CN112708143A - Novel MOFs lithium battery negative electrode material and preparation method and application thereof - Google Patents
Novel MOFs lithium battery negative electrode material and preparation method and application thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 94
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 65
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 73
- 239000011259 mixed solution Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- FWEOQOXTVHGIFQ-UHFFFAOYSA-N 8-anilinonaphthalene-1-sulfonic acid Chemical compound C=12C(S(=O)(=O)O)=CC=CC2=CC=CC=1NC1=CC=CC=C1 FWEOQOXTVHGIFQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
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- 238000001027 hydrothermal synthesis Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
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- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 claims description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 32
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- 239000010406 cathode material Substances 0.000 description 5
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- 230000002829 reductive effect Effects 0.000 description 5
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 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
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- 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
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- 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
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention discloses a novel MOFs lithium battery negative electrode material and a preparation method and application thereof. The preparation method comprises the following steps: s1, dissolving phenyl acid and nitrate in water to obtain a mixed solution, and adding an alkali reagent to adjust the pH of the mixed solution to 2-5; s2, reacting the mixed solution under a heating condition, and cooling to room temperature after reaction to obtain MOFs crystals; and S3, drying the MOFs crystal, and grinding uniformly to obtain the MOFs lithium battery negative electrode material. The preparation method is simple in process, low in process cost and suitable for large-scale production, and the MOFs lithium battery negative electrode material prepared has high specific capacity and good cycle rate, so that the preparation method has a good application prospect in the field of lithium ion battery negative electrode materials.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a novel MOFs lithium battery negative electrode material and a preparation method and application thereof.
Background
Lithium ion batteries consist of a negative electrode, an electrolyte, a separator and a positive electrode, the energy storage of which depends on reversible electrochemical reactions in the electrode material. However, the theoretical capacity (372mAh g) of conventional negative electrode materials such as graphite-1) Limited and poor rate performance; the silicon has higher theoretical specific capacity (4200mAh g)-1) However, during the charging and discharging process, the huge volume expansion causes many defects such as pulverization and shedding of the pole piece material, continuous increase of the SEI film, and continuous consumption of the lithium ions in the positive electrode.
The Metal Organic Frameworks (MOFs) are porous materials formed by coordination and complexation of metal ions and organic ligands, and have the advantages of high surface area, high porosity, low density, good thermal stability, stable and ordered crystal structure and the like. Therefore, in order to improve the capacity of the lithium ion battery, especially the energy density index of the lithium ion battery, the research of applying the MOFs material to the lithium ion battery cathode material is a research hotspot in the field of lithium batteries.
There have been many reports on the synthesis of MOFs crystals, but the efficient and stable preparation of uniform MOFs materials on a large scale remains challenging. The thermodynamics of the synthesis reaction of MOFs may vary significantly for different metal ions, organic ligands and different topologies, and therefore different preparation methods are usually tailored for each MOFs material.
Therefore, the problem to be solved by researchers in the field is to provide a novel high-capacity MOFs lithium battery negative electrode material and a preparation method of the MOFs lithium battery negative electrode material with a simple process.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a novel MOFs lithium battery negative electrode material.
The invention also aims to provide the novel MOFs lithium battery negative electrode material obtained by the preparation method.
The invention further aims to provide application of the novel MOFs lithium battery negative electrode material in a lithium battery negative electrode.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the novel MOFs lithium battery negative electrode material comprises the following steps:
s1, dissolving phenyl acid and nitrate in water to obtain a mixed solution, and adding an alkali reagent to adjust the pH of the mixed solution to 2-5;
s2, adding the mixed solution into a reaction kettle for hydrothermal reaction, cooling to room temperature after the reaction, and separating to obtain MOFs crystals;
and S2, drying the MOFs single crystal, and grinding uniformly to obtain the MOFs lithium battery negative electrode material.
