CN111342019B - Tin-based metal-organic framework, preparation method thereof and application of tin-based metal-organic framework as negative electrode material of lithium ion battery - Google Patents
Tin-based metal-organic framework, preparation method thereof and application of tin-based metal-organic framework as negative electrode material of lithium ion battery Download PDFInfo
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000007773 negative electrode material Substances 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012153 distilled water Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000010406 cathode material Substances 0.000 claims abstract description 12
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims abstract description 10
- ANPOYDAMHZJFFI-UHFFFAOYSA-N 1,4-dihydroxycyclohexa-3,5-diene-1,2-dicarboxylic acid Chemical compound OC(=O)C1C=C(O)C=CC1(O)C(O)=O ANPOYDAMHZJFFI-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 2, 5-dihydroxy phthalic acid ion Chemical class 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000013110 organic ligand Chemical group 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- GOEWOMATKBPGDT-UHFFFAOYSA-N 2,5-dihydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1O GOEWOMATKBPGDT-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000002500 ions Chemical group 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
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- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
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- BCEQKAQCUWUNML-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(O)C(C(O)=O)=C1 BCEQKAQCUWUNML-UHFFFAOYSA-N 0.000 claims description 2
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
A tin-based metal-organic framework, a preparation method thereof and application thereof as a negative electrode material of a lithium ion battery. The tin-based metal-organic framework has the chemical formula [ Sn 2 (dobpdc)] n Wherein dobpdc is 2, 5-dihydroxy phthalic acid ion; the preparation method comprises mixing stannous sulfate (SnSO) 4 ) Adding 2, 5-dihydroxy benzene dicarboxylic acid into distilled water, and carrying out hydrothermal reaction to obtain a target product. The tin-based metal-organic framework synthesized by the invention can be used as a lithium ion battery cathode material to assemble a CR2032 lithium ion button battery. The invention has the advantages of simple synthesis method, cheap and easily obtained raw materials, high yield and low cost. The alloy can be directly used in a lithium ion battery cathode material, can effectively relieve the volume expansion effect in the alloying process, and has the charge-discharge current density of 200mA g ‑1 The specific capacity of the complex is maintained at 1018mAh g after 200 times of circulation ‑1 . The electrochemical material also shows good stability and excellent electrochemical performance in a rate test.
Description
Technical Field
The invention relates to the field of lithium ion battery electrode materials, in particular to synthesis of a novel tin-based metal-organic framework with good stability, a lithium ion battery cathode plate and a lithium ion battery preparation method.
Background
The lithium ion battery is an energy storage device which takes lithium ions as carriers to complete the conversion between chemical energy and electric energy between a positive electrode and a negative electrode of the battery, has the outstanding advantages of high energy density, long cycle life, no memory effect, small volume, portability and the like, and is widely applied to portable electrical appliances such as mobile phones and notebook computers. With the development and popularization of new energy electric vehicles and energy storage power grids, higher requirements are put on the electrochemical properties of lithium ion batteries, but the theoretical lithium storage capacity of the commercial graphite cathode is only 372mAh g -1 Therefore, designing and synthesizing a high-capacity, long-cycle-life and safer negative electrode material is an important research direction.
The theoretical capacity of the tin-based negative electrode material reaches 990mAh g -1 The storage capacity of the element tin is very rich and the price is lowGreen and environment-friendly, and is one of cathode materials with great commercial prospect. However, metal tin undergoes severe volume expansion during charging and discharging to cause huge volume change, so that the electrode material is cracked and falls off, and the specific capacity and the cycling stability of the battery are reduced. In order to alleviate the volume effect of tin-based negative electrode materials during cycling, the current common methods are as follows: (1) the nano-scale is adopted, the volume expansion effect is reduced, and the binding force with a current collector is increased; (2) alloying, wherein one or two tin-based alloys are introduced to form a binary or ternary tin-based alloy with the inert components, and the introduction of the inert components can form a structural frame, so that the structural frame can buffer the volume expansion of tin and enhance the binding capacity with a current collector, thereby enhancing the cycling stability of the electrode; (3) and (3) compositing, namely forming a composite material by the tin-based material and the carbon material, relieving volume expansion of tin, and increasing conductivity, thereby improving electrochemical performance. However, none of these solutions can in theory completely eliminate the volume expansion due to charging and discharging, and the manufacturing process is usually complicated, relatively costly and not suitable for commercialization. Therefore, breaking through the existing synthesis strategy to prepare the tin-based negative electrode material with low price, easy obtaining and excellent electrochemical properties is the current research hotspot and difficulty.
