CN114695975A - Preparation method of low-temperature flexible zinc ion battery - Google Patents
Preparation method of low-temperature flexible zinc ion battery Download PDFInfo
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- CN114695975A CN114695975A CN202210279356.8A CN202210279356A CN114695975A CN 114695975 A CN114695975 A CN 114695975A CN 202210279356 A CN202210279356 A CN 202210279356A CN 114695975 A CN114695975 A CN 114695975A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001868 water Inorganic materials 0.000 claims abstract description 25
- 239000011701 zinc Substances 0.000 claims abstract description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 2
- 239000011230 binding agent Substances 0.000 claims 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims 1
- 239000010406 cathode material Substances 0.000 claims 1
- 239000006258 conductive agent Substances 0.000 claims 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims 1
- 229920002401 polyacrylamide Polymers 0.000 claims 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims 1
- QEORIOGPVTWFMH-UHFFFAOYSA-N zinc;bis(trifluoromethylsulfonyl)azanide Chemical compound [Zn+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QEORIOGPVTWFMH-UHFFFAOYSA-N 0.000 claims 1
- 239000000017 hydrogel Substances 0.000 abstract description 8
- 239000002000 Electrolyte additive Substances 0.000 abstract 1
- 125000001153 fluoro group Chemical group F* 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 230000008014 freezing Effects 0.000 description 10
- 238000007710 freezing Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 230000002528 anti-freeze Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000000499 gel Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000023445 Congenital pulmonary airway malformation Diseases 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- MHYCRLGKOZWVEF-UHFFFAOYSA-N ethyl acetate;hydrate Chemical compound O.CCOC(C)=O MHYCRLGKOZWVEF-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000004001 molecular interaction Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006299 self-healing polymer Polymers 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
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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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M2300/0002—Aqueous electrolytes
-
- 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
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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 provides a preparation method of a flexible battery which can keep flexibility at low temperature and can be stably circulated. The water system zinc ion battery mainly comprises a positive electrode, a negative electrode and a low-temperature-resistant flexible electrolyte, wherein the positive electrode is made of Prussian blue analogues, the negative electrode is made of metal zinc, the electrolyte is fluorine-containing zinc salt, and the hydrogel electrolyte prepared by using ethyl acetate as an electrolyte additive forms a primary battery system. The low-temperature-resistant flexible zinc ion battery provided by the invention can still keep flexibility at an extremely low temperature, the battery circulation at the low temperature can reach 500 times, the preparation process is simple, and the cost is low.
Description
Field of materials
The technology belongs to the field of electrolyte of a water-system zinc ion battery, and relates to a preparation method of antifreeze electrolyte of a water-system flexible zinc ion battery containing a low-temperature additive and the battery.
Background
Along with the rapid development of modern science and technology, more and more flexible wearable products are developed to satisfy the more convenient daily life demand of people, this has promoted the rapid development of flexible battery. To meet the use requirements of flexible wearable devices, the safety and durability of the flexible battery need to be ensured, and high energy density is maintained. The organic electrolyte used by the lithium ion battery has great potential safety hazard due to the flammability. Aqueous zinc batteries are a promising alternative to lithium ion batteries due to their good safety and high energy density. The high ionic conductivity of the water system electrolyte enables the battery to have good rate capability; and, it is simple in operation environment and easier to realize high durability than a lithium ion battery. In addition, the soft and elastic hydrogel electrolyte provides a durable characteristic for the flexible battery, and the mechanical property of the soft polymer network structure can absorb and disperse the stress generated by the battery in use and can bear the severe mechanical deformation of the battery for a long time. However, since the freezing point of water is high so that the water-based battery is difficult to use at low temperature, the electrolyte will freeze so that the electrolyte resistance increases sharply and the capacity decreases; failure of the polymer network, mechanical deformation of the battery, loss of toughness and elasticity of the flexible battery.
