CN116535667A - Squaric acid MOFs material, preparation method thereof and water-based zinc ion battery - Google Patents
Squaric acid MOFs material, preparation method thereof and water-based zinc ion battery Download PDFInfo
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- CN116535667A CN116535667A CN202310697160.5A CN202310697160A CN116535667A CN 116535667 A CN116535667 A CN 116535667A CN 202310697160 A CN202310697160 A CN 202310697160A CN 116535667 A CN116535667 A CN 116535667A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 35
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 claims abstract description 27
- IHXWECHPYNPJRR-UHFFFAOYSA-N 3-hydroxycyclobut-2-en-1-one Chemical compound OC1=CC(=O)C1 IHXWECHPYNPJRR-UHFFFAOYSA-N 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000003446 ligand Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 11
- 238000005342 ion exchange Methods 0.000 claims description 10
- 229940071125 manganese acetate Drugs 0.000 claims description 9
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 239000003273 ketjen black Substances 0.000 claims description 5
- 239000013110 organic ligand Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of zinc ion batteries, and provides a squaric acid MOFs material, a preparation method thereof and a water-based zinc ion battery. According to the preparation method, the squaric acid is used as an organic ligand, and the obtained squaric acid MOFs material is used as a positive electrode material of the water-based zinc ion battery, so that the capacity is high; the preparation method provided by the invention is simple to operate and low in cost. The invention also provides a water-based zinc ion battery, and the positive electrode material of the water-based zinc ion battery comprises the squaraine MOFs material. The invention uses the squaric acid MOFs material as the positive electrode material of the water-based zinc ion battery, and has the advantage of high capacity.
Description
Technical Field
The invention relates to the technical field of zinc ion batteries, in particular to a squaric acid MOFs material, a preparation method thereof and a water-based zinc ion battery.
Background
Under the large background of pushing a 'double carbon' target, the renewable energy source is pushed to be developed and utilized on a large scale, and the problems of discontinuity, instability and uncontrollability of wind power generation and photovoltaic power generation exist, and an energy storage technology is neededDevelopment, thereby realizing the possibility of industrialized mass production. Although the application of the lithium battery energy storage system can provide support for peak regulation and leveling of a power grid side and a power generation side, the lithium ion battery is faced with the problem of safety caused by the fact that the price of upstream lithium resources is increased, and the lithium battery adopts organic electrolyte, so that the low-cost, safe and reliable battery needs to be developed. The water-based zinc ion battery has high theoretical capacity (820 mAh.g) -1 ) Low oxidation-reduction potential (-0.76V vs. standard hydrogen electrode), abundant reserves, simple process, etc. MOFs materials are applied to water-based zinc ion anode materials by virtue of advantages of high specific surface area, porosity and the like. Chinese patent publication No. CN107887603a discloses a method for synthesizing MOF-5 using terephthalic acid as ligand DMF as solvent, but triethylamine is also added in the method. Chinese patent publication No. CN113698619a discloses a MOF using 2,3,6,7,10, 11-hexahydroxytriphenyl as a monomer, but the monomer used in this method is expensive and cumbersome to produce. In addition, the zinc storage properties of the MOFs obtained by both methods are less than ideal, resulting in low capacity.
Disclosure of Invention
In view of the above, the invention aims to provide a squaric acid MOFs material, a preparation method thereof and an aqueous zinc ion battery. The squaric acid MOFs material obtained by the preparation method provided by the invention has high capacity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of squaric acid MOFs material, which comprises the following steps:
dissolving squaraine and sodium hydroxide in water to obtain ligand solution;
dissolving water-soluble metal salt in water to obtain a metal salt solution;
adding the metal salt solution into the ligand solution, and performing ion exchange to obtain the squaraine MOFs material;
the water-soluble metal salt is one or more of water-soluble manganese salt, water-soluble zinc salt and water-soluble copper salt.
Preferably, the molar ratio of squaraine to sodium hydroxide is 1:2 to 2.2.
Preferably, the water-soluble manganese salt comprises manganese acetate, the water-soluble zinc salt comprises zinc acetate, and the water-soluble copper salt comprises copper acetate.
Preferably, the molar ratio of the water-soluble metal salt to the squaric acid is 1-1.2: 1.
preferably, the temperature of the ion exchange is room temperature and the time is 1-24 hours.
The invention also provides the squaric acid MOFs material obtained by the preparation method.
The invention also provides a water-based zinc ion battery, and the positive electrode material of the water-based zinc ion battery comprises the squaraine MOFs material.