Preferably, the content of the phenyl acid in S1 in water is 0.1-5mmol/mL, and the content of the nitrate in water is 1-5 mmol/mL.
Preferably, the phenyl acid in S1 includes at least one of benzenedicarboxylic acid, biphenyldicarboxylic acid, mellitic acid, terephthalic acid, trimesic acid, benzenetetracarboxylic acid, and the like; more preferably, the phenyl acid is biphenyldicarboxylic acid.
Preferably, the nitrate in S1 includes at least one of nickel nitrate hexahydrate, cobalt nitrate hexahydrate, manganese nitrate hexahydrate, and the like.
Preferably, the alkali agent in S1 includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like. The addition of the alkali reagent can neutralize the acidity of the reaction system, and the pH value of the reaction system is adjusted to 2-5, so that the growth speed of MOFs crystals can be accelerated, and the appearance of the crystals can be controlled.
Preferably, the concentration of the alkali agent in S1 is 0.05-5 mol/L.
Preferably, before the mixed solution is added into the reaction kettle in S2, the mixed solution may be filtered to remove impurities in the solution as much as possible, so as to avoid the impurities from affecting the growth rate, electrical properties and crystal shape of the crystal.
Preferably, the filling degree of the mixed solution in S2 added into the reaction kettle is 30-50%.
Preferably, the hydrothermal reaction in S2 is a constant temperature reaction at 100-200 ℃ for 12-120 h.
Preferably, the MOF crystals in S2 are of the formula C504H264M88O242(M is a transition metal such as Ni, Co, Mn, etc.), belongs to orthorhombic system, space group is P1, unit cell parameter is
α＝β＝γ＝90.000°。
Preferably, the separation in S2 may be performed by filtration or the like.
Preferably, the MOFs crystals obtained in S2 may be dried after washing with deionized water several times repeatedly.
Preferably, the drying in S3 is drying at 100-300 ℃ for 1-5 h.
The MOFs material prepared by the preparation method has the advantages of high surface area, high porosity, low density, good thermal stability, stable and ordered crystal structure and the like, and has good application prospect in the lithium battery negative electrode material.
Preferably, the chemical formula of the MOF crystal in the MOFs lithium battery negative electrode material is C504H264M88O242(M is a transition metal such as Ni, Co, Mn, etc.), belongs to orthorhombic system, space group is P1, unit cell parameter is
α＝β＝γ＝90.000°。
Compared with the prior art, the invention has the following advantages and technical effects:
(1) according to the preparation method, the MOFs lithium battery cathode material is prepared by taking the phenyl acid with high carboxylic acid content as the organic ligand and taking transition metals such as nickel, cobalt and manganese as central ions through a hydrothermal reaction.
(2) The MOFs cell of the MOFs lithium battery negative electrode material provided by the invention is of a layered or columnar structure, the surface area is high, the porosity is high, the density is low, the crystal structure is stable, and an electrochemical test after thermal activation shows that the MOFs lithium battery negative electrode material has high specific capacity and excellent cycle performance, the first-circle discharge specific capacity can reach more than 1600mAh/g under the current density of 500mA/g, the capacity can still keep about 1600mAh/g after 200 cycles, and the specific capacity and the cycle performance are far beyond the conventional MOFs lithium battery negative electrode material.
(3) The charge-discharge mechanism of the novel MOFs lithium battery cathode material developed by the invention mainly comprises the following steps: during discharging, the transition metal is reduced to be dissociated with the ligand, and the lithium ions are combined with active sites on the ligand; during charging, lithium ions are detached from the ligands, and the metal is oxidized to reconcile with the ligands. The novel MOFs lithium battery negative electrode material mainly has the lithium intercalation site which is carboxylic acid group, the specific capacity contribution of the novel MOFs lithium battery negative electrode material is far larger than that of a benzene ring framework, and the proportion of the carboxylic acid group in the MOFs material is improved, so that the specific capacity and the cycling stability of the material are improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a structural diagram of biphenyldicarboxylic acid used in example 1 of the present invention;
FIG. 2 is a diagram showing the coordination of biphenyldicarboxylic acid complex with a transition metal Ni according to example 1 of the present invention;
FIG. 3 is a structural diagram of a columnar Ni-MOFs crystal prepared in example 1 of the present invention;
fig. 4 is a charge-discharge curve diagram of the button cell prepared in example 1 of the present invention;
fig. 5 is a graph of the cycling capacity of the button cell prepared in example 1 of the invention.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments and specific examples, but the embodiments of the present invention are not limited thereto. All the raw materials and reagents used in the present invention are commercially available raw materials and reagents, unless otherwise specified.
