyte for 12 hours:
η＝(W t –W 0 )/W 0 ×100％ (1)
wherein, W 0 And W t Respectively representing the mass of the dry film and the mass of the electrolyte after being fully absorbed.The liquid absorption rates of ZA and SA obtained by the methods of examples 1 and 2 were 78% and 190%, respectively, and the liquid absorption rates of the glass fiber membranes in the comparative examples were 179% and 175%, respectively.
The conductivity is calculated from equation (2):
σ＝l/(R b A)(S cm -1 ) (2)
where σ is the conductivity, R b Is the impedance of the film, l is the thickness of the film, and A is the pole piece area. The room temperature conductivity of ZA and SA obtained by the methods of examples 1 and 2 is 1.24mS cm -1 、1.76mS cm -1 The room-temperature conductivity of the electrolyte-saturated glass fiber separators in comparative examples 1 and 2 was 15.6mS cm -1 、14.9mS cm -1 。
The ion transport number is calculated by formula (3):
Figure BDA0003646589730000071
wherein, I ss Is a steady-state current value obtained by a chronometric electric quantity method, I 0 Is the initial state current value obtained by a timing electric quantity method. The room temperature ion transference numbers of ZA and SA obtained by the methods of examples 1 and 2 were 0.59 and 0.82, respectively, and the liquid absorption rates of the glass fiber membranes in the comparative examples were 0.21 and 0.45, respectively.
Compared with the comparative example and the embodiment, the prepared polysaccharide gel polymer electrolyte has the characteristics of good thermal stability, low price, high safety and the like, has good compatibility with a battery electrode, and can effectively prevent short circuit of the battery. Compared with the traditional commercial diaphragm, the gel polymer electrolyte prepared by the embodiment has more excellent ion migration number and charge-discharge performance, and has important significance for the development of high-power and high-energy-density electric automobiles and large energy storage equipment.

Claims (10)

1. The preparation method of the polymer electrolyte based on the polysaccharide material is characterized by comprising the following steps:
(1) dissolving polysaccharide in a solvent to obtain a uniform and clear solution;
(2) the thickness of the polysaccharide polymer film prepared by a casting method, a coating method, a hot pressing method, a freeze drying method, an electrostatic spinning method, a phase conversion method, a dipping method, a foaming method or a Bellcore method is controlled to be 5-500 mu m;
(3) placing the polysaccharide polymer film obtained in the step (2) in a vacuum drying oven, drying at room temperature to 300 ℃, and removing trace solvent;
(4) and (3) soaking the polysaccharide polymer membrane obtained in the step (3) after drying in a liquid electrolyte for 1 minute to 24 hours to obtain the polysaccharide polymer electrolyte.
2. The method for preparing a polymer electrolyte based on polysaccharide material according to claim 1, wherein the dissolving process in step (1) is performed by stirring at room temperature for 4-6 hours.
3. The method of claim 1, wherein the liquid electrolyte in step (4) is composed of zinc salt, lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, and aluminum salt of electrolyte dissolved in carbonate, ether, or pure water or ionic liquid, and has a concentration of 0.1mol L-1-50mol L-1.
4. The method for preparing a polymer electrolyte based on polysaccharide material according to claim 3, wherein the zinc salt comprises one or a mixture of zinc sulfate (ZnSO4), zinc acetate ((CH3COO)2Zn), zinc trifluoromethanesulfonate (Zn (CF3SO3)2), zinc chloride (ZnCl), zinc nitrate (Zn (NO3) 2); the lithium salt comprises one or a mixture of lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium bistrifluoromethanesulfonylimide (LiTFSI) and lithium bistrifluorosulfonylimide (LiFSI); the sodium salt comprises one or a mixture of sodium perchlorate (NaClO4), lithium hexafluorophosphate (NaPF6), sodium bistrifluoromethanesulfonylimide (NaTFSI), sodium sulfate (Na2SO4), sodium acetate (CH3COONa) and sodium bistrifluorosulfonylimide (NaFSI); the potassium salt includes potassium perchlorate (KClO4), potassium hexafluorophosphate (KPF6), potassium tetrafluoroborate (KBF4), potassium hexafluoroarsenate (KAsF6), and bis (potassium bis-ammonium bis (phosphonium) borate)Potassium trifluoromethanesulfonylimide (KTFSI) and potassium bis (trifluoromethanesulfonyl) imide (KN (CF) 3 SO 2 ) 2 ) One or a mixture thereof; the calcium salt comprises calcium hexafluorophosphate (Ca (PF) 6 ) 2 ) Calcium chloride (CaCl) 2 ) Calcium sulfate (CaSO) 4 ) Calcium triflate ((CF) 3 SO 3 ) 2 Ca), calcium perchlorate (Ca (ClO) 4 ) 2 ) One or a mixture thereof; the aluminum salt comprises one or more of aluminum trifluoromethanesulfonate (Al (OTf)3), aluminum chloride (AlCl3), aluminum nitrate (Al (NO3)3) and aluminum sulfate (Al2(SO4) 3).
5. The method of claim 3, wherein the solvent is carbonate, ether or pure water, and comprises one or more of ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, ethylene glycol diether, tetrahydrofuran, dioxolane, and pure water.
6. A polymer electrolyte based on a polysaccharide material, characterized in that it is prepared by the following steps,
(1) dissolving polysaccharide in a solvent to obtain a uniform and clear solution;
(2) the thickness of the polysaccharide polymer film prepared by a casting method, a coating method, a hot pressing method, a freeze drying method, an electrostatic spinning method, a phase conversion method, a dipping method, a foaming method or a Bellcore method is controlled to be 5-500 mu m;
(3) placing the polysaccharide polymer film obtained in the step (2) in a vacuum drying oven, drying at room temperature to 300 ℃, and removing trace solvent;
(4) and (3) soaking the polysaccharide polymer membrane obtained in the step (3) after drying in a liquid electrolyte for 1 minute to 24 hours to obtain the polysaccharide polymer electrolyte.
7. The polysaccharide material-based polymer electrolyte of claim 6,
the polysaccharide includes but is not limited to chitosan, starch, sodium alginate, zinc alginate, agar, inulin, cellulose acetate, methyl cellulose, sodium carboxymethyl cellulose.
8. The polysaccharide material-based polymer electrolyte according to claim 6, wherein the dissolving process in step (1) is performed at room temperature with stirring for 4-6 hours.
9. The polysaccharide material-based polymer electrolyte of claim 6, wherein the liquid electrolyte in step (4) is composed of zinc, lithium, sodium, potassium, calcium, magnesium, and aluminum electrolytes dissolved in carbonate, ether, or pure water or ionic liquids at a concentration of 0.1mol L-1-50mol L-1.
10. Applications of the polysaccharide material based polymer electrolyte according to claims 6-9 include, but are not limited to, batteries, fuel cells, supercapacitors, flow batteries.
CN202210531658.XA 2022-05-17 2022-05-17 Polymer electrolyte based on polysaccharide material, preparation method of electrolyte and application of electrolyte Pending CN114976300A (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN117164899A (en) * 2023-11-01 2023-12-05 中科南京绿色制造产业创新研究院 Gel electrolyte, preparation method thereof and zinc ion battery containing gel electrolyte

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117164899A (en) * 2023-11-01 2023-12-05 中科南京绿色制造产业创新研究院 Gel electrolyte, preparation method thereof and zinc ion battery containing gel electrolyte
CN117164899B (en) * 2023-11-01 2024-02-02 中科南京绿色制造产业创新研究院 Gel electrolyte, preparation method thereof and zinc ion battery containing gel electrolyte

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