CN113851739B - Preparation and application of gel electrolyte for antifreeze zinc-based battery - Google Patents
Preparation and application of gel electrolyte for antifreeze zinc-based battery Download PDFInfo
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- CN113851739B CN113851739B CN202111237402.XA CN202111237402A CN113851739B CN 113851739 B CN113851739 B CN 113851739B CN 202111237402 A CN202111237402 A CN 202111237402A CN 113851739 B CN113851739 B CN 113851739B
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Gel electrolyte suitable for zinc-based battery at-20deg.C, and its preparation and application are provided. The invention discloses a preparation method of an antifreeze gel electrolyte for a zinc-based battery, and aims to reduce the freezing temperature of the gel electrolyte taking sodium alginate-polyacrylamide as a matrix through the synergistic hydration of zinc salt and lithium salt. The freeze-resistant hydrogel immersed in zinc salt and lithium salt is used as electrolyte, shows good freeze resistance and mechanical property, and has excellent low-temperature tolerance and cycle stability. The invention aims to solve the problems that the prior electrolyte cannot work normally due to limited use below zero, the preparation process is complicated and the ionic conductivity is low.
Description
Technical Field
The invention relates to the technical field of electrochemical device energy storage, in particular to an antifreeze gel electrolyte of a zinc-based battery, and a preparation method and application thereof.
Background
The metallic lithium (Li) has high theoretical specific capacity (3860 mAh g) -1 ) The lithium secondary battery has the advantages of high energy density, extremely low electrode potential and the like, is considered to be an ideal battery cathode material, and is widely applied to the field of electrochemical energy storage. However, most lithium ion batteries are organic electrolytes, and have a series of potential safety hazards such as toxicity, easy liquid leakage, flammability and the like. The emerging aqueous zinc ion secondary batteries are of great interest because of their inherent safety and low cost. The aqueous mixed zinc-based battery has been developed in recent years as a very promising alternative to lithium ion batteries. The zinc reserves are abundant, the cost is low, and meanwhile, the assembly condition of the water system battery is mild. Therefore, the water system zinc-lithium mixed battery composed of zinc and the lithium-rich material has good safety and environmental friendliness, and has great prospect in the future energy storage large-scale field.
However, the liquid water-based electrolyte is inevitably frozen at sub-zero temperatures, and thus the use of zinc ion batteries in low temperature environments is limited. Meanwhile, the use of polymer electrolyte to replace traditional electrolyte is one of effective ways to improve the safety of the battery, and the development of low-temperature-resistant flexible zinc ion batteries is a current research hotspot. It is reported that an ethylene glycol-aqueous anionic polyurethane acrylate (EG-waPUA) antifreeze gel electrolyte has high ionic conductivity at a low temperature of-20 ℃ and good low-temperature electrochemical stability and mechanical durability when applied to a flexible zinc-manganese battery. For flexible zinc-based batteries, the current technical difficulty is that the electrolyte of the zinc ion battery is limited by low-temperature conditions and cannot be charged and discharged normally, the types of gel polymer electrolytes are few, the ionic conductivity is low, and the preparation is complex.
Disclosure of Invention
The method aims to solve the problems that the conventional flexible zinc-based battery cannot resist low temperature and normally works, the ionic conductivity of gel electrolyte is low, and the preparation conditions are harsh. The invention provides an antifreeze gel electrolyte of a zinc-based battery and a preparation method and application thereof.
A preparation method of an antifreeze gel electrolyte of a zinc-based battery comprises the following steps:
(1) Heating and dissolving sodium alginate in deionized water at a certain temperature, and uniformly stirring to obtain a uniform mixture of sodium alginate and water;
(2) Uniformly mixing an initiator, a cross-linking agent, a monomer and the mixture obtained in the step (1), transferring the mixture into a polytetrafluoroethylene mould, and carrying out free radical polymerization reaction at a certain temperature for a certain time to obtain the anti-freezing hydrogel;
(3) Zinc salt and lithium salt are dissolved in water to obtain liquid electrolyte;
(4) Immersing the hydrogel obtained in the step (2) into the liquid electrolyte obtained in the step (3) for a certain time to obtain the gel electrolyte.
In the step (1), the heating temperature is 50-80 ℃, and the mass concentration of the sodium alginate dissolved in water is 1-40 mg/ml.
In the step (2), the initiator is ammonium persulfate, potassium persulfate, benzoyl oxide, tert-butyl hydroperoxide, benzoin diethyl ether or photoinitiator 2959. The cross-linking agent is N, N' -methylene bisacrylamide, ethylene glycol diacrylate, ethylene glycol dimethacrylate or divinylbenzene. The monomers are acrylamide and [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide.
In the step (2), the temperature is 40-80 ℃ and the time is 6-12 h.
In the step (3), the zinc salt is selected from one or more of zinc sulfate, zinc chloride, zinc acetate, zinc nitrate, zinc perchlorate, zinc trifluoromethane sulfonate, zinc fluoroborate or zinc bis (trifluoromethane sulfonyl) imide.
In the step (3), the lithium salt is selected from lithium chloride.