S1 preparation of MOFs precursor solution
In one embodiment, the phenyl acid includes at least one of benzene dicarboxylic acid, biphenyl dicarboxylic acid, mellitic acid, terephthalic acid, trimesic acid, benzene tetracarboxylic acid, etc., i.e., the phenyl acid in the present invention is preferably an aromatic carboxylic acid, which has several advantages: (1) the coordination modes are various, and can form an integrated coordination or can be coordinated as a bridging ligand. The carboxylic acid ligand has strong coordination capability, can be coordinated with different metals or metal oxygen clusters, can form various types, and greatly enriches the composition of coordination compounds; (2) because the carboxyl group can lose proton or not, the carboxylic acid ligand can be used as an oxygen acceptor in an oxygen bond or a hydrogen donor, and is very beneficial to further assembling a low-dimensional complex into a high-dimensional complex; (3) the aromatic ring can lead the ligand to have certain rigidity, is beneficial to crystal growth and is beneficial to forming a high-dimensional porous structure; (4) the conjugation in the aromatic ring is beneficial to the transfer of electrons, the electrons in the formed coordination compound have rich energy levels, and the transition of the electrons between the energy levels can be mutually transferred with the electrons of the metal ions. More preferably, the phenyl acid is biphenyldicarboxylic acid. The MOFs crystal structure has longer organic molecules serving as pillars between nickel cluster nodes, so that the pores of the MOFs crystal are enlarged, and lithium ions and electrons are more favorably transferred at an electrolyte/electrode interface.
In one embodiment, the nitrate comprises at least one of nickel nitrate hexahydrate, cobalt nitrate hexahydrate, manganese nitrate hexahydrate, and the like. The invention preferably adopts one of the MOFs materials for preparation, wherein the synthesis method of the single-metal MOFs material is simple, the synthesis path is easy to control, and the crystal morphology and structure are easier to control. Of course, in another embodiment, the nitrate may be at least two of nickel nitrate hexahydrate, cobalt nitrate hexahydrate, manganese nitrate hexahydrate, and the like, and the synergistic effect of multiple active metals may enable the MOFs material to have good conductivity and richer oxidation active sites.
In one embodiment, in order to promote the solubility of the phenyl acid and the nitrate in water, increase the dissolution rate, and the uniformity of the precursor mixed solution, the dissolution operation may be performed by stirring dissolution, ultrasonic dissolution, or the like. The stirring dissolution can be carried out for 0.5-3h under the conditions of 600-1200 r/min. The ultrasonic dissolution can be 80-120W/cm2Ultrasonic treatment is carried out for 0.2-1h under power.
In one embodiment, an alkali reagent is added to adjust the pH value of the mixed solution to 2-5, the pH value is a key parameter for synthesizing MOFs crystals through a hydrothermal reaction, the solubility of a precursor and the growth speed of the crystals can be influenced, more importantly, the structure of a basic element is changed, and the structure, the shape, the size and the crystallization starting temperature of the crystals are finally determined.
