CN112201786B - Potassium phosphate metal salt organic compound cathode material with vanadium as substrate and preparation method thereof - Google Patents

Potassium phosphate metal salt organic compound cathode material with vanadium as substrate and preparation method thereof Download PDF

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CN112201786B
CN112201786B CN202010804764.1A CN202010804764A CN112201786B CN 112201786 B CN112201786 B CN 112201786B CN 202010804764 A CN202010804764 A CN 202010804764A CN 112201786 B CN112201786 B CN 112201786B
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vanadium
metal salt
organic compound
potassium phosphate
phosphate metal
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CN112201786A (en
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欧星
范鑫铭
罗弼
张佳峰
张宝
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Central South University
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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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/005—Compounds of elements of Group 5 of the Periodic System without metal-carbon linkages
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

The potassium phosphate metal salt organic compound anode material with vanadium as a substrate and the preparation method thereof are disclosed, wherein the molecular formula of the anode material is as follows: c2H10K2O16P2V2The anode material is prepared by doping a carbon nano tube conductive agent and a potassium source, and belongs to a monoclinic system structure. The method comprises the following steps: (1) adding a vanadium-containing compound into water, dispersing, then adding a phosphorus source, stirring, adding a potassium source, and uniformly dispersing; (2) carrying out hydrothermal reaction, filtering, washing the precipitate, and drying to obtain a K-organic framework structure material; (3) mixing with carbon nanotube conductive agent, and grinding. The cathode material has high discharge capacity, good rate capability, stable cycle performance and coulombic efficiency; the method has the advantages of low synthesis temperature, simple operation, low cost, strong controllability and good repeatability, and is suitable for industrial production.

Description

Potassium phosphate metal salt organic compound cathode material with vanadium as substrate and preparation method thereof
Technical Field
The invention relates to a potassium ion cathode material and a preparation method thereof, in particular to a potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate and a preparation method thereof.
Background
In recent years, with the rapid development in the fields of electronic equipment, electric tools, small-power electric vehicles and the like, the research of energy storage materials with high energy efficiency, rich resources and environmental friendliness is a necessary condition for realizing sustainable development of the human society. In order to meet the large-scale market demand, it is far from sufficient to rely on the performance such as energy density, charge-discharge rate to measure the battery material.
Novel organic materials and metal organic framework Materials (MOFs) also show potential application prospects as electrode materials of sodium-ion batteries. The greatest obstacles to MOF materials as sodium ion battery materials compared to current cathode materials are the difficulty of mass production and isolation of the redox metal center and the framework. These drawbacks have been the main reason to hinder the commercialization of MOF materials as positive electrode materials for sodium ion batteries. Based on the reason, the energy storage performance of the novel phosphate hybrid material has the characteristics of good cycle performance and high-rate charge-discharge capacity.
CN108172831A discloses a graphene-like carbon-coated vanadium sodium phosphate material, a preparation method thereof and application of the material as a sodium ion battery anode material, wherein an anionic surfactant, a phosphorus source, a hydrocarbon mixture, a vanadium source and a sodium source are sequentially subjected to ball milling and mixing to obtain a vanadium sodium phosphate precursor, and the vanadium sodium phosphate precursor is placed in a protective atmosphere to be calcined to obtain the vanadium sodium phosphate material. However, since the material needs to be calcined at high temperature in a protective atmosphere, the energy consumption is high, the cost is high, and the commercial application of the material is inhibited.
CN 107195886A discloses a sodium vanadium pyrophosphate @ carbon composite positive electrode material, preparation and application thereof, wherein a solution containing a carbon source and a vanadium source is subjected to hydrothermal reaction, and a hydrothermal reaction product is subjected to primary sintering to prepare vanadium oxycarbide; carrying out wet ball milling on the prepared vanadium oxide coated with carbon, a sodium source and a phosphorus source, and then carrying out spray drying to obtain a precursor; the precursor is subjected to secondary sintering to obtain the composite cathode material, the surface of the nanoparticle is coated with a uniform carbon layer, the material is subjected to nanocrystallization, carbon coating is realized, and the defect of poor electronic conductivity of the sodium vanadium pyrophosphate is well overcome. However, the material needs ball milling, spray drying and multi-stage calcination, so the technical difficulty is high and the process cost is high.
CN107317017A discloses a binderless Na3V2(PO4)3/C composite sodium ion battery anode and a preparation method thereof, wherein a sodium source and a vanadium source are subjected to hydrothermal reaction, a phosphorus source and an organic carbon source are weighed and placed in a beaker, deionized water is added, the mixture is stirred for 20min until the mixture is completely dissolved, then naturally cooled intermediate phase liquid is slowly dripped into a container in which the phosphorus source and the organic carbon source are dissolved, the mixture is stirred for 20min until the solution becomes orange yellow, and the mixture is heated and concentrated to a certain volume. And then soaking the carbon matrix in the liquid phase precursor, drying, pre-burning and calcining at high temperature to obtain the binder-free Na3V2(PO4)3/C electrode, which improves the air storage performance, high-temperature storage performance and cycle performance of the material. However, the material has many manufacturing steps, the process flow is complex, and a large amount of waste liquid is generated in the process, so that the pollution is high, and the environmental protection performance is poor.
