CN109546117B - Layered metal organic phosphate framework sodium ion positive electrode material and preparation method thereof - Google Patents

Layered metal organic phosphate framework sodium ion positive electrode material and preparation method thereof Download PDF

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CN109546117B
CN109546117B CN201811377465.3A CN201811377465A CN109546117B CN 109546117 B CN109546117 B CN 109546117B CN 201811377465 A CN201811377465 A CN 201811377465A CN 109546117 B CN109546117 B CN 109546117B
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sodium
metal organic
organic phosphate
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electrode material
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CN109546117A (en
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郑俊超
林可博
范鑫铭
刘洋
贺振江
童汇
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Jiangxi Chaoshi New Energy Technology Co ltd
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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
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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
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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
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Abstract

The anode material is a layered material formed by doping a carbon conductive agent in a metal organic phosphate framework sodium ion anode material; the single crystal molecular formula of the metal organic phosphate framework sodium ion anode material is as follows: c2H10Na2O16P2V2The molecular structure belongs to a monoclinic system structure with a space group being a chiral noncentral space group. The method comprises the following steps: (1) adding a vanadium source into water, dispersing, then adding phosphoric acid and oxalic acid dihydrate, stirring, adding a sodium source, and uniformly dispersing; (2) carrying out hydrothermal reaction, filtering, washing the precipitate, and drying to obtain a Na-MOF material; (3) mixing with carbon 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

