CN116759670A - Porphyrin water-based zinc ion battery electrolyte additive and application thereof - Google Patents
Porphyrin water-based zinc ion battery electrolyte additive and application thereof Download PDFInfo
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- CN116759670A CN116759670A CN202310903189.4A CN202310903189A CN116759670A CN 116759670 A CN116759670 A CN 116759670A CN 202310903189 A CN202310903189 A CN 202310903189A CN 116759670 A CN116759670 A CN 116759670A
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- ion battery
- porphyrin
- zinc
- zinc ion
- battery electrolyte
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 28
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 55
- 239000011701 zinc Substances 0.000 claims description 36
- PBHVCRIXMXQXPD-UHFFFAOYSA-N chembl2369102 Chemical group C1=CC(S(=O)(=O)O)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(=CC=1)S(O)(=O)=O)=C1C=CC(=N1)C(C=1C=CC(=CC=1)S(O)(=O)=O)=C1C=CC(N1)=C1C=2C=CC(=CC=2)S(O)(=O)=O)=C2N=C1C=C2 PBHVCRIXMXQXPD-UHFFFAOYSA-N 0.000 claims description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 22
- 239000011368 organic material Substances 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 125000004151 quinonyl group Chemical group 0.000 claims 1
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical group O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000654 additive Substances 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 8
- -1 Porphyrin compounds Chemical class 0.000 description 7
- 229960001763 zinc sulfate Drugs 0.000 description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 210000001787 dendrite Anatomy 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 108091006149 Electron carriers Proteins 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- 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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
-
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
Abstract
The invention relates to a porphyrin water system zinc ion battery electrolyte additive and application thereof, belonging to the technical field of new energy materials. The porphyrin aqueous zinc ion battery electrolyte additive is porphyrin complex with different functional groups on the periphery, and the composite electrolyte is used as aqueous zinc ion battery electrolyte. The porphyrin water system zinc ion battery electrolyte additive provided by the invention contains the sulfonic porphyrin, so that the cycle life and the battery performance of the water system zinc ion battery can be effectively improved, the porphyrin water system zinc ion battery electrolyte additive is matched with a high-efficiency organic positive electrode material, the capacity attenuation of an all-electric battery is greatly reduced, the zinc ion transmission dynamics is accelerated, and the performance is excellent.
Description
Technical Field
The invention belongs to the technical field of new energy materials, relates to an expansion application of porphyrin molecules, and is used for improving the safety problem caused by side reactions such as dendrite growth and the like in a water-based zinc ion battery.
Background
At present, renewable energy sources are fully and reasonably utilized, and the energy crisis caused by excessive consumption of fossil fuel is effectively improved. However, the intermittent and non-dispatchability of these renewable energy sources has forced the search for more reliable electrochemical energy storage systems.
The aqueous zinc ion battery is widely used for new generation energy storage equipment due to its low cost, high safety and environmental protection. However, despite these unique advantages, metallic zinc anodes present some obstacles in practical use, mainly including the presence of dendrites due to the presence of non-uniform electric fields during cell commercialization; meanwhile, the battery has the problems of poor reversibility and the like. These all lead to a reduced battery life and an increased safety risk, preventing further use thereof. In this regard, scientists have proposed a series of modification methods to suppress metallic zinc anode side reactions, including zinc alloying, adjusting the orientation of the crystal planes of the deposited zinc and electrolyte additives. Although these strategies have achieved primary success, there are still significant technical hurdles and application limitations in practical applications.
In recent years, organic matters are attracting attention as superquality material competitors of next-generation green batteries, and the wonderful organic chemistry and synthesis endow the organic matters with structural adjustability and customizability, so that redox active sites/potential/polarity, structural stability and electronic conductivity can be adjusted. In addition, coordination chemistry makes it possible to construct organometallic complexes composed of organic linkers and metal ions, which have the advantage of metal active sites and of adjustable structure of the organic groups. Porphyrin compounds are widely used in hot subjects such as new fields of material science, life science, information science and the like due to the special macrocyclic aromatic structure, the effect of selectively complexing metal ions and the biophysical activity. Furthermore, the good electron carrier capability, the strong carrier capability and the high carrier mobility of porphyrin compounds have led to their tendency to develop very much in energy storage and conversion devices.
Disclosure of Invention
The invention aims to solve the problems, and provides a porphyrin water-based zinc ion battery electrolyte additive and application thereof, which can inhibit side reactions on the surface of zinc metal by adjusting the solvation structure of hydrated zinc ions; meanwhile, the zinc ions are deposited along a (002) crystal face which is more stable in thermodynamics by introducing the additive, so that the inhibition effect of dendrites is favorably influenced, the utilization rate of zinc metal is improved, and the cycle performance and the service life of the battery are finally improved. The method has simple process and good effect, and has great value for promoting the industrialization application of the water-based zinc ion battery.