The metal-organic framework is a three-dimensional coordination polymer formed by metal ions or metal clusters and organic ligands in a self-assembly mode. In recent years, the metal-organic framework has attracted the attention of scientists due to the advantages of abundant and changeable chemical structure, simple synthesis, low cost and the like, and is widely applied to the aspects of gas storage and separation, heterogeneous catalysis, magnetic materials, fluorescent probes, catalysis, energy storage and the like. In the field of energy storage, metal-organic frameworks have been used as electrode materials for lithium ion batteries because of their abundant lithium storage active sites and structural stability. Therefore, it is possible to construct a metal-organic framework by bonding active organic ligands to metallic tin as a node, from the viewpoint of both cost reduction and alleviation of the volume expansion effect of tin element. At present, direct application of tin-based metal-organic framework materials to battery materials is also rarely reported.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides a tin-based metal-organic framework which is simple to synthesize and low in cost, and is used as an active material to be applied to a lithium ion battery cathode. The method effectively inhibits the volume expansion effect of tin, so that the tin-based metal-organic framework material has higher capacity property and better cycle stability in the lithium ion battery cathode.
The technical scheme of the invention is as follows:
a tin-based metal-organic framework of the formula [ Sn ] 2 (dobpdc)] n In the formula: n is a natural number from 1 to infinity, and dobpdc is an acid radical of 2, 5-dihydroxy-benzene dicarboxylic acid; the tin-based metal-organic framework is composed of Sn 2+ Ions and organic ligands form a three-dimensional network structure through coordination bonds, wherein the organic ligands are 2, 5-dihydroxy benzene dicarboxylic acid radical ions; the unit cell contains a crystallographically independent Sn 2+ Ionic, half dobpdc 4- A ligand; sn (tin) 2+ Ion passage dobpdc 4- The ligands are bridged to form a one-dimensional chain structure; then through dobpdc 4- The ligands are linked to form a three-dimensional framework structure.
A process for preparing Sn-base metal-organic frame from SnSO 4 Is a metal salt, with H 4 dobpdc is 2, 5-dihydroxyisophthalic acid (H) 4 dobpdc) as a ligand and water as a solvent, and the synthesis steps are as follows:
1) adding SnSO into stannous sulfate 4 And 2, 5-Dihydroxyisophthalic acid (H) 4 dobpdc) mixture is placed into a container, then distilled water solution containing lithium hydroxide is added, and the mixture is stirred uniformly to obtain mixed solution;
2) placing the mixed solution in an oven at 80-95 ℃ for reaction for 24-72 hours, and then naturally cooling to room temperature to obtain a light yellow flaky crystal;
3) the crystals were washed with distilled water and ethanol and air dried naturally.
Wherein, the mixed solution contains stannous sulfate SnSO 4 2, 5-dihydroxyisophthalic acid (H) 4 dobpdc) and lithium hydroxide in a molar ratio of (2-4) to (1) (4-6); SnSO stannous sulfate 4 The dosage ratio of the distilled water to the distilled water is 0.1mmol:6-10mL。
The application of the tin-based metal-organic framework as the lithium ion battery cathode material directly uses the tin-based metal-organic framework as the lithium ion battery cathode material, and the specific method comprises the following steps:
1) weighing the dried tin-based metal-organic framework, the Ketjen black and the polyvinylidene fluoride according to the mass ratio of 7:2:1, adding N-methyl pyrrolidone, grinding and mixing uniformly to form slurry, coating the slurry on a copper foil, drying for 12 hours at the temperature of 80 ℃ in vacuum, and cutting into circular electrode plates with the diameter of 12 mm;
2) lithium plate as counter electrode, Celgard 2400 membrane as separator, 1mol/L lithium hexafluorophosphate (LiPF) 6 ) Taking a solution of Ethylene Carbonate (EC)/diethyl carbonate (DEC) (in a volume ratio of 1:1) as an electrolyte, and taking the electrode slice obtained in the step 1) as a negative electrode to assemble a CR2032 lithium ion button cell;
3) and testing the assembled lithium ion battery on a blue battery testing system. The temperature is room temperature during testing, and the voltage range in constant current charge and discharge testing is 0.01-3V. The test current density is 200mAg -1 Constant current charge and discharge performance and cycle performance under the condition of high current density of 500mAg -1 The cycle performance of the following. At current densities of 100, 200, 500, 1000, 2000mAg -1 Rate capability in time.