In one embodiment, the phenyl acid is present in the water in an amount of 0.1 to 5mmol/mL and the nitrate is present in the water in an amount of 1 to 5 mmol/mL. The proper concentration of the precursor can enable the crystal substance to have larger solubility and a sufficiently large temperature coefficient of solubility, so that the growth speed of the crystal is improved, and the growth of the crystal is not facilitated when the concentration of the precursor is too high and the viscosity of a reaction system is increased to a certain degree, so that the proper concentration range of the precursor is optimized.
S2 preparation of MOFs crystal
According to the invention, a hydrothermal reaction is adopted to synthesize MOF crystals, namely reactants are dissolved in a hydrothermal medium in the form of ions or molecular groups under the hydrothermal condition, strong convection is formed by utilizing the temperature difference of the upper part and the lower part of a solution in a reaction kettle, ions, ion groups and molecules in a high-temperature region are conveyed to a low-temperature region with seed crystals to form a supersaturated solution, and crystals are separated out. The ions, ion groups and molecules are reacted in the process of conveying to form the polymer with a spatial geometrical configuration, namely a growth unit. The formation process of the growth element is inseparable from the hydrothermal reaction condition. The synthesis of MOFs crystals by the hydrothermal reaction has the advantages of medium-low temperature liquid phase control, low energy consumption, wide application range, more reaction raw material choices, relative cheapness and easy acquisition, high yield of the obtained target product, high purity, good crystallinity, simple process operation, suitability for industrial production and the like.
In one embodiment, the mixed solution is filtered and purified before being added into the reaction kettle, on one hand, undissolved precursors in the mixed solution are removed, so that the uniformity of the mixed solution is improved, on the other hand, insoluble impurities are removed, the impurities have obvious influence on the growth speed of the crystal, and in a supersaturated state, more impurities in the solution have an inhibiting effect on the growth speed of the crystal, namely the grown crystal has an adsorption effect on the impurities, so that the relative growth speed is changed, and the morphology of the crystal is finally influenced. Therefore, further, in order to reduce the influence of soluble and insoluble impurities on the crystal growth, the reagent used in the preparation process is preferably a high-purity reagent, and the introduction of impurities is avoided from the source, and preferably, the purity of the phenyl acid is more than 99.9%, and the purity of the nitrate is more than 99%.
In one embodiment, the hydrothermal reaction is carried out at constant temperature of 100-200 ℃ for 12-120 h. The temperature of the hydrothermal reaction has a significant influence on the crystal structure of the generated MOFs crystal, and under different temperature conditions, the steam pressure and the temperature difference generated in the reaction kettle are different, so that the crystal configurations obtained by preparation are obviously different, and in order to further improve the surface area and the porosity, the thermal stability and the crystal structure stability and order of the MOFs crystal structure prepared by the invention, the temperature of the hydrothermal reaction is preferably 140-160 ℃; meanwhile, under the same other reaction conditions, when the reaction time is shorter, the higher the crystal face index exposed by the generated crystal grains is, the more irregular the aggregated particle form is, the wider the particle size distribution of the powder is along with the increase of the reaction time, the larger the average particle size is, the higher the crystal form regularity is, but the longer the reaction time is, the more the crystal regularity is obviously reduced, and preferably, the reaction time of the hydrothermal reaction is preferably 48 to 72 hours.
In one embodiment, the hydrothermal reaction is followed by natural cooling to room temperature. In order to improve the morphology of the MOFs crystals, in another embodiment, the hydrothermal reaction is followed by programmed cooling, and the cooling rate of the programmed cooling is 3-5 ℃/h.
S3 preparation of MOFs negative electrode material
In one embodiment, the drying is performed at 100-300 ℃ for 1-5 h. The drying operation is mainly used for removing excessive crystal water existing in MOFs crystals, and water is used as a common impurity, so that the hydrolysis of electrolyte lithium salt is easily caused, the impedance of the battery is further increased, the irreversible capacity loss of the battery is increased, the voltage platform is reduced, the solid electrolyte interface film structure is damaged, the safety performance of the battery is reduced, and the method is an index which needs to be controlled strictly in the production process of the lithium ion battery.