Hong Kong City university (Energy)&Environmental Science,2019,12(2):706-715) prepares an EG-waPUA/PAM hydrogel electrolyte by fixing ethylene glycol molecules on a PAM polymer network through a series of complex processes, wherein hydrogen bonds formed by the polymer and water can fix water molecules, and the hydrogel has obvious frost resistance and long-term stability at the temperature of-20 ℃. Harbin university of industry (battieries)&Supercaps,2021,4(10):1627-4A hybrid battery. The use of the double-layer electrolyte well meets the working mechanism of the hybrid battery and is close to LiFePO4One side of the cathode is provided with Li+Zn is provided close to one side of the Zn anode2+The cell was able to operate at-20 ℃. But the complex synthesis flow of gel is greatly limitedThe commercial application of the battery is made; a concentrated double salt solution (2M ZnSO) was prepared at the German university of Deleston Industrial Materials (Advanced Functional Materials,2020,30(6):1907218)4And 4M LiCl, abbreviated as ZL-PAM) assembles a flexible antifreeze Zn/LiFePO4Battery, hydrated cation Zn2+And Li+) The synergistic effect of (A) reduces the freezing temperature of ZL-PAM; the antifreeze self-healing polymer gel electrolyte (AF-SH-CPAM) was prepared directly by in situ polymerization in a water/ethylene glycol solution of acrylamide monomer at the university of Beijing university of Physician (nergy Storage Materials,2022,44: 517-526). The flexible antifreeze Zn-MnO hydrogel is developed by using borax cross-linked PVA/glycerol (PVA-B-G) hydrogel as an electrolyte, and is used at Nanjing university of Materials Chemistry A,2020,8(14):6828-2A battery. The product is a glycerol/salt solution (2M ZnSO) added with borax4And 0.2MMnSO4) A binary solvent of (a). The ethylene glycol can inhibit the water molecules from freezing and dynamically adjust the molecular interaction between the polymer chain and the water, and simultaneously realize the freezing resistance and the self-healing of the electrolyte. As rich hydrogen bonds are formed among PVA, glycerol and water molecules, an integrated three-dimensional network is constructed, the transmission of ions is promoted, and the freezing point of electrolyte is reduced. Too high a concentration of salt will cause irreversible damage to the gel network and as the temperature is lowered, the solubility of the salt decreases, and precipitation on the gel surface will occur.
Based on the above, the invention provides a preparation method of the antifreeze hydrogel electrolyte with low salt concentration and simple preparation process, and the hydrogel electrolyte can still keep a soft state at minus dozens of degrees.
Disclosure of Invention
The invention provides a low-concentration and simple-preparation antifreeze electrolyte configuration method aiming at the points that a low-temperature-resistant flexible electrolyte has a complex preparation process and a gel network is irreversibly damaged due to high salt concentration, so as to solve the problems that a water-based battery is frozen at zero temperature, a polymer network fails and the battery is irreversibly mechanically deformed to greatly lose capacity.
The invention provides a preparation method of a flexible antifreeze electrolyte, which comprises the following raw materials in percentage by volume:
electrolyte: 0.5-2M fluorine-containing zinc salt;
solvent: 20-60 vol% water; 80-40 vol% of an ester additive;
polymer network: PAM
Photoinitiator (2): 1 to 2% mol
A crosslinking agent: 0.02-0.04% mol
The principle of the invention is as follows:
ester additives with hydrophilic groups and PAM are combined with water of the electrolyte through hydrogen bonds to fix free water molecules, so that the number of hydrogen bonds formed between the free water molecules is reduced, and the aim of reducing the freezing point of the electrolyte is fulfilled. The polymer network provided by the PAM provides a channel for ion transmission, and the reduction speed of the ionic conductivity at low temperature is reduced. The added ester additive interacts with groups on a polymer network, so that the van der Waals force among polymer molecules is weakened, the mobility of polymer molecular chains is increased, and the ionic conductivity of the electrolyte is improved.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a low-concentration and simple-preparation antifreeze electrolyte configuration method, which aims to solve the problems that a water-based battery is frozen at zero temperature, a polymer network fails, and the battery is subjected to irreversible mechanical deformation to greatly lose capacity. By selecting an organic solvent and a polymer network which can bring a large number of hydrophilic groups, a novel flexible electrolyte design method is provided, the freezing point of the flexible electrolyte is greatly reduced, so that the battery can keep flexibility and elasticity at ultralow temperature, and irreversible damage of ice crystals to a battery device caused by temperature reduction is avoided. The selected fluorine-containing zinc salt enables the slightly water-soluble ester additive to be mutually soluble with water and uniformly dispersed in the gel network, and the fluorine-containing zinc salt, the ester additive, the polymer network and the water have obvious interaction, so that the flexible electrolyte system is more stable.
The freezing point of the low-temperature resistant flexible electrolyte containing a large number of hydrophilic groups is greatly reduced through tests, and the flexible battery stably operates at low temperature.
Drawings
Fig. 1 is a graph comparing battery cycles at-10 ℃ for flexible batteries provided in example 1 of the present invention and comparative example 1 without low temperature additives.
Detailed Description
By passing through 1MZn (TFSI)2The present invention is further illustrated by the example of ethyl acetate volume fraction of 60 vol%, using 3g AM monomer, 1 mol% photoinitiator, 0.03 mol% crosslinker.
The preparation method of the electrolyte with low freezing point and high capacity retention rate comprises the following steps:
step 1: preparation of low temperature resistant flexible electrolyte
1. Mixing 6.61g Zn (TFSI)2·2H2Dissolving the O solid in 10mL of EA water solution with the volume fraction of 60%, and stirring for 20min to obtain a clear and uniform solution A. Meanwhile, preparing an electrolyte solution with a solvent of 100% water by volume fraction, and marking as a solution B.
2. 3g of AM (acrylamide), 0.094g of photoinitiator (2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone), 0.00195g of MBA (N, N-methylene bisacrylamide) were added to the solution A and the solution B, stirred to a uniform solution, and after removing oxygen and charging nitrogen by a vacuum pump, the solution was poured into a mold, and after 1 hour of initiation under ultraviolet light, a flexible electrolyte was obtained, which was respectively recorded as an example and a comparative example.