Preferably, the positive electrode material of the aqueous zinc ion battery further comprises a conductive agent and a binder; the conductive agent comprises ketjen black and the binder comprises polyvinylidene fluoride.
Preferably, the mass ratio of the squaric acid MOFs material, the conductive agent and the binder in the positive electrode material of the water-based zinc ion battery is 6:3:1.
the invention provides a preparation method of squaric acid MOFs material, which comprises the following steps: dissolving squaraine and sodium hydroxide in water to obtain ligand solution; dissolving water-soluble metal salt in water to obtain a metal salt solution; adding the metal salt solution into the ligand solution, and performing ion exchange to obtain the squaraine MOFs material; the water-soluble metal salt is one or more of water-soluble manganese salt, water-soluble zinc salt and water-soluble copper salt.
According to the invention, light-weight small molecular squaric acid is used as an organic ligand, and squaric acid with multiple active sites can be combined with more metal ions to prepare squaric acid MOFs material which is used as a positive electrode material of a water-based zinc ion battery, so that high capacity can be brought; the preparation method provided by the invention is simple to operate and low in cost.
The invention also provides a water-based zinc ion battery, and the positive electrode material of the water-based zinc ion battery comprises the squaraine MOFs material. The invention uses the squaric acid MOFs material as the positive electrode material of the water-based zinc ion battery, and has the advantage of high capacity.
Drawings
FIG. 1 is an infrared spectrum of Mn-SQ cathode material obtained in example 1;
FIG. 2 is a cycle stability test of the Mn-SQ cathode material obtained in example 1;
FIG. 3 is an infrared spectrum of the ZnMn-SQ cathode material obtained in example 2;
FIG. 4 is a graph showing the rate performance test of the ZnMn-SQ cathode material obtained in example 2;
FIG. 5 shows that the Cu-SQ positive electrode material obtained in example 3 was prepared at 0.1 A.g -1 And the charge-discharge curve under.
Detailed Description
The invention provides a preparation method of squaric acid MOFs material, which comprises the following steps:
dissolving squaraine and sodium hydroxide in water to obtain ligand solution;
dissolving water-soluble metal salt in water to obtain a metal salt solution;
adding the metal salt solution into the ligand solution, and performing ion exchange to obtain the squaraine MOFs material;
the water-soluble metal salt is one or more of water-soluble manganese salt, water-soluble zinc salt and water-soluble copper salt.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
In the invention, squaric acid and sodium hydroxide are dissolved in water to obtain ligand solution.
In the present invention, the water is preferably deionized water. In the present invention, the molar ratio of the squaraine to the sodium hydroxide is preferably 1:2 to 2.2.
In the present invention, the dissolving of squaraine and sodium hydroxide in water preferably comprises: dissolving Fang Suanrong in water, and adding sodium hydroxide after the squaraine is completely dissolved.
The invention dissolves water-soluble metal salt in water to obtain metal salt solution.
In the present invention, the water is preferably deionized water. In the invention, the water-soluble metal salt is one or more of water-soluble manganese salt, water-soluble zinc salt and water-soluble copper salt. In the present invention, the water-soluble manganese salt preferably includes manganese acetate, the water-soluble zinc salt preferably includes zinc acetate, and the water-soluble copper salt preferably includes copper acetate.
In the present invention, the molar ratio of the water-soluble metal salt to squaric acid is preferably 1 to 1.2:1.
after ligand solution and metal salt solution are obtained, the metal salt solution is added into the ligand solution to perform ion exchange, so that the squaraine MOFs material is obtained.
In the present invention, the manner of addition is preferably dropwise addition, and the dropwise addition is preferably completed in 10 minutes.
In the invention, the temperature of the ion exchange is preferably room temperature, and the time is preferably 1-24 h; the ion exchange is preferably carried out under stirring.
After the ion exchange, the invention preferably further comprises the steps of sequentially carrying out suction filtration and drying. In the present invention, the drying temperature is preferably 60 to 80℃and the time is preferably 6 to 12 hours.
The invention also provides the squaric acid MOFs material obtained by the preparation method.
The invention also provides a water-based zinc ion battery, and the positive electrode material of the water-based zinc ion battery comprises the squaraine MOFs material.
In the present invention, the positive electrode material of the aqueous zinc-ion battery preferably further includes a conductive agent and a binder. In the present invention, the conductive agent preferably includes ketjen black. In the present invention, the binder preferably includes polyvinylidene fluoride.