In one embodiment, the grinding can be performed by ball milling; the ball milling time can be 0.5-2 h. The particle size of the MOFs lithium battery negative electrode material has a significant influence on the electrical property of the MOFs lithium battery negative electrode material, so that the prepared MOFs lithium battery negative electrode material is more uniform in particle size, and the uniformly ground negative electrode material is further screened by a standard sieve. The particle size of the MOFs lithium battery negative electrode material is preferably 15-40 μm.
The following is a detailed description of the embodiments.
Example 1
S1, adding 20mmol of biphenyldicarboxylic acid and 60mmol of nickel nitrate hexahydrate into 50mL of deionized water, stirring and dissolving to obtain a mixed solution, and adding 0.5mol/L of NaOH solution to adjust the pH value of the mixed solution to 4.1;
s2, filtering the mixed solution, adding the filtered mixed solution into a reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 72 hours, naturally cooling to room temperature after the reaction, filtering and washing the obtained product to obtain pure Ni-MOFs crystals;
s3, drying the Ni-MOFs single crystal at 210 ℃ for 3h, and uniformly grinding to obtain the MOFs lithium battery negative electrode material.
Characterization of Ni-MOFs Crystal Structure
The phase of the Ni-MOFs crystals was characterized by means of a German D8Advance X-ray diffractometer (CuK radiation, 40kV, 40 mA).
The crystal structure parameters of Ni-MOFs are shown in Table 1. The Ni-MOFs belong to the orthorhombic system and have space group P1. The whole molecule comprises 9 symmetrical units containing 88 nickel atoms and 63 biphenyldicarboxylic acids (FIG. 1), and the formula is C504H264Ni88O242. Since the biphenyldicarboxylic acid has 2 carboxylic acid groups which can participate in coordination, the biphenyldicarboxylic acid has various coordination modes, and the coordination mode of the biphenyldicarboxylic acid and the transition metal is that two adjacent carboxylic acid groups are coordinated with the same metal ion as a monodentate ligand by controlling reaction conditions, as shown in FIG. 2. The crystal structure has longer organic molecules acting as "pillars" between the nickel cluster nodes, as shown in fig. 3.
TABLE 1 Ni-MOFs Crystal Structure parameters
Electrical Performance testing
In order to test the electrical properties of the MOFs lithium battery negative electrode material prepared in example 1, the MOFs lithium battery negative electrode material obtained in example 1 was prepared into a button lithium ion battery for testing. Wherein the mass ratio of the cathode material to the conductive acetylene black to the PVDF binder is 8: 1, and the cathode material to the conductive acetylene black to the PVDF binder are mixedCoating the synthetic slurry on copper foil, drying in a vacuum drying oven for 12 hours to prepare a negative plate, forming a button lithium ion battery with a metal lithium plate, and using LiPF with 1mol/L electrolyte6/(EC + DME), the membrane was Celgard2400 membrane.
Constant current charge and discharge experiments were performed on the assembled batteries using the Land battery program-controlled tester by wuhanxinnuo electronics.
Fig. 4 is a charge-discharge curve diagram of a Ni-MOFs button cell at 25 ℃ and at a current density of 100mA/g, the first discharge of the cell has a wider platform at 1.75V, and then a longer slope is formed until the discharge end point, the first discharge specific capacity can reach 2100mAh/g, the reversible specific capacity is also higher than 1600mAh/g, the first coulombic efficiency is about 75%, in the second charge-discharge, the discharge specific capacity and the reversible specific capacity can both be kept above 1650mAh/g, that is, the coulombic efficiency in the secondary charge-discharge process is above 98%.
FIG. 5 is a graph of specific capacity of Ni-MOFs button cell batteries at 25 ℃ after 200 cycles at a current density of 500mA/g, the specific capacity of the first cycle of discharge is up to 1618mAh/g, the capacity is maintained at 1590 mAh/g after 200 cycles, and the capacity attenuation is very small, i.e., the novel MOFs lithium battery negative electrode material provided by the invention can improve the cycle stability of the battery and prolong the service life of the battery when applied to the battery.