Therefore, an ion cathode material which is easy to synthesize, low in synthesis temperature, simple in synthesis conditions, free of precursor preparation and sintering, low in energy required by synthesis, convenient and environment-friendly is urgently needed to be found.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing the potassium phosphate metal salt organic compound cathode material which is high in discharge capacity, good in rate capability, stable in cycle performance and coulombic efficiency and takes vanadium as a substrate.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide the preparation method of the potassium phosphate metal salt organic compound cathode material which does not need the preparation and sintering of a precursor, has low synthesis temperature, simple operation, low cost, strong controllability and good repeatability and is suitable for industrial production and takes vanadium as a substrate.
The technical scheme adopted by the invention for solving the technical problems is as follows: the potassium phosphate metal salt organic compound anode material with vanadium as a substrate is prepared from a doped carbon nano tube conductive agent and a potassium source; the single crystal molecular formula of the anode material is as follows: C2H10K2O16P2V2, belonging to monoclinic system structure. Novel organic materials and metal organic framework Materials (MOFs) show potential application prospects as potassium ion battery electrode materials, but the biggest obstacles of the existing MOF materials as commercial potassium ion battery materials are that: difficult mass production and isolation of the redox metal center from the framework. The potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate is a special MOF material, is a multi-dimensional space structure hybrid material formed by cross-linking simple organic ligands by transition metal phosphate, and can package various alkali metals such as Li + and K + ions between layers correspondingly in the structure, and compared with other MOFs, the lithium metal phosphate organic compound cathode material has the advantages that: the inorganic phosphate anion provides stability to the material, reduces the required synthesis temperature, enhances the versatility provided by the organic ligand by enhancing the redox performance of the transition metal ion, and provides more possible two-dimensional migration paths of the alkali metal ion, which makes the synthesis of the metal organic phosphate framework material with the redox active metal center simpler and more convenient.
Preferably, the size of the crystal grains of the single crystal molecules is 0.1 to 5 μm.
Preferably, the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate is in a layered structure, the width of the layered structure is 0.1-5 μm, and the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate can generate HPO 42-and C2O 42-groups after being combined by a frame, so that a layered three-dimensional structure is formed.
Preferably, the doping amount of the carbon nanotube conductive agent is 0.1-5% of the mass of the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate. The material is formed by doping a carbon nano tube conductive agent into a metal organic phosphate framework material, and the MOF material has the characteristics of high specific surface area, high porosity, low density and the like, so that the material has excellent doping property, and the carbon nano tube conductive agent can be well doped in the material; the doping of the carbon nanotube conductive agent can obtain stronger conductivity, so that the composite material shows better sodium storage capacity than the original sample; and the doping of the carbon nano tube conductive agent can also be used as a buffer of volume change during potassium cycle, thereby bringing better energy storage; in addition, after the carbon nanotube conductive agent is ground, a small amount of carbon particles can be grafted with a porous structure of the MOF material to form a multilevel pore structure in the anode, so that more attachment sites are provided for particles such as VO2 generated by V3+ oxidation in the material and a carbon layer (similar to a shell), thereby promoting the transfer of electrons and ions and improving the stability of the whole structure. Therefore, after the material is coated by the carbon nano tube conductive agent, the conductivity of the material is enhanced, and the diffusion coefficient of the material is increased, so that the cycle and rate performance of the material as a sodium ion battery are improved.
Preferably, the particle size of the carbon nano tube conductive agent doped in the layered structure is 0.02-0.20 μm.
Preferably, the carbon nanotube conductive agent is acidified before use, and the specific method comprises the following steps: adding the carbon nano tube conductive agent into mixed acid, performing ultrasonic dispersion at normal temperature, cooling to room temperature, adding water for dilution, performing suction filtration by using a microporous filter membrane, washing, repeating the operations until the water washing solution is neutral, and finally performing vacuum drying to constant weight to obtain the acidified carbon nano tube conductive agent.
Preferably, the mixed acid is prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a molar ratio of 1-3: 1. The mass fraction of the concentrated sulfuric acid is 90-98%, and the mass fraction of the concentrated nitric acid is 60-68%.
Preferably, the mass-to-volume ratio (g/mL) of the carbon nanotube conductive agent to the mixed acid is 0.1-0.3: 100.
Preferably, the frequency of ultrasonic dispersion is 1000-6000 Hz, and the time is 2-3 h.
Preferably, the mass of the water for dilution is 2-4 times of the mass of the mixed acid.
Preferably, the pore size of the microporous filter membrane is 800-2000 meshes.
Preferably, the temperature of the vacuum drying is 80-100 ℃, and the vacuum degree is kept at 0.01-0.2 MPa.