The invention has the advantages and beneficial effects that:
the tin-based metal-organic framework with a novel structure is successfully prepared by a simple chemical synthesis method and is successfully applied to the cathode material of the lithium ion battery. The material can effectively relieve the volume expansion effect in the charge-discharge process, and the charge-discharge current density is 200mAg -1 The specific capacity of the complex is maintained at 1018mAh g after 200 times of circulation -1 . The tin-based electrode material has good stability and excellent electrochemical performance during rate test, is beneficial to enhancing and improving the performance of the tin-based electrode material, and is expected to promote the research progress of the tin-based metal-organic framework.
Drawings
FIG. 1 is [ Sn ] 2 (dobpdc)] n Structural unit diagram of crystal.
FIG. 2 is [ Sn ] 2 (dobpdc)] n Three-dimensional frame diagram of the crystal.
FIG. 3 is [ Sn ] 2 (dobpdc)] n X-ray powder diffraction spectrum of the crystal.
FIG. 4 is [ Sn ] 2 (dobpdc)] n The crystal is used as the cathode material of the lithium ion battery at 200mAg -1 Constant current charge-discharge diagram.
FIG. 5 is [ Sn ] 2 (dobpdc)] n The crystal is used as the cathode material of the lithium ion battery at 200mAg -1 Charge-discharge cycle diagram of (1).
FIG. 6 is [ Sn ] 2 (dobpdc)] n When the crystal is used as the cathode material of a lithium ion battery, the crystal is 500mAg -1 Charge-discharge cycle diagram of (1).
FIG. 7 is [ Sn ] 2 (dobpdc)] n The crystal is used as a multiplying power performance diagram of the lithium ion battery cathode material.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described in more complete detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the following specific embodiments.
Preparation of mono, tin-based metal-organic frameworks
Example 1:
1) weighing stannous sulfate SnSO 4 (0.4mmol,85.6mg) and 2, 5-dihydroxyphthalic acid (0.2mmol,54.8mg) were placed in a glass bottle, followed by addition of 25mL of a distilled aqueous solution containing lithium hydroxide (0.8mmol,32mg) and stirring well to give a mixed solution;
2) placing the uniformly mixed solution in an oven at 80 ℃ for reaction for 72 hours, and then naturally cooling to room temperature to obtain a light yellow flaky crystal;
3) washing the obtained crystal with distilled water and ethanol, and naturally airing to obtain the tin-based metal-organic framework.
Example 2:
1) weighing stannous sulfate SnSO 4 (0.4mmol,85.6mg) and 2, 5-dihydroxyisophthalic acid (0.1mmol,27.4mg) were placed in a glass vial followed by 15mL of a solution containing lithium hydroxide (0.6mmol,24 mg) of the distilled water solution, and uniformly stirring to obtain a mixed solution;
2) placing the uniformly mixed solution in an oven at 85 ℃ for reaction for 48 hours, and then naturally cooling to room temperature to obtain a light yellow flaky crystal;
3) the crystals were washed with distilled water and ethanol and air dried naturally.
Example 3:
1) weighing stannous sulfate SnSO 4 (0.3mmol,64.2mg) and 2, 5-dihydroxyphthalic acid (0.1mmol,27.4mg) were placed in a glass bottle, followed by addition of 45mL of a distilled aqueous solution containing lithium hydroxide (0.5mmol,20mg) and stirring well to obtain a mixed solution;
2) placing the uniformly mixed solution in an oven at 95 ℃ for reaction for 24 hours, and then naturally cooling to room temperature to obtain a light yellow flaky crystal;
3) the crystals were washed with distilled water and ethanol and air dried naturally.