As can be seen from fig. 4 and 5, the novel MOFs lithium battery negative electrode material provided by the present invention exhibits good electrical properties, has high capacity and good cycling stability, only the lithium insertion sites of the ligand are not enough to achieve such high specific capacity, but through reasonable design, active carboxylic acid sites are introduced into the porous MOFs, and the abundant carboxylic acid active sites and the synergistic effect of the porous cage structure greatly improve the cycling specific capacity of the negative electrode material and the cycling stability of the negative electrode material. Meanwhile, the unique porous cage-shaped structure of M-MOFs (M is Ni, Co and Mn) is beneficial to electrolyte diffusion and lithium ion intercalation into an active phase, and the volume change of the negative electrode in the intercalation/deintercalation process is weakened.
Example 2
S1, adding 150mmol of benzenedicarboxylic acid and 250mmol of manganese nitrate hexahydrate into 50mL of deionized water, stirring and dissolving to obtain a mixed solution, and adding 0.5mol/L of NaOH solution to adjust the pH value of the mixed solution to 3;
s2, filtering the mixed solution, adding the filtered mixed solution into a reaction kettle, carrying out hydrothermal reaction at 100 ℃ for 120h, naturally cooling to room temperature after the reaction, filtering and washing the obtained product to obtain pure Ni-MOFs crystals;
s3, drying the Ni-MOFs single crystal at 300 ℃ for 1h, and uniformly grinding to obtain the MOFs lithium battery negative electrode material.
The MOFs lithium battery negative electrode material prepared in the embodiment 2 is prepared into a button type lithium ion battery, the preparation method of the button type lithium ion battery is the same as that of the embodiment 1, and the electrical property of the button type lithium ion battery is equivalent to that of the button type lithium ion battery prepared in the embodiment 1.
Example 3
S1, adding 100mmol of mellitic acid and 200mol of cobalt nitrate hexahydrate into 50mL of deionized water, stirring and dissolving to obtain a mixed solution, and adding 3mol/L of LiOH solution to adjust the pH value of the mixed solution to 5;
s2, filtering the mixed solution, adding the filtered mixed solution into a reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 96 hours, naturally cooling to room temperature after the reaction, filtering and washing the obtained product to obtain pure Ni-MOFs crystals;
s3, drying the Ni-MOFs single crystal at 200 ℃ for 2h, and uniformly grinding to obtain the MOFs lithium battery negative electrode material.
The MOFs lithium battery negative electrode material prepared in the embodiment 3 is prepared into a button type lithium ion battery, the preparation method of the button type lithium ion battery is the same as that of the embodiment 1, and the electrical property of the button type lithium ion battery is equivalent to that of the button type lithium ion battery prepared in the embodiment 1.
Example 4
S1, adding 250mmol of mellitic acid and 200mol of cobalt nitrate hexahydrate into 50mL of deionized water, performing ultrasonic dissolution to obtain a mixed solution, and adding 5mol/L of KOH solution to adjust the pH value of the mixed solution to 2;
s2, filtering the mixed solution, adding the filtered mixed solution into a reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 48 hours, naturally cooling to room temperature after the reaction, filtering and washing the obtained product to obtain pure Ni-MOFs crystals;
s3, drying the Ni-MOFs single crystal for 4 hours at 150 ℃, and uniformly grinding to obtain the MOFs lithium battery negative electrode material.
The MOFs lithium battery negative electrode material prepared in the embodiment 4 is prepared into a button type lithium ion battery, the preparation method of the button type lithium ion battery is the same as that of the embodiment 1, and the electrical property of the button type lithium ion battery is equivalent to that of the button type lithium ion battery prepared in the embodiment 1.