The technical problems are realized by the following technical scheme:
the porphyrin water-based zinc ion battery electrolyte additive has the following structure:
R＝SO 3 H、NH 2 COOH or F;
M＝Zn 2+ 。
preferably, the porphyrin-based aqueous zinc ion battery electrolyte additive is 5,10,15, 20-tetra (4-sulfophenyl) porphyrin, which is marked as TPPS.
The application of the porphyrin water-based zinc ion battery electrolyte additive is used for preparing a water-based zinc ion battery, and comprises the following steps: preparing electrolyte from soluble zinc salt, the porphyrin water-based zinc ion battery electrolyte additive and deionized water, taking zinc metal material as a negative electrode, taking organic material as a positive electrode, and separating the positive electrode from the negative electrode by a diaphragm to obtain the water-based zinc ion battery.
Preferably, the soluble zinc salt is zinc sulfate hydrate; the concentration of zinc salt after the electrolyte is prepared is 0.5mol/L to 3mol/L, preferably 2mol/L.
Preferably, the concentration of the porphyrin-based aqueous zinc ion battery electrolyte additive in the prepared electrolyte is 2-8 mg/mL, preferably 4mg/mL.
Preferably, the organic material used as the positive electrode is a quinone fused azaphenol.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, porphyrin organic compounds are introduced into the electrolyte, so that zinc ions are desolvated and adsorbed on the surface of the zinc foil to regulate and control the zinc deposition direction, inhibit the deterioration of zinc dendrites, inhibit side reactions of hydrogen evolution and the like, and the reversibility and the safety of the zinc ion battery are comprehensively improved, so that the zinc ion battery has excellent electrochemical performance.
2. The porphyrin water-based zinc ion battery electrolyte additive provided by the invention has excellent performance in an all-electric battery when being used as the electrolyte of a zinc ion battery, and is 1A g when being matched with an organic material -1 Exhibits a current density of 200mAh g -1 The left and right capacities can continue to cycle 1000 turns without significant attenuation.
3. The porphyrin water-based zinc ion battery electrolyte additive can promote H when used as the electrolyte of a zinc ion battery + Calculated to be 62% of the organic material content derived from H + Storing the rest of the components derived from Zn 2+ Is stored in the memory. It is the intercalation of hydrogen ions that results in high specific capacities of the organic material;
description of the drawings:
FIG. 1 is the cycle performance of the composite electrolyte of example 2 in a zinc symmetric cell;
FIG. 2 is the coulombic efficiency of the example 2 composite electrolyte in a zinc-copper asymmetric cell;
FIG. 3 is the rate capability of the composite electrolyte of example 2 in a zinc symmetric cell;
FIG. 4 is a comparison of the symmetrical cell impedance of the composite electrolyte of example 2 and zinc sulfate electrolyte;
FIG. 5 is a comparison of nucleation overpotential after cycling of a zinc symmetric cell in the composite electrolyte of example 2 and zinc sulfate electrolyte;
FIG. 6 shows the composite electrolyte of example 3 as a zinc ion battery cell electrolyte at 1A g -1 A cycle chart at current density;
FIG. 7 shows the composite electrolyte of example 3 as a zinc ion battery cell electrolyte at 1A g -1 A charge-discharge curve graph at current density;
FIG. 8 is a magnification view of the composite electrolyte of example 3 as a zinc ion battery cell electrolyte;
FIG. 9 is a cyclic voltammogram of the composite electrolyte of example 3 as a zinc ion cell battery electrolyte;
FIG. 10 is a graph showing the impedance of the composite electrolyte of example 3 as a zinc ion battery cell electrolyte before and after cycling;
FIG. 11 is a graph of UV measurements of electrolyte addition to TPPS at different concentrations in example 3.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
The experimental methods used in the examples below are conventional, unless otherwise specified.
Reagents, materials, and the like used in the following examples were obtained commercially unless otherwise specified.
Example 1
The invention provides a novel strategy, namely a porphyrin compound is used as an electrolyte additive of a zinc ion battery, the porphyrin compound is 5,10,15, 20-tetra (4-sulfophenyl) porphyrin (marked as TPPS), and the synthetic route is as follows:
using benzaldehyde (marked as a compound 1) and pyrrole (marked as a compound 2) as raw materials, and synthesizing a compound 3 by reacting in a propionic acid solution at 140 ℃ for 2 hours through an Adler method;
the compound 3 is reacted with concentrated sulfuric acid to obtain the compound 4, namely 5,10,15, 20-tetra (4-sulfophenyl) porphyrin.