The technical scheme adopted for further solving the technical problems is as follows: the preparation method of the potassium phosphate metal salt organic compound cathode material with vanadium as a substrate comprises the following steps:
(1) adding a vanadium-containing compound, a potassium source and a phosphorus source into water, stirring, and dispersing uniformly by adopting an ultrasonic method to obtain a mixed solution;
(2) placing the mixed solution obtained in the step (1) in a closed reaction kettle for hydrothermal reaction, filtering, washing the precipitate, and drying to obtain a K-organic framework structure material;
(3) and (3) mixing the K-organic framework structure material obtained in the step (2) with a carbon nano tube conductive agent, and grinding to obtain the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate.
The idea of the method is that firstly C2H2K2O14P2V2 (hereinafter referred to as K-organic framework structure) material is directionally synthesized, and then the carbon nano tube conductive agent is doped into the K-organic framework structure material by adopting an ex-situ mechanical doping method, so as to form the anode material with stronger conductivity.
Preferably, in the step (1), the molar volume ratio (mmol/mL) of the vanadium element in the vanadium-containing compound to water is 0.2-1.0: 1. If the concentration of vanadium is too high or too low, a stable and pure MOPOF material is difficult to form.
Preferably, in the step (1), the vanadium-containing compound is vanadium dioxide and/or vanadium pentoxide, etc.
Preferably, in the step (1), the stirring and dispersing speed is 100-400 r/min, more preferably 110-250 r/min, and the stirring and dispersing time is 5-30 min, more preferably 7-20 min.
Preferably, in the step (1), the molar ratio of the phosphorus element in the phosphorus source to the vanadium element in the vanadium-containing compound is 0.5-5: 1. The phosphorus source used in the method of the invention is used as a reactant and also has the function of adjusting the pH value, and the performance of the K-organic framework structure material prepared under the molar ratio is optimal.
Preferably, in the step (1), the molar ratio of the potassium element in the potassium source to the vanadium element in the vanadium-containing compound is 0.1-4.0: 1, and more preferably 1-3: 1. If the content is not in the range, other side reactions may occur to contaminate the target product.
Preferably, in step (1), the potassium source is one or more of potassium oxalate monohydrate, anhydrous potassium oxalate, potassium trioxalate ferrate, and potassium oxalate cuprate.
Preferably, in the step (1), the power of the ultrasound is 100-600W, more preferably 200-500W, and the time of the ultrasound is 1-100 min, more preferably 5-50 min.
Preferably, in the step (2), the volume of the mixed solution accounts for 20-70% of the volume of the closed reaction kettle, and more preferably 25-40%.
Preferably, in the step (2), the temperature of the hydrothermal reaction is 90-180 ℃, more preferably 95-160 ℃, still more preferably 100-140 ℃, the time of the hydrothermal reaction is 24-80 hours, more preferably 36-72 hours, and the pressure is 5MPa-15 MPa. The oxalate is connected with phosphate and vanadate to form a layered structure material, and finally a metal organic phosphate framework Material (MOPOF) is formed, the material is a multi-dimensional space structure hybrid material formed by cross-linking simple organic ligands by transition metal phosphate, and various alkali metal (such as Li + and K +) ions can be correspondingly encapsulated between layers in the structure. At said temperature and time, the growth of the material is more favored.
Preferably, in the step (2), the washing refers to the sequential cross washing by deionized water and ethanol, and the washing times are more than or equal to 3 times. The purpose of washing is to wash the residual reactants clean.
Preferably, in the step (2), the drying temperature is 180-220 ℃, and the drying time is 8-18 h.
Preferably, in the step (3), the amount of the carbon nanotube conductive agent is 2 to 20% (more preferably 5 to 15%) of the mass of the K-organic framework structure material.
Preferably, in the step (3), the grinding time is 20-60 min, and more preferably 25-40 min.
The invention has the following beneficial effects:
(1) the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate is assembled into a potassium ion battery, the first discharge gram capacity can reach 70.9mAh/g under the current density of 0.1C (12.5mA/g) within the voltage range of 2.5-4.5V, the coulombic efficiency is stable, after 100 times of circulation, the discharge gram capacity can reach 51.3mAh/g, and the discharge gram capacity retention rate can reach 72.4%; the battery assembled by the potassium phosphate metal salt organic compound cathode material taking vanadium as the substrate has better discharge capacity and excellent cycle stability;
(2) the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate is assembled into a potassium ion battery, the first discharge gram capacity can reach 70.9mAh/g in the voltage range of 2.5-4.5V and under the current density of 0.1C, and the coulombic efficiency is stable; under the current density of 0.3C, the discharge gram capacity can reach 51.7 mAh/g; under the current density of 0.5C, the discharge gram capacity can reach 34.3 mAh/g; under the current density of 1C, the discharge gram capacity can reach 8.1mAh/g, which shows that the battery assembled by the potassium phosphate metal salt organic compound cathode material taking vanadium as the substrate has better rate capability;
(3) the method does not need preparation and sintering of precursors, has low synthesis temperature, simple operation, low cost, strong controllability and good repeatability, and is suitable for industrial production;
(4) the cathode material disclosed by the invention is novel in structure, can provide ideas and develop thinking for future research on the metal organic phosphate framework material, and has remarkable scientific research value.