In the step (3), the concentration of the zinc salt is 0.5mol/L to 10mol/L, and the concentration of the lithium salt is 0.5mol/L to 5mol/L.
In the step (4), the immersion time is 1-24 hours.
The invention provides an antifreeze gel electrolyte.
Based on the technical scheme, the antifreeze gel electrolyte provided by the invention has good low-temperature tolerance, high ionic conductivity and good flexibility due to strong hydration of polyacrylamide, zwitterion and chloride ion, can be charged and discharged normally at the temperature of-20 ℃ and has excellent electrochemical performance.
The invention also provides application of the gel electrolyte as an electrolyte material of a water-based zinc ion battery, and the gel electrolyte is applied to a zinc-lithium hybrid battery, wherein a positive electrode material of the zinc ion battery is lithium iron phosphate.
The invention has the beneficial effects that:
(1) The antifreeze gel electrolyte applied to the water-based zinc ion battery is environment-friendly, and has stable and excellent electrochemical performance;
(2) Due to the strong hydration of polyacrylamide, zwitterions and chloride ions, the coagulation temperature of the gel electrolyte provided by the invention is reduced, and the zinc ion battery can be ensured not to be frozen at-20 ℃ to be charged and discharged normally;
(3) The addition of the zwitterion promotes ion migration, and has high water retention capacity, thus ensuring higher ion conductivity.
Drawings
FIG. 1 is a physical view of the antifreeze gel electrolyte of the embodiment 3;
FIG. 2 is a tensile stress-strain curve of the freeze resistant gel electrolyte of example 3;
fig. 3 is a schematic diagram of example 3 application of a gel electrolyte to a zinc lithium hybrid battery;
fig. 4 shows the charge and discharge performance of the battery of example 3 at different rates at-20 ℃.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
3g sodium alginate was dissolved in 40mL deionized water at 30 ℃. Sequentially adding 10g of acrylamide monomer and zwitterionic monomer, stirring uniformly, adding potassium persulfate and N, N '-methylenebisacrylamide, enabling the potassium persulfate to be 0.05% mol of the monomer and the N, N' -methylenebisacrylamide to be 0.01% mol of the monomer in the mixture, fully and uniformly mixing, injecting into a polytetrafluoroethylene mold with the thickness of 1mm, reacting for 3 hours at 60 ℃ and forming the hydrogel through free radical polymerization. 30g of zinc chloride and 10g of lithium chloride were dissolved in 50mL of deionized water to prepare a water electrolyte. Immersing the collected hydrogel into the water electrolyte for 3 hours at the temperature of 30 ℃ to finally obtain the gel electrolyte.
Example 2
2.5g sodium alginate was dissolved in 40mL deionized water at 40 ℃. Sequentially adding an acrylamide monomer with the total mass of 15g and a zwitterionic monomer, stirring uniformly, then adding potassium persulfate and N, N '-methylenebisacrylamide, enabling the potassium persulfate in the mixture to be 0.1% mol of the monomer and the N, N' -methylenebisacrylamide to be 0.02% mol of the monomer, fully and uniformly mixing, injecting into a polytetrafluoroethylene mold with the thickness of 1mm, reacting for 4 hours at 60 ℃ and forming the hydrogel through free radical polymerization. 30g of zinc chloride and 10g of lithium chloride were dissolved in 50mL of deionized water to prepare a water electrolyte. Immersing the polymerized hydrogel into the water electrolyte for 4 hours at 40 ℃ to finally obtain the gel electrolyte.
Example 3
2g sodium alginate was dissolved in 40mL deionized water at 50 ℃. Sequentially adding 25g of acrylamide monomer and zwitterionic monomer, stirring uniformly, adding potassium persulfate and N, N '-methylenebisacrylamide, enabling the potassium persulfate to be 0.15% mol of the monomer and the N, N' -methylenebisacrylamide to be 0.03% mol of the monomer in the mixture, fully and uniformly mixing, injecting into a polytetrafluoroethylene mold with the thickness of 1mm, reacting for 5 hours at 60 ℃ and forming the hydrogel through free radical polymerization. 30g of zinc sulfate and 10g of lithium chloride were dissolved in 50mL of deionized water to prepare a water electrolyte. Immersing the polymerized hydrogel into the water electrolyte for 12 hours at the temperature of 30 ℃ to finally obtain the gel electrolyte.
Example 4
1.25g sodium alginate was dissolved in 40mL deionized water at 60 ℃. Sequentially adding 20g of acrylamide monomer and zwitterionic monomer, stirring uniformly, adding potassium persulfate and N, N '-methylenebisacrylamide, enabling the potassium persulfate to be 0.2% mol of the monomer and the N, N' -methylenebisacrylamide to be 0.04% mol of the monomer in the mixture, fully and uniformly mixing, injecting into a polytetrafluoroethylene mold with the thickness of 1mm, reacting for 6 hours at 60 ℃ and forming the hydrogel through free radical polymerization. 30g of zinc sulfate and 10g of lithium chloride were dissolved in 50mL of deionized water to prepare a water electrolyte. Immersing the polymerized hydrogel into the water electrolyte for 24 hours at 20 ℃ to finally obtain the gel electrolyte.