The method comprises the following specific steps:
step 1:
benzaldehyde (5.0 mL,49.0 mmol) was added to a 250mL two-necked flask, dissolved with 120mL of propionic acid, 6.0mL of DMSO was added, freshly distilled pyrrole (3.4 mL,49.0 mmol) was added to a constant pressure dropping funnel, diluted with 20mL of propionic acid, and the temperature was raised to 140℃until reflux of the solvent in the flask occurred, and the addition of pyrrole was started. After the completion of the dropwise addition, the reaction was continued at 140 ℃ for 2 hours, then cooled to 60 ℃,15 ml of methanol was added, stirred for 30 minutes, after the completion of the reaction, the mixture was allowed to stand overnight, the next day was filtered under reduced pressure, and the filtrate was washed with methanol until it became clear, then washed with water until the filtrate became neutral (ph=7.0), and the filter cake was collected and dried under vacuum for 24 hours. The crude product was purified by column chromatography with dichloromethane as eluent. 2.4g (31% yield) of a violet solid (designated compound 3) are obtained.
Step 2:
in a round-bottomed flask, 0.5g of compound 3 was dissolved in 17mL of concentrated sulfuric acid and heated with stirring to 120 ℃. The reaction is continued for 4 hours at constant temperature, cooled to room temperature and poured into 500mL of ice water, concentrated NaOH solution and NaHCO solution are used 3 The diluted solution was adjusted to pH 7, concentrated to 200mL, filtered with ice water, the sodium sulfate was removed, and the filter cake was washed with methanol until the filtrate was colorless. To the obtained filtrate, 100mL of methanol was further added to precipitate sodium sulfate and removed by filtration, and the mixture was dried by spinning, and a small amount of sodium sulfate was removed by filtration again with 200mL of methanol solution, and the reaction was repeated three times to obtain a crude product, which was dissolved in 100mL of hot methanol, and 1000mL of acetone was added, and the precipitate was precipitated by stirring and repeated three times to obtain a green product TPPS.
Example 2
The TPPS prepared in example 1 and a 2mol/L zinc sulfate solution were prepared into a composite electrolyte, and zinc electrodeposition test was performed by using a blue cell test system, so as to verify the effect of TPPS on inducing zinc ions to deposit in a (002) crystal face.
Step 1: 14.387g of zinc sulfate heptahydrate and 0.1g of TPPS are added into 25mL of deionized water at room temperature, and the deionized water is completely dispersed by ultrasonic treatment for 20min to prepare 25mL of electrolyte containing 2mol/L of zinc sulfate and 4g/L of TPPS;
step 2: and (3) the composite electrolyte obtained in the step (1) is used for assembling a Zn/Zn symmetrical battery and a Zn/Cu half battery.
FIG. 1 shows that the composite electrolyte obtained in this example was used to prepare a Zn/Zn symmetric cell at 0.5 in the presence or absence of TPPS additivemA cm -2 ，0.25mAh cm -2 Cycling performance plot at current density. When the electrolyte contains TPPS additive, the zinc symmetrical battery shows more excellent stability in circulation, has a great improvement in service life, can stably work for more than 900 hours, and the battery assembled without the additive influences the zinc nucleation process due to the reasons of reduced ion conductivity, overlarge hysteresis voltage and the like, so that the battery performance is reduced. FIG. 2 shows a Zn/Cu cell at 1mA cm assembled with or without TPPS additives obtained in the composite electrolyte of this example -2 ，1mAh cm -2 Cyclic coulombic efficiency plot at current density. When the electrolyte contains TPPS additive, the zinc-copper asymmetric battery shows more excellent stability and reversibility during circulation, the battery assembled by the electrolyte containing the TPPS additive can keep high coulomb efficiency of 99 percent for more than 600 hours, and the battery assembled by the electrolyte without the additive can influence reversible deposition and stripping behaviors of zinc due to the reasons of reduced ion conductivity, overlarge hysteresis voltage and the like, so that the battery performance is reduced. FIG. 3 shows that the Zn/Zn symmetry cell assembled with the composite electrolyte obtained in this example in the presence or absence of TPPS additive has a fixed area capacity of 1mAh cm -2 The current densities were 0.5,1,3,5 mAcm, respectively -2 The following cycle rate graph. When the electrolyte contains TPPS additive, the zinc symmetrical battery shows more excellent multiplying power performance during circulation, and can stabilize output voltage, and the battery assembled without the additive electrolyte can influence the polarization voltage of zinc due to the reasons of reduced ionic conductivity, overlarge hysteresis voltage and the like, so that the battery performance is reduced. Fig. 4 and fig. 5 are respectively an impedance diagram and a nucleation overpotential diagram of a Zn/Zn symmetric battery assembled by the composite electrolyte obtained in this embodiment under the condition of containing a TPPS additive or not, when the electrolyte contains the TPPS additive, the Zn symmetric battery shows smaller interface resistance and nucleation barrier, and due to good electron carrier capability of the TPPS molecule, the strong carrier capability and high carrier mobility can promote faster zinc ion transport kinetics, and the interface resistance and nucleation barrier of zinc ions are reduced.