In the invention, the mass ratio of the squaric acid MOFs material, the conductive agent and the binder in the positive electrode material of the water-based zinc ion battery is preferably 6:3:1.
in the present invention, the electrolyte of the aqueous zinc-ion battery is preferably 2 mol.L -1 ZnSO 4 Aqueous solution or 2 mol.L -1 ZnSO 4 +0.1mol·L -1 MnSO 4 The aqueous solution is more preferably 2 mol.L -1 ZnSO 4 +0.1mol·L -1 MnSO 4 An aqueous solution.
The squaraine MOFs material, the preparation method thereof and the aqueous zinc-ion battery provided by the invention are described in detail below with reference to examples, but they are not to be construed as limiting the scope of the invention.
Example 1
5mmol of squaric acid is weighed and dissolved in 20mL of deionized water, and after the squaric acid is completely dissolved, 10mmol of sodium hydroxide is added to obtain ligand solution.
5mmol of manganese acetate was weighed and dissolved in 20mL of deionized water to obtain a manganese acetate solution.
Slowly dripping the manganese acetate solution into the ligand solution, controlling the dripping time to be about 10min, stirring for 4h, carrying out suction filtration, and carrying out vacuum drying at 80 ℃ for 12h to obtain the squaric acid MOFs material, which is marked as Mn-SQ anode material.
The Mn-SQ cathode material prepared in the example was subjected to infrared test, the result is shown in FIG. 1, and the result is shown in FIG. 1, 532cm -1 The appearance of the O-Mn peak at this location confirms the synthesis of Mn-SQ.
The mass ratio of Mn-SQ positive electrode material, conductive agent and binder is 6:3:1 to prepare an electrode sheet. Weighing 60mg of Mn-SQ positive electrode material, 30mg of Keqin black, putting into an agate mortar, uniformly grinding, dropwise adding 500mg of NMP solution containing 2% PVDF, continuously grinding, uniformly smearing the prepared slurry on a stainless steel mesh, and drying in vacuum at 80 ℃ for 12 hours. Cutting the dried electrode slice into electrode slices with the diameter of 1cm, assembling according to the sequence of an anode shell, the electrode slice, electrolyte, a diaphragm, electrolyte, a zinc slice, a gasket, an elastic slice and a cathode shell, and compacting the battery by a tablet press after the assembling is finished, thus obtaining the water-based zinc ion button cell.
The electrolyte used was 2 mol.L -1 ZnSO 4 +0.1mol·L -1 MnSO 4 An aqueous solution.
The assembled battery was subjected to electrochemical performance test, and the results are shown in fig. 2, and it can be seen from fig. 2: at 0.2 A.g -1 Is activated at current density of (2)After conversion, the specific capacity was 380.8 mAh.g -1 The positive electrode material of the aqueous zinc-ion battery prepared in example 1 was confirmed to have excellent specific capacity.
Example 2
5mmol of squaric acid is weighed and dissolved in 20mL of deionized water, and after the squaric acid is completely dissolved, 10mmol of sodium hydroxide is added to obtain ligand solution.
5mmol of manganese acetate was weighed and dissolved in 20mL of deionized water to obtain a manganese acetate solution.
5mmol of zinc acetate was weighed and dissolved in 20mL of deionized water to obtain a zinc acetate solution.
And (3) slowly dripping the manganese acetate solution and the zinc acetate solution into the ligand solution at the same time, and controlling the dripping time to be about 10 minutes. Stirring for 4h, suction filtering, vacuum drying at 80 ℃ for 12h to obtain the squaric acid MOFs material, which is marked as ZnMn-SQ positive electrode material.
The result of infrared test on the ZnMn-SQ positive electrode material prepared in the example is shown in FIG. 3, and can be seen from FIG. 3: 532cm -1 The presence of the O-M peak at this location confirms the synthesis of ZnMn-SQ.
The mass ratio of the ZnMn-SQ anode material to the conductive agent to the binder is 6:3:1 to prepare an electrode sheet. 60mg of ZnMn-SQ positive electrode material, 30mg of ketjen black, putting into an agate mortar, uniformly grinding, dropwise adding 500mg of NMP solution containing 2% PVDF, continuously grinding, uniformly smearing the prepared slurry on a stainless steel mesh, and drying in vacuum at 80 ℃ for 12 hours. Cutting the dried electrode slice into electrode slices with the diameter of 1cm, assembling according to the sequence of an anode shell, the electrode slice, electrolyte, a diaphragm, electrolyte, a zinc slice, a gasket, an elastic slice and a cathode shell, and compacting the battery by a tablet press after the assembling is finished, thus obtaining the water-based zinc ion button cell.