Step 2: preparation of electrode materials
2mmol of K4Fe(CN)6·3H2O and 0.035 mmoleFeSO4·7H2O and 0.065mmol MnSO4·H2O is dissolved in 100ml and 80ml of saturated KCl solution respectively. The latter solution was slowly added dropwise to the former solution at 60 ℃ with magnetic stirring. After 12h, the precipitate formed was centrifuged and washed thoroughly with deionized water. Finally, the product is dried in air at 80 ℃ for 12h to obtain the Prussian blue analogue.
And step 3: preparation of positive plate
Mixing the active material with Ketjen black and PVDF at a weight ratio of 7Mixing 2:1, dissolving PVDF in NMP, stirring the mixture for more than 4h to prepare slurry, and coating the slurry on the surface of the substrate
And (3) drying the hydrophobic carbon cloth in an oven at 80 ℃ for one night to obtain the positive plate, wherein the mass of active substances on the plate is about 1 mg/plate.
And 4, step 4: preparation of negative plate
And (3) polishing a zinc sheet with the thickness of 100 mu m by using sand paper, and cutting the zinc sheet into a negative plate with the diameter of 14 mm.
And 5: assembled full cell
Assembling the CR2032 button cell according to the sequence of a negative electrode shell, an elastic sheet, a zinc sheet, a flexible electrolyte, a positive electrode sheet and a positive electrode shell, packaging the assembly by a cell packaging machine, standing the cell for one hour, and preparing for testing.
Step 6: testing
And (3) testing the low-temperature-resistant water-based zinc ion battery assembled in the step (5): the battery test system test (LANHE CT2001A 5V10mA) was used, the test voltage range of Zn | | PBAs was 0.6-2.2V, the charge-discharge cycle performance of the battery was tested at a temperature of-10 ℃, and the current density and specific capacity of the full battery were based on the active mass of the cathode in each electrode.
The low-temperature-resistant flexible zinc ion battery prepared by the invention has the following properties:
the freezing point of the flexible electrolyte is lower than-65 ℃, and the flexible electrolyte has 6.10mS cm at-20 DEG C-1At-10 ℃ in the total cell, the ionic conductivity of (A) is 0.5 A.g-1Shows 105mAh · g at a current density of-1The capacity retention rate is 80% after 500 cycles of the cycle.
Claims (8)
1. A low-temperature flexible zinc ion battery. The method comprises the following steps: the flexible electrolyte is characterized by using fluorine-containing zinc salt, an ester organic solvent with poor solubility in water and a polymer network; the cathode is a Prussian blue analogue.
2. The low-temperature aqueous zinc ion battery according to claim 1, characterized in that the flexible electrolyte contains a soluble fluorine-containing zinc salt and a water-immiscible ester additive.
3. The low-temperature zinc ion battery according to claim 1, wherein the soluble fluorine-containing zinc salt comprises one of zinc trifluoromethanesulfonate and zinc bis (trifluoromethylsulfonyl) imide, the ester additive comprises one or more of ethyl formate, methyl acetate, ethyl acetate and derivatives thereof, and the polymer network is polyacrylamide.
4. The flexible electrolyte of claim 2 is prepared by: will: 0.5-2M of fluorine-containing zinc salt, 20-60 vol% of water and 80-40 vol% of ester additive are prepared into a solution, acrylamide monomer, 1-2% of acrylamide photoinitiator and 0.02-0.04% of acrylamide cross-linking agent are added into the solution and stirred to form a uniform solution, the solution is deaerated and filled with nitrogen by a vacuum pump, poured into a mould and initiated for (1-2) hours under ultraviolet rays, and the low-temperature resistant flexible electrolyte is prepared.
5. The device of claim 3, wherein the negative electrode is a zinc sheet, a zinc foil or a zinc powder.
6. The low-temperature zinc ion battery of claim 1, wherein the concentration of the fluorine-containing zinc salt is 0.5-2mol/L, and the volume ratio of the ester additive to water is 20-80%.
7. The low-temperature zinc ion battery of claim 4, wherein the specific preparation method of the cathode material is as follows: 2mmol of K4Fe (CN) 6.3H 2O and 0.035mmol of FeSO 4.7H 2O and 0.065mmol of MnSO 4. H2O are dissolved in 100ml and 80ml of saturated KCl solution respectively. The latter solution was slowly added dropwise to the former solution at 60 ℃ with magnetic stirring. After 12h, the precipitate formed was centrifuged and washed thoroughly with deionized water. Finally, the product is dried in air at 80 ℃ for 12h to obtain the Prussian blue analogue.
8. The method as claimed in claim 5, wherein the cathode is prepared by mixing the prussian blue analogue with the conductive agent and the binder at a weight ratio of (7-8): (2-1):1, dissolving the binder with N-methylpyrrolidone, stirring the mixture for (4-12) h, coating the slurry on the current collector, and drying at 60-80 ℃ for 6-12h to obtain the cathode.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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