Example 3
The composite electrolyte prepared in example 2 was used as an electrolyte of a zinc ion organic battery to verify the performance and application in an all-electric battery.
Step 1: adding solvent NMP into organic materials, acetylene black and PVDF according to the mass ratio of 4:5:1, grinding into uniform slurry, coating on a stainless steel net, then placing in an oven at 85 ℃ for 12 hours, removing residual solvent, and cutting into round electrode plates with the diameter of 12mm for standby;
step 2: and adopting 2025 type button cell standard, sequentially placing a round electrode plate, a diaphragm, a composite electrolyte, a zinc plate, a gasket, an elastic sheet and a positive electrode shell in a negative electrode shell, then packaging by a packaging machine to obtain a water system zinc ion 2025 type button cell, and carrying out constant current charge and discharge test by using a blue electric cell test system.
As can be seen from the cycle chart of FIG. 6, the battery prepared by the invention has a battery power of 1Ag -1 The stability is good at the current density, and the cycle capacity attenuation is less through 1000 circles. The charge-discharge curve of FIG. 7 shows that the cell in the composite electrolyte is at 1A g -1 Exhibits a current density of 200mAh g -1 The specific capacity of the electrolyte is greatly exceeding that of zinc sulfate electrolyte. At the same time, the full cell was tested for rate performance at different current densities, when the current density reached 5A g -1 When the capacity is still more than 100mAh g -1 When the current returns to 200mA g again -1 The capacity is also higher than the full cell in the zinc sulfate electrolyte. It can be seen from the CV curves shown in fig. 9 that there are two distinct pairs of redox peaks representing two redox processes and that the polarization in the composite electrolyte is less than that of the zinc sulfate electrolyte. In order to study the kinetic behavior of the cell, the cell was tested for impedance, and as shown in fig. 10, the impedance was greatly reduced after 300 cycles, and it is the introduction of TPPS that desolvates zinc hexahydrate ions, accelerates the kinetics of zinc deposition, and reduces the interfacial impedance. Meanwhile, ultraviolet tests are carried out on TPPS with the same dosage added into electrolyte with different concentrations under the same conditions as shown in figure 11, and the results show that zinc ions are matched at the cavities of TPPS molecules, only the intensity is changed along with the concentration change, the peak position is not changed, and the dehydration of zinc ions hydrate is provedThe solvation process accelerates the transport kinetics of zinc ions.
In conclusion, when the composite electrolyte prepared by the invention is applied to the negative electrode protection of a water-based zinc ion battery, side reactions and dendrite growth can be obviously inhibited, and the performance is excellent.
Claims (7)
1. A porphyrin water system zinc ion battery electrolyte additive has the following structure:
R＝SO 3 H、NH 2 COOH or F;
M＝Zn 2+ 。
2. the porphyrin-based aqueous zinc ion battery electrolyte additive according to claim 1, wherein the porphyrin-based aqueous zinc ion battery electrolyte additive is 5,10,15, 20-tetra (4-sulfophenyl) porphyrin.
3. The application of the porphyrin-based aqueous zinc-ion battery electrolyte additive in the preparation of an aqueous zinc-ion battery, comprising the following steps: preparing electrolyte from soluble zinc salt, the porphyrin water-based zinc ion battery electrolyte additive and deionized water, taking zinc metal material as a negative electrode, taking organic material as a positive electrode, and separating the positive electrode from the negative electrode by a diaphragm to obtain the water-based zinc ion battery.
4. The use of a porphyrin-based aqueous zinc-ion battery electrolyte additive according to claim 3, wherein the soluble zinc salt is zinc sulfate hydrate; after the electrolyte is prepared, the concentration of zinc salt is 0.5 mol/L-3 mol/L.
5. The use of a porphyrin-based aqueous zinc-ion battery electrolyte additive according to claim 3, wherein the concentration of the porphyrin-based aqueous zinc-ion battery electrolyte additive in the prepared electrolyte is 2-8 mg/mL.
6. The use of a porphyrin-based aqueous zinc-ion battery electrolyte additive according to claim 3, wherein the organic material used as the positive electrode is quinone fused azaphenol.
7. The use of a porphyrin-based aqueous zinc-ion battery electrolyte additive according to claim 3, wherein the concentration of zinc salt after the electrolyte is prepared is 2mol/L, and the concentration of the porphyrin-based aqueous zinc-ion battery electrolyte additive is 4mg/mL.
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