Characterization of the Di, Sn-based Metal-organic framework
The crystals obtained in the above examples were placed on a glass slide, appropriate crystals were selected under a microscope, tested on a Supernova X-ray single crystal diffractometer, and Mo-Ka rays monochromatized with a graphite monochromator
Is a source of incident radiation, in
The diffraction points were collected by scanning, their coordinates and their anisotropic parameters were corrected by the least squares method, the position of the hydrogen atoms was obtained by theoretical hydrogenation, and all calculations were performed using the SHELXL-97 and SHELXL-97 packages. Crystal structure analysis, element analysis and thermogravimetric analysis are carried out according to Olex-2 software, and the structural formula of the complex is finally determined to be [ Sn 2 (dobpdc)] n In which H is 4 dobpdc is 2, 5-dihydroxyisophthalic acid. The complex belongs to a monoclinic system, space group P21/c and unit cell parameter is
α ═ γ ═ 90 °, β ═ 92.329(3) ° and unit cell volume
Z＝4，Dc＝2.317g/cm 3 . The metal-organic framework is composed of Sn 2+ Ions and organic ligands form a three-dimensional network structure through coordination bonds, wherein the organic ligands are 2, 5-dihydroxy benzene dicarboxylic acid; the unit cell contains a crystallographically independent Sn 2+ Ionic, half dobpdc 4- A ligand; sn (tin) 2+ Ion passage dobpdc 4- The ligands are bridged to form a one-dimensional chain structure; then through dobpdc 4- The ligands are linked to form a three-dimensional framework structure. The structure diagram is drawn using Diamond software. FIG. 1 is [ Sn ] 2 (dobpdc)] n FIG. 2 is a view showing coordination environment of the crystal, [ Sn ] 2 (dobpdc)] n Three-dimensional frame diagram of the crystal.
Thirdly, characterization of the purity of the tin-based metal-organic framework:
the tin-based metal-organic framework was collected in large amounts to give pale yellow crystals. To further characterize the purity of the synthesized tin-based metal-organic framework, we tested the X-ray diffraction pattern of the complex. Referring to fig. 3, it can be seen that the diffraction patterns of the synthesized bulk samples are consistent with the X-ray diffraction patterns obtained by simulation of the crystal data, indicating that the purity of the synthesized tin-based metal-organic framework is high.
Fourthly, preparing an electrode plate and assembling the lithium ion battery:
the invention also provides a method for preparing the electrode plate of the lithium ion battery by using the tin-based metal-organic framework as the negative electrode material of the lithium ion battery. The specific steps are that the tin-based metal-organic framework crystals collected in the above examples are dried in a vacuum oven for 10 hours at 80 ℃. Respectively weighing a tin-based metal-organic frame, ketjen black and polyvinylidene fluoride according to a mass ratio of 7:2:1, adding N-methyl pyrrolidone, grinding and uniformly mixing to form slurry, coating the slurry on a copper foil, drying for 12 hours at a vacuum temperature of 80 ℃, and cutting into circular electrode plates with the diameter of 12 mm.
Using lithium sheet as counter electrodeCelgard 2400 membrane as separator, 1mol/L lithium hexafluorophosphate (LiPF) 6 ) The solution of Ethylene Carbonate (EC)/diethyl carbonate (DEC) (volume ratio 1:1) is used as electrolyte, and the obtained electrode plate is used as a negative electrode to assemble the CR2032 lithium ion button cell.
Fifth, testing electrochemical performance
The constant current charge and discharge test is performed in a blue test system (25 ℃), and the voltage range is set to be 0.01-3.0V. Please refer to fig. 4, which is a constant current charge-discharge diagram of a lithium ion battery prepared from the negative electrode material of the lithium battery of the present invention, when the current density is 200mAg -1 The first discharge capacity was 1961mAh g -1 First cycle charge capacity of 938mAh g -1 And has a lower charging and discharging platform. Referring to FIG. 5, the current density is 200mAg -1 The specific capacity can be stabilized at 1018mAh g after 200 times of charge-discharge circulation -1 And the coulombic efficiency is higher, and the electrochemical performance is good. Referring to FIG. 6, at 500mA g -1 Circulating for 600 weeks, and the capacity is 590mAh g -1 Left and right, and keep stable, [ Sn ] 2 (dobpdc)] n The method has good cycling stability and good application prospect.