Example 5
S1, adding 20mmol of biphenyldicarboxylic acid and 60mmol of nickel nitrate hexahydrate into 50mL of deionized water, stirring and dissolving to obtain a mixed solution, and adding 0.5mol/L of NaOH solution to adjust the pH value of the mixed solution to 4.1;
s2, filtering the mixed solution, adding the filtered mixed solution into a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 12 hours, naturally cooling to room temperature after the reaction, filtering and washing the obtained product to obtain pure Ni-MOFs crystals;
s3, drying the Ni-MOFs single crystal at 210 ℃ for 3h, and uniformly grinding to obtain the MOFs lithium battery negative electrode material.
The MOFs lithium battery negative electrode material prepared in the embodiment 5 is prepared into a button type lithium ion battery, the preparation method of the button type lithium ion battery is the same as that of the embodiment 1, and the electrical property of the button type lithium ion battery is equivalent to that of the embodiment 1.
Comparative example 1
S1, adding 20mmol of biphenyldicarboxylic acid and 60mmol of nickel nitrate hexahydrate into 50mL of deionized water, and stirring to dissolve to obtain a mixed solution;
s2, filtering the mixed solution, adding the filtered mixed solution into a reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 72 hours, naturally cooling to room temperature after the reaction, filtering and washing the obtained product to obtain pure Ni-MOFs crystals;
s3, drying the Ni-MOFs single crystal at 210 ℃ for 3h, and uniformly grinding to obtain the MOFs lithium battery negative electrode material.
The MOFs lithium battery negative electrode material prepared in the comparative example 1 is prepared into a button type lithium ion battery, the preparation method of the battery is the same as that of the battery in the example 1, and then the 200-turn cyclic specific capacity is tested under the condition of 25 ℃ and the current density of 500mA/g, wherein the preferred specific discharge capacity is 818mAh/g, and the capacity after 200 cycles is 723 mAh/g. Compared with example 1, the difference of comparative example 1 is that pH is not adjusted in step S1, and it is possible that hydrogen atoms on the carboxyl group of the phenyl acid are activated and sensitive to acid-base conditions in the reaction system, and the acid-base property is different, and the deprotonation degrees of the carboxyl groups are often greatly different, which causes different coordination modes of the ligands, and meanwhile, when the acidity in the reaction system is higher, the solubility of the phenyl acid which is an acidic compound in the reaction system is increased, the growth rate and crystal form of the MOFs crystal also have significant influence, and finally, the electrical performance of the MOFs lithium battery negative electrode material is influenced.
Comparative example 2
S1, adding 20mmol of biphenyldicarboxylic acid and 60mmol of nickel nitrate hexahydrate into 50mL of deionized water, stirring and dissolving to obtain a mixed solution, and adding 0.5mol/L of NaOH solution to adjust the pH value of the mixed solution to 4.1;
s2, filtering the mixed solution, adding the filtered mixed solution into a reaction kettle, carrying out hydrothermal reaction at 80 ℃ for 6 hours, naturally cooling to room temperature after the reaction, filtering and washing the obtained product to obtain pure Ni-MOFs crystals;
s3, drying the Ni-MOFs single crystal at 210 ℃ for 3h, and uniformly grinding to obtain the MOFs lithium battery negative electrode material.
The MOFs lithium battery negative electrode material prepared in the comparative example 2 is prepared into a button type lithium ion battery, the preparation method of the battery is the same as that of the battery in the example 1, and then the 200-turn specific cyclic capacity is tested under the condition of 25 ℃ and the current density of 500mA/g, wherein the preferred specific discharge capacity is 846mAh/g, and the capacity after 200 cycles is 729 mAh/g. Compared with example 1, comparative example 1 is different in the hydrothermal reaction conditions in the step S2, and it can be seen that parameters of the hydrothermal reaction have a significant influence on the growth of MOFs crystals, and when the hydrothermal reaction conditions are not reasonably designed, the electrical performance of the MOFs lithium battery negative electrode material is finally significantly reduced.