Drawings
FIG. 1 is an XRD pattern of a vanadium-based potassium phosphate metal salt organic compound positive electrode material according to example 1 of the present invention;
FIG. 2 is an IR diagram of a potassium phosphate metal salt organic compound positive electrode material based on vanadium according to example 1 of the present invention;
FIG. 3 is an SEM image of a vanadium-based potassium phosphate metal salt organic compound positive electrode material in example 1 of the present invention;
FIG. 4 is a TEM image of a vanadium-based potassium phosphate metal salt organic compound positive electrode material of example 1 of the present invention;
FIG. 5 is a graph showing discharge cycle characteristics of potassium phosphate metal salt organic compound cathode material based on vanadium of example 1 of the present invention and K-organic framework structure material obtained in comparative example 1;
FIG. 6 is a graph showing discharge rate characteristics of potassium phosphate metal salt organic compound cathode material based on vanadium of example 1 of the present invention and K-organic frame structure material obtained in comparative example 1.
Detailed Description
The invention is further illustrated by the following examples and figures.
The mass fraction of the phosphoric acid used in the embodiment of the invention is 85%, and the density is 1.874 g/mL; the carbon nanotubes and the conductive carbon black used in the reference examples or the examples of the present invention are available from Aladdin; the mass fraction of the concentrated sulfuric acid used in the reference example of the invention is 98%, and the mass fraction of the concentrated nitric acid is 68%; the chemicals used in the reference examples or examples of the present invention are commercially available in a conventional manner unless otherwise specified.
Reference example 1
The carbon nano tube used in the embodiment of the invention is firstly acidized before use, and the specific method comprises the following steps: adding 0.2g of carbon nano tube into 100mL (mixed by concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3: 1) of mixed acid, performing ultrasonic dispersion for 4 hours at normal temperature under 300W, cooling to room temperature, adding 400mL of water for dilution, performing suction filtration by using a microfiltration membrane with the aperture of 0.45 mu m, washing, repeating the operations until the washing solution is neutral, and finally performing vacuum drying at 90 ℃ to constant weight to obtain the acidified carbon nano tube.
Vanadium-based potassium phosphate metal salt organic compound positive electrode material example 1
The potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate is a layered material formed by doping acidified carbon nano tubes in a metal organic phosphate framework potassium ion cathode material; the single crystal molecular formula of the metal organic phosphate framework potassium ion cathode material is as follows: C2H10K2O16P2V2, wherein the molecular structure belongs to a monoclinic system structure of which the space group is a chiral noncentral space group; the size of the single crystal molecular crystal grain is 2.1 mu m; the potassium phosphate metal salt organic compound positive electrode material taking vanadium as a substrate is of a layered structure, and the width of the layered structure is 0.1-3 mu m; the doping amount of the acidified carbon nano tube is 5% of the mass of the metal organic phosphate framework potassium ion anode material.
As shown in fig. 1, the potassium phosphate organic compound cathode material based on vanadium in the embodiment of the present invention belongs to a monoclinic system structure with a space group as a chiral noncentral space group, and is a C2H10K2O16P2V2 pure phase.
As shown in FIG. 2, in the potassium phosphate metal salt organic compound cathode material based on vanadium of the embodiment of the present invention, characteristic peaks associated with V ═ O and V-O bonds appear at 993cm-1 and 482cm-1, while characteristic peaks appearing at 1118cm-1, 1074cm-1 and 1031cm-1 are antisymmetric stretching vibration modes of HPO 42-; the antisymmetric and symmetric C ═ O stretching vibration bands of the oxalate group (C2O42-) appear at 1675cm-1 and 1357cm-1, indicating the chelating bidentate bridged coordination pattern of the oxalate ligand.
As shown in FIG. 3, the potassium phosphate metal salt organic compound cathode material using vanadium as a substrate in the embodiment of the invention has a layered structure as a whole, and the width of the layered structure is 0.1-5 μm.
As shown in fig. 4, in the embodiment of the present invention, carbon nanotubes are doped and coated in the layered structure of the potassium phosphate organic compound cathode material using vanadium as a substrate.