Please refer to fig. 7, which is [ Sn ] 2 (dobpdc)] n And the rate performance graph is used as a lithium ion battery cathode material. At current densities of 100, 200, 300, 500, 1000, 2000mAg -1 The next 10 weeks, the capacity values are respectively about 960, 950, 940, 880,774,588mAh g -1 . When the current density returns to 100mAg -1 In the process, the capacity of the battery can be restored to an initial value, which shows that the metal-organic framework has good cycle stability and rate capability under high current, and has great potential in the aspect of being used as a negative electrode material of a lithium ion battery.
The above description is intended to be illustrative of the preferred embodiments and not to limit the scope of the patent claims, and any substantially equivalent substitutions, process optimizations, modifications, and combinations of conditions are intended to be within the scope of the patent claims. A few terms are necessary in the description and illustration, nor are they intended to be limiting of the invention.
Claims (3)
1. The application of the tin-based metal-organic framework as the lithium ion battery cathode material is characterized in that the specific application method comprises the following steps:
1) weighing the dried tin-based metal-organic framework, the Ketjen black and the polyvinylidene fluoride according to the mass ratio of 7:2:1, adding N-methyl pyrrolidone, grinding and mixing uniformly to form slurry, coating the slurry on a copper foil, drying in vacuum, and cutting into circular electrode plates;
2) a lithium sheet is used as a counter electrode, a Celgard 2400 membrane is used as a diaphragm, 1mol/L ethylene carbonate/diethyl carbonate solution of lithium hexafluorophosphate with the volume ratio of 1:1 is used as electrolyte, and the electrode sheet obtained in the previous step is used as a negative electrode to assemble the CR2032 lithium ion button battery;
the tin-based metal-organic framework has a chemical formula of [ Sn 2 (dobpdc)] n In the formula: n is a natural number from 1 to infinity, and dobpdc is an acid radical of 2, 5-dihydroxy-benzene dicarboxylic acid; the tin-based metal-organic framework is composed of Sn 2+ Ions and organic ligands form a three-dimensional network structure through coordination bonds, wherein the organic ligands are 2, 5-dihydroxy benzene dicarboxylic acid; the unit cell contains a crystallographically independent Sn 2+ Ionic, half dobpdc 4- A ligand; sn (tin) 2+ Ion passage dobpdc 4- The ligands are bridged to form a one-dimensional chain structure; then through dobpdc 4- The ligands are connected to form a three-dimensional framework structure;
the tin-based metal-organic framework belongs to the monoclinic system, space group P21/c, and the unit cell parameter is
α ═ γ ═ 90 °, β ═ 92.329(3) ° and unit cell volume
Z＝4，Dc＝2.317g/cm 3 。
2. A process for the preparation of a tin-based metal-organic framework for use according to claim 1, characterized in that: using stannous sulfate SnSO 4 As metal salt, with 2, 5-dihydroxyisophthalic acid (H) 4 dobpdc) as a ligand and water as a solvent, and comprises the following synthesis steps:
1) adding SnSO into stannous sulfate 4 And 2, 5-Dihydroxyisophthalic acid (H) 4 dobpdc) mixture is put into a container, then distilled water solution containing lithium hydroxide is added, and mixed solution is obtained after uniform stirring; SnSO in the mixed solution 4 2, 5-dihydroxyl-phthalic acid H 4 The molar ratio of the dobpdc to the lithium hydroxide is (2-4) to 1 (4-6);
2) placing the mixed solution in an oven at 80-95 ℃ for reaction for 24-72 hours, and then naturally cooling to room temperature to obtain a light yellow flaky crystal;
3) the crystals were washed with distilled water and ethanol and air dried naturally.
3. A method for preparing a tin-based metal-organic framework according to claim 2, characterized in that: the stannous sulfate SnSO 4 The dosage ratio of the distilled water to the distilled water is 0.1mmol:6-10 mL.
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