Comparative example 3
S1, adding 2mol of biphenyldicarboxylic acid and 6mol of nickel nitrate hexahydrate into 50mL of deionized water, stirring and dissolving to obtain a mixed solution, and adding 0.5mol/L of NaOH solution to adjust the pH value of the mixed solution to 4.1;
s2, filtering the mixed solution, adding the filtered mixed solution into a reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 72 hours, naturally cooling to room temperature after the reaction, filtering and washing the obtained product to obtain pure Ni-MOFs crystals;
s3, drying the Ni-MOFs single crystal at 210 ℃ for 3h, and uniformly grinding to obtain the MOFs lithium battery negative electrode material.
The MOFs lithium battery negative electrode material prepared in the comparative example 3 is prepared into a button type lithium ion battery, the preparation method of the battery is the same as that of the battery in the example 1, and then the 200-turn cyclic specific capacity is tested under the condition of 25 ℃ and the current density of 500mA/g, wherein the preferred specific discharge capacity is 917mAh/g, and the capacity after 200 cycles is 852 mAh/g. Comparative example 1 is different from example 1 in that the concentrations of the phenyl acid and the nitrate in the step of S1 are different, and as described above, the precursor concentration is too high, and the viscosity of the reaction system increases to some extent, which is disadvantageous for the growth of crystals, thereby causing a decrease in electrical properties thereof.
The above embodiments are the best mode for carrying out the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent substitutions and are included in the scope of the present invention.
Claims (10)
1. A preparation method of a novel MOFs lithium battery negative electrode material is characterized by comprising the following steps:
s1, dissolving phenyl acid and nitrate in water to obtain a mixed solution, and adding an alkali reagent to adjust the pH of the mixed solution to 2-5;
s2, adding the mixed solution into a reaction kettle for hydrothermal reaction, cooling to room temperature after the reaction, and separating to obtain MOFs crystals;
and S3, drying the MOFs crystal, and grinding uniformly to obtain the MOFs lithium battery negative electrode material.
2. The method for preparing the novel MOFs lithium battery negative electrode material of claim 1, wherein: the content of the phenyl acid in the S1 in water is 0.1-5 mmol/mL; the content of the nitrate in water is 1-5 mmol/mL.
3. The method for preparing the novel MOFs lithium battery negative electrode material of claim 1, wherein: the phenyl acid in S1 includes at least one of benzenedicarboxylic acid, biphenyldicarboxylic acid, mellitic acid, terephthalic acid, trimesic acid, and benzenetetracarboxylic acid.
4. The method for preparing the novel MOFs lithium battery negative electrode material of claim 1, wherein: the nitrate in S1 includes at least one of nickel nitrate hexahydrate, cobalt nitrate hexahydrate and manganese nitrate hexahydrate.
5. The method for preparing the novel MOFs lithium battery negative electrode material of claim 1, wherein: the alkali reagent in S1 comprises at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide.
6. The method for preparing the novel MOFs lithium battery negative electrode material of claim 1, wherein: the reaction in S2 is constant temperature reaction at 100-200 ℃ for 12-120 h.
7. The method for preparing the novel MOFs lithium battery negative electrode material of claim 1, wherein: the drying in S3 is drying for 1-5h at the temperature of 100-300 ℃.
8. Novel MOFs lithium battery negative electrode material, characterized in that it is obtained by the preparation method according to any one of claims 1 to 7.
9. The novel MOFs lithium battery negative electrode material of claim 8, wherein: the chemical formula of MOFs crystal in the MOFs lithium battery negative electrode material is C504H264M88O242M is Ni, Co, Mn, belongs to orthorhombic system, space group is P1, unit cell parameter is
α＝β＝γ＝90.000°。
10. Use of the novel MOFs lithium battery negative electrode material according to any one of claims 8 to 9 in a lithium battery negative electrode material.
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