Preparation method of vanadium-based potassium phosphate metal salt organic compound positive electrode material example 1
(1) Adding 59.0mg of vanadium pentoxide (0.324mmol) into 10mL of deionized water, stirring and dispersing for 15min at a stirring speed of 120r/min, then adding 0.4mL of phosphoric acid (6.87mmol) and 140.0mg of potassium oxalate monohydrate (0.760mmol), stirring, and performing ultrasonic treatment at 300W for 10min until uniform dispersion is achieved, thus obtaining 15mL of mixed solution;
(2) placing 15mL of mixed solution obtained in the step (1) in a 50mL closed reaction kettle, carrying out hydrothermal reaction for 72h at 120 ℃, filtering, using deionized water and ethanol to sequentially and alternately wash and precipitate for 3 times, and drying for 12h at 180 ℃ to obtain 3.88g of a K-organic framework structure material;
(3) and (3) mixing the 0.03g K-organic framework structure material obtained in the step (2) with 0.0015g of acidified carbon nano tubes, and grinding for 30min by using an agate mortar to obtain the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate.
Assembling the battery: 0.03g of potassium phosphate metal salt organic compound anode material taking vanadium as a substrate in the embodiment is respectively weighed as an anode material, 0.0125g of acetylene black (SP) as a conductive agent and 0.0075g of PVDF (HSV-900) as a binder are added into the anode material after being fully ground, 2mL of MP is added for dispersion and mixing, after uniform size mixing, the anode material is prepared by pulling slurry on an aluminum foil with the thickness of 16 mu m, and a button cell of CR2025 is assembled by taking a metal sodium sheet as a cathode, taking a glass fiber Whatman GF/D pcs model as a diaphragm and 1mol/L of sodium phosphate as electrolyte. And testing the constant current charge and discharge performance of the assembled sodium ion battery under the voltage range of 2.5-4.5V.
As shown in fig. 5, the assembled sodium ion battery has a reversible specific capacity of 70.9mAh/g for the first discharge within a voltage range of 2.5-4.5V and a current density of 0.1C, and the reversible specific capacity of the discharge is still maintained at 51.3mAh/g after 100 cycles, with a capacity retention rate of 72.4%.
As shown in fig. 6, the first discharge gram capacity of the assembled sodium-ion battery can reach 58.7mAh/g in the voltage range of 2.5-4.5V and under the current density of 0.1C, and the coulomb efficiency is stable; under the current density of 0.1C, the discharge gram capacity can reach 51.7 mAh/g; under the current density of 0.3C, the discharge gram capacity can reach 34.3 mAh/g; under the current density of 0.5C, the discharge gram capacity can reach 20.6 mAh/g; under the current density of 1C, the discharge gram capacity can reach 17.7mAh/g, which shows that the battery assembled by the potassium phosphate metal salt organic compound cathode material taking vanadium as the substrate has better rate capability.
From the above, the battery assembled by the potassium phosphate metal salt organic compound cathode material with vanadium as the substrate obtained in the embodiment of the invention has better specific discharge capacity, rate capability and excellent cycling stability.
Vanadium-based potassium phosphate metal salt organic compound positive electrode material example 2
The potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate is a layered material formed by doping acidified carbon nano tubes in a metal organic phosphate framework potassium ion cathode material; the single crystal molecular formula of the metal organic phosphate framework potassium ion cathode material is as follows: C2H10K2O16P2V2, wherein the molecular structure belongs to a monoclinic system structure of which the space group is a chiral noncentral space group; the grain size of the single crystal molecules is 1.5 mu m; the potassium phosphate metal salt organic compound positive electrode material taking vanadium as a substrate is of a layered structure, and the width of the layered structure is 3-4 microns; the doping amount of the acidified carbon nano tube is 8% of the mass of the metal organic phosphate framework potassium ion anode material.
Through detection, the potassium phosphate metal salt organic compound cathode material taking vanadium as the substrate in the embodiment of the invention belongs to a monoclinic system structure with a space group as a chiral noncentral space group, and is a C2H10K2O16P2V2 pure phase.
According to the detection result, V ═ O and V-O bonds and HPO 42-and C2O 42-groups exist in the potassium phosphate organic compound cathode material taking vanadium as a substrate in the embodiment of the invention, and the chelate bidentate bridging coordination mode of the oxalate ligand is shown.
According to the embodiment of the invention, the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate is integrally in a layered structure, and the width of the layered structure is 5-10 μm.
Through detection, the carbon nano tube is doped and wrapped in the layered structure of the potassium phosphate metal salt organic compound cathode material taking vanadium as the substrate in the embodiment of the invention.
Preparation method of vanadium-based potassium phosphate metal salt organic compound positive electrode material example 2
(1) Adding 298.0mg of vanadium pentoxide (1.64mmol) into 10mL of deionized water, stirring and dispersing for 10min at a stirring speed of 110r/min, then adding 2.2mL of phosphoric acid (35.76mmol) and 413.48mg of potassium oxalate monohydrate (3.28mmol), stirring, and performing ultrasonic treatment at 350W for 30min until the mixture is uniformly dispersed to obtain 13mL of mixed solution;
(2) putting 13mL of mixed solution obtained in the step (1) into a 50mL closed reaction kettle, carrying out hydrothermal reaction for 54h at 100 ℃, filtering, cross-washing and precipitating with deionized water and ethanol for 3 times, and drying for 14h at 200 ℃ to obtain 22.21g of a K-organic framework structure material;
(3) and (3) mixing the 0.05g K-organic framework structure material obtained in the step (2) with 0.004g of acidified carbon nanotubes, and grinding for 35min by using an agate mortar to obtain the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate.