FIG. 1 is a physical view of the antifreeze gel electrolyte of example 3, showing good adhesion and stretchability. FIG. 2 is a tensile stress-strain curve of the antifreeze gel electrolyte of the embodiment 3, showing good flexibility, and the maximum tensile stress of the hydrogel is 131kPa, and the elongation is 592%. Fig. 3 is a graph showing the cyclic charge and discharge performance of-20 ℃ at a rate of 1C when the gel electrolyte is applied to a zinc-lithium hybrid battery in example 3. The initial discharge capacity of the assembled battery was 87.4mAh g -1 The final capacity was 56mAh g -1 After 1000 charge and discharge cycles, the capacity retention was 64.1%, which demonstrates the low temperature resistance and long term stability of the antifreeze electrolyte. Fig. 4 shows the charge and discharge performance of the battery of example 3 at different rates at-20 ℃. The initial discharge capacity of Zn-LFP equipped with this gel electrolyte at 0.5C was 95.3mAh g -1 . With the discharge rate gradually increased to 1, 3 and 5 ℃, the specific capacity gradually decreased to 74.1, 44 and 32.4mAh g respectively -1 . The specific capacity of the battery decreased with the increase in the rate, and when the battery was recovered to 0.5C, the discharge capacity of the battery was recovered to 91.9mAh g -1 The capacity retention rate at the 41 st turn is close to 94%, and the display is performedThe cell is shown to still have rapid reaction kinetics at-20 ℃.
While embodiments of the present invention have been illustrated and described above, it will be appreciated that the above described embodiments are exemplary and should not be construed as limiting the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for preparing a gel electrolyte for a freeze-resistant zinc-based battery, which is characterized by comprising the following steps:
(1) Heating and dissolving sodium alginate in deionized water, and uniformly stirring to obtain a uniform mixture of sodium alginate and water;
(2) Uniformly mixing an initiator, a cross-linking agent, a monomer and the mixture obtained in the step (1), transferring the mixture into a polytetrafluoroethylene mould, and carrying out free radical polymerization reaction at a certain temperature for a certain time to obtain an anti-freezing gel; the monomers are acrylamide and [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide;
(3) Zinc salt and lithium salt are dissolved in water to obtain liquid electrolyte;
(4) Immersing the hydrogel obtained in the step (2) into the liquid electrolyte obtained in the step (3) for a certain time to obtain a gel electrolyte;
in the step (3), the zinc salt is selected from one or more of zinc sulfate, zinc chloride, zinc acetate, zinc nitrate, zinc perchlorate, zinc trifluoromethane sulfonate, zinc fluoroborate or zinc bis (trifluoromethane sulfonyl) imide; the lithium salt is selected from lithium chloride.
2. The preparation method of the gel electrolyte for the antifreeze zinc-based battery, according to claim 1, is characterized in that in the step (1), the heating temperature is 50-80 ℃, and the mass concentration of the sodium alginate dissolved in water is 1-40 mg/ml.
3. The method for preparing the gel electrolyte for the antifreeze zinc-based battery according to claim 1, wherein in the step (2), the initiator is ammonium persulfate, potassium persulfate, benzoyl oxide, tert-butyl hydroperoxide, benzoin diethyl ether or photoinitiator 2959; the cross-linking agent is N, N' -methylene bisacrylamide, ethylene glycol diacrylate, ethylene glycol dimethacrylate or divinylbenzene.
4. The method for preparing the gel electrolyte for the antifreeze zinc-based battery according to claim 1, wherein in the step (2), the temperature is 40-80 ℃ and the time is 6-12 h.
5. The method for preparing the gel electrolyte for the antifreeze zinc-based battery according to claim 1, wherein in the step (3), the zinc salt concentration is 0.5mol/L to 10mol/L, and the lithium salt concentration is 0.5mol/L to 5mol/L.
6. The method for preparing a gel electrolyte for a freeze-resistant zinc-based battery according to claim 1, wherein in the step (4), the immersion time is 1 to 24 hours.
7. A gel electrolyte prepared by the method for preparing a gel electrolyte for a freeze-resistant zinc-based battery according to any one of claims 1 to 6.
8. Use of the gel electrolyte according to claim 7 as a freeze resistant electrolyte material for zinc-based batteries, wherein the positive electrode material of the zinc-based battery is lithium iron phosphate.
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| CN116666843A (en) * | 2022-02-18 | 2023-08-29 | 复旦大学 | Polymer electrolyte and preparation method and application thereof |
| CN114725336A (en) * | 2022-03-16 | 2022-07-08 | 武汉理工大学 | Protective layer modified zinc anode material and preparation method and application thereof |
| CN114759274A (en) * | 2022-03-21 | 2022-07-15 | 电子科技大学 | Preparation method of hydrogel electrolyte with high adhesion |
| CN115097677B (en) * | 2022-05-09 | 2024-01-16 | 上海大学 | Electrochromic energy storage dual-function device, preparation method and application thereof |
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