The electrolyte used was 2 mol.L -1 ZnSO 4 +0.1mol·L -1 MnSO 4 An aqueous solution.
The assembled battery was subjected to electrochemical performance test, and the results are shown in FIG. 4, and 0.2 A.g was tested in FIG. 4 -1 As can be seen from fig. 4, the current density at which the current density is higher: the current density is 0.2, 0.3, 0.5, 0.7And 1 A.g -1 The specific capacity was 504.4mAh g -1 、481.13mAh·g -1 、353.5mAh·g -1 、251.mAh·g -1 And 143.8 mAh.g -1 When the current density returns to 0.2 A.g -1 The specific capacity still can reach 542.6 mAh.g -1 The positive electrode material of the water-based zinc ion battery prepared in example 2 was confirmed to have excellent rate performance.
Example 3
5mmol of squaric acid is weighed and dissolved in 20mL of deionized water, and after the squaric acid is completely dissolved, 10mmol of sodium hydroxide is added to obtain ligand solution.
5mmol of copper acetate was weighed and dissolved in 20mL of deionized water to obtain a copper acetate solution.
Slowly dripping the copper acetate solution into the ligand solution, and controlling the dripping time to be about 10 minutes. Stirring for 4h, suction filtering, vacuum drying at 80 ℃ for 12h to obtain the squaric acid MOFs material, which is marked as Cu-SQ positive electrode material.
The mass ratio of the Cu-SQ anode material to the conductive agent to the binder is 6:3:1 to prepare an electrode sheet. 60mg of Cu-SQ positive electrode material, 30mg of ketjen black, putting into an agate mortar, uniformly grinding, dropwise adding 500mg of NMP solution containing 2% PVDF, continuously grinding, uniformly smearing the prepared slurry on a stainless steel mesh, and drying in vacuum at 80 ℃ for 12 hours. Cutting the dried electrode slice into electrode slices with the diameter of 1cm, assembling according to the sequence of an anode shell, the electrode slice, electrolyte, a diaphragm, electrolyte, a zinc slice, a gasket, an elastic slice and a cathode shell, and compacting the battery by a tablet press after the assembling is finished, thus obtaining the water-based zinc ion button cell.
The electrolyte used was 2 mol.L -1 ZnSO 4 An aqueous solution.
The assembled battery was subjected to electrochemical performance test, and the results are shown in fig. 5, and it can be seen from fig. 5: cu-SQ positive electrode material is 0.1 A.g -1 The discharge specific capacity of the first turn reaches 248 mAh.g -1 It was revealed that the Cu-SQ positive electrode material of example 3 had a good specific discharge capacity.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A preparation method of squaric acid MOFs material comprises the following steps:
dissolving squaraine and sodium hydroxide in water to obtain ligand solution;
dissolving water-soluble metal salt in water to obtain a metal salt solution;
adding the metal salt solution into the ligand solution, and performing ion exchange to obtain the squaraine MOFs material;
the water-soluble metal salt is one or more of water-soluble manganese salt, water-soluble zinc salt and water-soluble copper salt.
2. The method according to claim 1, wherein the molar ratio of squaraine to sodium hydroxide is 1:2 to 2.2.
3. The method of preparation of claim 1, wherein the water-soluble manganese salt comprises manganese acetate, the water-soluble zinc salt comprises zinc acetate, and the water-soluble copper salt comprises copper acetate.
4. A method of preparation according to claim 1 or 3, wherein the molar ratio of water-soluble metal salt to squaric acid is 1 to 1.2:1.
5. the method according to claim 1, wherein the ion exchange is carried out at room temperature for 1 to 24 hours.
6. The squaraine MOFs material obtained by the preparation method according to any one of claims 1 to 5.
7. An aqueous zinc ion battery, wherein the positive electrode material of the aqueous zinc ion battery comprises the squaraine MOFs material of claim 6.
8. The aqueous zinc-ion battery of claim 7, wherein the positive electrode material of the aqueous zinc-ion battery further comprises a conductive agent and a binder; the conductive agent comprises ketjen black and the binder comprises polyvinylidene fluoride.
9. The aqueous zinc-ion battery according to claim 8, wherein the mass ratio of the squaric acid MOFs material, the conductive agent and the binder in the positive electrode material of the aqueous zinc-ion battery is 6:3:1.
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