Assembling the battery: the same as in example 1. And testing the constant current charge and discharge performance of the assembled sodium ion battery under the voltage range of 2.5-4.5V.
Through detection, the first discharge reversible specific capacity of the assembled sodium-ion battery can reach 68.3mAh/g within the voltage range of 2.5-4.5V and under the current density of 0.1C, the discharge reversible specific capacity is still maintained at 50.2mAh/g after 100 cycles, and the capacity retention rate is 73.4%.
Through detection, the first discharge gram capacity of the assembled sodium-ion battery can reach 57.9mAh/g within the voltage range of 2.5-4.5V and under the current density of 0.1C, and the coulombic efficiency is stable; under the current density of 0.1C, the discharge gram capacity can reach 50.3 mAh/g; under the current density of 0.3C, the discharge gram capacity can reach 35.6 mAh/g; under the current density of 0.5C, the discharge gram capacity can reach 25.5 mAh/g; the battery assembled by the potassium phosphate metal salt organic compound cathode material taking vanadium as the substrate has better rate performance.
From the above, the battery assembled by the potassium phosphate metal salt organic compound cathode material with vanadium as the substrate obtained in the embodiment of the invention has better specific discharge capacity, rate capability and excellent cycling stability.
Vanadium-based potassium phosphate metal salt organic compound positive electrode material example 3
The potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate is a layered material formed by doping acidified carbon nano tubes in a metal organic phosphate framework potassium ion cathode material; the single crystal molecular formula of the metal organic phosphate framework potassium ion cathode material is as follows: C2H10K2O16P2V2, wherein the molecular structure belongs to a monoclinic system structure of which the space group is a chiral noncentral space group; the grain size of the single crystal molecules is 2.0 μm; the potassium phosphate metal salt organic compound positive electrode material taking vanadium as a substrate is of a layered structure, and the width of the layered structure is 0.5-3.5 micrometers; the doping amount of the acidified carbon nano tube is 10% of the mass of the metal organic phosphate framework potassium ion anode material.
Through detection, the potassium phosphate metal salt organic compound cathode material taking vanadium as the substrate in the embodiment of the invention belongs to a monoclinic system structure with a space group as a chiral noncentral space group, and is a C2H10K2O16P2V2 pure phase.
According to the detection result, V-O and V-O bonds and HPO 42-and C2O 42-groups exist in the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate in the embodiment of the invention, and the bidentate chelate coordination mode of the oxalate ligand is shown.
According to the embodiment of the invention, the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate is integrally in a layered structure, and the width of the layered structure is 5-15 μm.
Through detection, the carbon nano tube is doped and wrapped in the layered structure of the potassium phosphate metal salt organic compound cathode material taking vanadium as the substrate in the embodiment of the invention.
Preparation method of vanadium-based potassium phosphate metal salt organic compound positive electrode material example 3
(1) Adding 447.0mg of vanadium pentoxide (2.46mmol) into 10mL of deionized water, stirring and dispersing for 20min at a stirring speed of 200r/min, then adding 3.3mL of phosphoric acid (53.64mmol) and 1240.4mg of potassium oxalate monohydrate (9.84 mmol), stirring, and performing ultrasonic treatment at 250W for 20min until the mixture is uniformly dispersed to obtain 14mL of mixed solution;
(2) placing 14mL of mixed solution obtained in the step (1) in a 50mL closed reaction kettle, carrying out hydrothermal reaction for 66h at 110 ℃, filtering, cross-washing the precipitate for 3 times by using deionized water and ethanol, and drying for 16h at 195 ℃ to obtain 24.03g of a K-organic framework structure material;
(3) and (3) mixing the 0.1g K-organic framework structure material obtained in the step (2) with 0.01g of acidified carbon nano tubes, and grinding for 25min by using an agate mortar to obtain the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate.
Assembling the battery: the same as in example 1. And testing the constant current charge and discharge performance of the assembled sodium ion battery under the voltage range of 2.5-4.5V.
Through detection, the first discharge reversible specific capacity of the assembled sodium-ion battery can reach 68.3mAh/g within the voltage range of 2.5-4.5V and under the current density of 0.1C, the discharge reversible specific capacity is still maintained at 48.0mAh/g after 100 cycles, and the capacity retention rate is 70.3%.
Through detection, the first discharge gram capacity of the assembled sodium-ion battery can reach 57.4mAh/g within the voltage range of 2.5-4.5V and under the current density of 0.1C, and the coulombic efficiency is stable; under the current density of 0.1C, the discharge gram capacity can reach 49.6 mAh/g; under the current density of 0.3C, the discharge gram capacity can reach 33.5 mAh/g; under the current density of 0.5C, the discharge gram capacity can reach 19.8 mAh/g; the battery assembled by the potassium phosphate metal salt organic compound cathode material taking vanadium as the substrate has better rate performance.
From the above, the battery assembled by the potassium phosphate metal salt organic compound cathode material with vanadium as the substrate obtained in the embodiment of the invention has better specific discharge capacity, rate capability and excellent cycling stability.
Vanadium-based potassium phosphate metal salt organic compound positive electrode material example 4
The potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate is a layered material formed by doping acidified carbon nano tubes in a metal organic phosphate framework potassium ion cathode material; the single crystal molecular formula of the metal organic phosphate framework potassium ion cathode material is as follows: C2H10K2O16P2V2, wherein the molecular structure belongs to a monoclinic system structure of which the space group is a chiral noncentral space group; the grain size of the single crystal molecules is 1.9 μm; the potassium phosphate metal salt organic compound positive electrode material taking vanadium as a substrate is of a layered structure, and the width of the layered structure is 1-10 micrometers; the doping amount of the acidified conductive carbon black is 8% of the mass of the metal organic phosphate framework potassium ion cathode material.
Through detection, the potassium phosphate metal salt organic compound cathode material taking vanadium as the substrate in the embodiment of the invention belongs to a monoclinic system structure with a space group as a chiral noncentral space group, and is a C2H10K2O16P2V2 pure phase.
According to the detection result, V ═ O and V-O bonds and HPO 42-and C2O 42-groups exist in the potassium phosphate organic compound cathode material taking vanadium as a substrate in the embodiment of the invention, and the chelate bidentate bridging coordination mode of the oxalate ligand is shown.
According to the embodiment of the invention, the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate is integrally in a layered structure, and the width of the layered structure is 0.1-5 μm.
Through detection, the carbon nano tube is doped and wrapped in the layered structure of the potassium phosphate metal salt organic compound cathode material taking vanadium as the substrate in the embodiment of the invention.
Preparation method of vanadium-based potassium phosphate metal salt organic compound positive electrode material example 4
(1) Adding 610.4mg of vanadium dioxide (7.36mmol) into 10mL of deionized water, stirring and dispersing for 7min at the stirring speed of 150r/min, then adding 5.38mL of phosphoric acid (87.45mmol) and 1391.7mg of potassium oxalate monohydrate (11.04 mmol), stirring, and performing ultrasonic treatment at 500W for 5min until the mixture is uniformly dispersed to obtain 16mL of mixed solution;
(2) placing 16mL of mixed solution obtained in the step (1) in a 50mL closed reaction kettle, carrying out hydrothermal reaction for 48h at 105 ℃, filtering, using deionized water and ethanol to sequentially and alternately wash and precipitate for 4 times, and drying for 18h at 210 ℃ to obtain 23.89g of a K-organic framework structure material;
(3) and (3) mixing the 0.06g K-organic framework structure material obtained in the step (2) with 0.0048g of acidified carbon nano tubes, and grinding for 40min by using an agate mortar to obtain the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate.
Assembling the battery: the same as in example 1. And testing the constant current charge and discharge performance of the assembled sodium ion battery under the voltage range of 2.5-4.5V.
Through detection, the first discharge reversible specific capacity of the assembled sodium-ion battery can reach 66.8mAh/g within the voltage range of 2.5-4.5V and the current density of 0.1C, the discharge reversible specific capacity is still maintained at 50.5mAh/g after 100 cycles, and the capacity retention rate is 75.6%.
Through detection, the first discharge gram capacity of the assembled sodium-ion battery can reach 58.1mAh/g within the voltage range of 2.5-4.5V and under the current density of 0.1C, and the coulomb efficiency is stable; under the current density of 0.1C, the discharge gram capacity can reach 51.1 mAh/g; under the current density of 0.3C, the discharge gram capacity can reach 33.2 mAh/g; under the current density of 0.5C, the discharge gram capacity can reach 26.3 mAh/g; the battery assembled by the potassium phosphate metal salt organic compound cathode material taking vanadium as the substrate has better rate performance.
From the above, the battery assembled by the potassium phosphate metal salt organic compound cathode material with vanadium as the substrate obtained in the embodiment of the invention has better specific discharge capacity, rate capability and excellent cycling stability.
Comparative example 1
Comparative example 1 differs from example 1 only in that: and (4) removing the step (3) to obtain the K-organic framework structure material.
Assembling the battery: the same as in example 1. And testing the constant current charge and discharge performance of the assembled sodium ion battery under the voltage range of 2.5-4.5V.
As shown in fig. 6, the initial discharge reversible specific capacity of the assembled sodium-ion battery is 23.7mAh/g in the voltage range of 2.5 to 4.5V and at the current density of 0.1C, and after 100 cycles, the discharge reversible specific capacity is only 13.1mAh/g, and the capacity retention rate is only 55.2%, which indicates that the cycle performance is poor.
From the above, the addition of the carbon nanotube can effectively improve the cycle and rate performance of the cathode material.

Claims (10)

1. The vanadium-based potassium phosphate metal salt organic compound cathode material is characterized in that the cathode material is prepared by doping a carbon nano tube conductive agent into a K-organic framework structure material, wherein the K-organic framework structure material is a single crystal material and has a molecular formula of C2H10K2O16P2V2Belongs to a monoclinic structure.
2. The vanadium-based potassium phosphate metal salt organic compound positive electrode material according to claim 1, characterized in that: the grain size of the single crystal molecules is 0.1-5 mu m; the potassium phosphate metal salt organic compound positive electrode material taking vanadium as a substrate is of a layered structure, and the width of the layered structure is 0.1-5 microns.
3. The vanadium-based potassium phosphate metal salt organic compound positive electrode material according to claim 2, characterized in that: the doping amount of the carbon nano tube conductive agent is 0.1-5% of the mass of the anode material; the carbon nano tube conductive agent is subjected to acidification treatment before use, and the specific method comprises the following steps: adding a carbon nano tube conductive agent into mixed acid, performing ultrasonic dispersion at normal temperature, cooling to room temperature, adding water for dilution, performing suction filtration by using a microporous filter membrane, washing, repeating the operations until a water washing solution is neutral, and finally performing vacuum drying to constant weight to obtain an acidified carbon nano tube conductive agent; the mixed acid is formed by mixing concentrated sulfuric acid and concentrated nitric acid in a molar ratio of 1-3: 1; the mass volume ratio of the carbon nano tube conductive agent to the mixed acid is 0.1-0.3: 100; the frequency of the ultrasonic dispersion is 1000-6000 Hz, and the time is 2-3 h; the mass of the water for dilution is 2-4 times of the mass of the mixed acid; the pore diameter of the microporous filter membrane is 800-2000 meshes; the temperature of the vacuum drying is 80-100 ℃, and the vacuum degree is kept at 0.01-0.2 MPa.
4. A method for preparing a vanadium-based potassium phosphate metal salt organic compound cathode material according to any one of claims 1 to 3, comprising the steps of:
(1) adding a vanadium-containing compound, a potassium source and a phosphorus source into water, stirring, and dispersing uniformly by adopting an ultrasonic method to obtain a mixed solution;
(2) carrying out hydrothermal reaction on the mixed solution obtained in the step (1), filtering, washing the precipitate, and drying to obtain a K-organic framework structure material;
(3) and (3) mixing the K-organic framework structure material obtained in the step (2) with a carbon nano tube conductive agent, and grinding to obtain the potassium phosphate metal salt organic compound cathode material taking vanadium as a substrate.
5. The method for preparing a vanadium-based potassium phosphate metal salt organic compound positive electrode material according to claim 4, wherein: in the step (1), the molar volume ratio of the vanadium element in the vanadium-containing compound to water is 0.2-1.0: 1; the vanadium-containing compound is vanadium dioxide and/or vanadium pentoxide; the stirring and dispersing speed is 100-400 r/min, and the stirring and dispersing time is 5-30 min.
6. The method for preparing a vanadium-based potassium phosphate metal salt organic compound positive electrode material according to claim 4 or 5, wherein: in the step (1), the molar ratio of phosphorus in the phosphorus source to vanadium in the vanadium-containing compound is 0.5-5: 1, and the phosphorus source is one or more of phosphoric acid, metaphosphoric acid and pyrophosphoric acid; the molar ratio of potassium element in the potassium source to vanadium element in the vanadium-containing compound is 0.1-4.0: 1; the potassium source is one or more of potassium oxalate monohydrate, anhydrous potassium oxalate, potassium tris oxalate ferrate and potassium bis oxalate cuprate.
7. The method for preparing a vanadium-based potassium phosphate metal salt organic compound positive electrode material according to claim 4, wherein: in the step (1), the power of the ultrasound is 100-600W, and the time of the ultrasound is 10-100 min.
8. The method for preparing a vanadium-based potassium phosphate metal salt organic compound positive electrode material according to claim 4, wherein: in the step (2), the volume of the mixed solution accounts for 20-70% of the volume of the closed reaction kettle; the temperature of the hydrothermal reaction is 90-180 ℃, the time of the hydrothermal reaction is 24-80 h, and the pressure is 5-15 MPa.
9. The method for preparing a vanadium-based potassium phosphate metal salt organic compound positive electrode material according to claim 4, wherein: in the step (2), the washing refers to that deionized water and ethanol are used for washing in sequence in a crossed manner, and the washing times are more than or equal to 3 times; the drying temperature is 180-220 ℃, and the drying time is 8-18 h.
10. The method for preparing a vanadium-based potassium phosphate metal salt organic compound positive electrode material according to claim 4, wherein: in the step (3), the amount of the carbon nano tube is 2-20% of the mass of the K-organic framework structure material; the grinding time is 20-60 min.
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