Layered metal organic phosphate framework sodium ion positive electrode material and preparation method thereof
Technical Field
The invention relates to a sodium ion anode material and a preparation method thereof, in particular to a layered metal organic phosphate framework sodium ion anode material 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 Na without adhesive3V2(PO4)3A/C composite sodium-ion battery positive electrode and a preparation method thereof are characterized in that a sodium source and a vanadium source are subjected to hydrothermal reaction, a phosphorus source and an organic carbon source are weighed and put into a beaker, deionized water is added, the mixture is stirred for 20min until the phosphorus source and the organic carbon source are completely dissolved, then a 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. Then soaking the carbon matrix in the liquid phase precursor, drying, presintering and calcining at high temperature to obtain the binder-free Na3V2(PO4)3an/C electrode which improves the air storage, high temperature storage and cycling 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, a sodium 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 layered metal organic phosphate framework sodium ion positive electrode material which has high discharge capacity, better rate capability, stable cycle performance and coulombic efficiency.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide the preparation method of the layered metal organic phosphate framework sodium ion 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.
The technical scheme adopted by the invention for solving the technical problems is as follows: the layered metal organic phosphate frame sodium ion anode material is formed by doping a carbon conductive agent in a metal organic phosphate frame sodium ion anode materialA layered material; the single crystal molecular formula of the metal organic phosphate framework sodium ion anode material is as follows: c2H10Na2O16P2V2The molecular structure belongs to a monoclinic system structure with a space group being a chiral noncentral space group. Novel organic materials and metal organic framework Materials (MOFs) show potential application prospects as sodium-ion battery electrode materials, but the biggest obstacles of the existing MOF materials as commercial sodium-ion battery materials are as follows: difficult mass production and isolation of the redox metal center from the framework. The layered metal organic phosphate framework sodium ion positive electrode material is a special MOF material, and is a multi-dimensional space structure hybrid material formed by cross-linking simple organic ligands by transition metal phosphate, and various alkali metals such as Li can be correspondingly encapsulated between layers by the structure+、Na+And K+The advantages of ions over other MOFs are: 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 unit cell volume of the single crystal molecule is 620-720 Å3The grain size is 110-140 nm, and the crystallinity is 85-100%.
Preferably, the layered metal organic phosphate framework sodium ion positive electrode material is in a layered nanosheet structure, and the width of the nanosheet is 1-20 μm. The layered metal organic phosphate framework sodium ion positive electrode material can generate HPO after being combined by the framework4 2-、C2O4 2-And (c) a group, thereby forming a layered three-dimensional structure.
Preferably, the doping amount of the carbon conductive agent is 2-20% (more preferably 5-15%) of the mass of the metal organic phosphate framework sodium ion positive electrode material. The material of the invention is formed by doping a carbon conductive agent into a metal organic phosphate framework material, and the MOF materialThe material has the characteristics of high specific surface area, high porosity, low density and the like, so that the material has excellent adsorbability, and the carbon conductive agent can be well adsorbed in the material; the doping of the carbon 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 conductive agent can also be used as a buffer for volume change during sodium cycle, thereby bringing better energy storage; in addition, after the carbon conductive agent is ground, a small amount of carbon particles can be grafted with the porous structure of the MOF material to form a multistage pore structure in the anode, namely V in the material3+VO generated by oxidation2The layer of particles and carbon (similar to the shell) provides more attachment sites, thereby facilitating the transfer of electrons and ions and improving the stability of the overall structure. Therefore, after the material is coated by the carbon 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 conductive agent doped in the nano sheet is 0.02-0.20 μm.
Preferably, the carbon conductive agent is one or more of carbon nanotubes, graphene, conductive carbon black and the like.
Preferably, the carbon conductive agent is acidified before use, and the specific method comprises the following steps: adding a carbon 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 conductive agent.
Preferably, the mixed acid is formed by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 2-4: 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 conductive agent to the mixed acid is 0.1-0.3: 100.
Preferably, the power of the ultrasonic dispersion is 100-600W, and the time is 3-5 h.
Preferably, the volume of water used for dilution is 3 to 5 times the volume of the mixed acid.
Preferably, the pore diameter of the microporous filter membrane is 0.4-0.5 μm.
Preferably, the temperature of the vacuum drying is 80-100 ℃.
The technical scheme adopted for further solving the technical problems is as follows: the preparation method of the layered metal organic phosphate framework sodium ion cathode material comprises the following steps:
(1) adding a vanadium source into water, stirring and dispersing, then adding phosphoric acid and oxalic acid dihydrate, stirring, adding a sodium source, and carrying out ultrasonic treatment until the mixture is uniformly dispersed to obtain a mixed solution A;
(2) placing the mixed solution A obtained in the step (1) in a closed reaction kettle for hydrothermal reaction, filtering, washing the precipitate, and drying to obtain a Na-MOF material;
(3) and (3) mixing the Na-MOF material obtained in the step (2) with a carbon conductive agent, and grinding to obtain the layered metal organic phosphate framework sodium ion positive electrode material.
The idea of the method is to firstly synthesize C in a directional way2H2Na2O14P2V2(Na-MOF) material, and then a carbon conductive agent is doped into the Na-MOF material by adopting an ex-situ mechanical doping method, thereby forming the sodium ion positive electrode material with stronger electric conductivity.
Preferably, in the step (1), the molar volume ratio (mmol/mL) of the vanadium element in the vanadium source to the 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 source is vanadium dioxide and/or vanadium pentoxide, etc.
Preferably, in the step (1), the mass fraction of the phosphoric acid is 83-98%.
Preferably, in the step (1), the stirring and dispersing speed is 100 to 400r/min (more preferably 110 to 250 r/min), and the stirring and dispersing time is 5 to 30min (more preferably 7 to 20 min).
Preferably, in the step (1), the molar ratio of the phosphoric acid, the oxalic acid dihydrate and the vanadium element in the vanadium source is 5-50: 0.5-5.0: 1 (more preferably 10-15: 1-2: 1). The phosphoric acid used in the method of the invention has the function of adjusting the pH value besides serving as a reactant, and the NA-MOF prepared at the molar ratio has the optimal performance.
Preferably, in the step (1), the molar ratio of the sodium element in the sodium source to the vanadium element in the vanadium source is 0.1-4.0: 1 (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 the step (1), the sodium source is one or more of sodium hydroxide, sodium bicarbonate or sodium chloride.
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 a accounts for 20-70% (more preferably 25-40%) of the volume of the closed reaction kettle.
Preferably, in the step (2), the temperature of the hydrothermal reaction is 90 to 180 ℃ (more preferably 95 to 160 ℃, and still more preferably 100 to 140 ℃), and the time of the hydrothermal reaction is 24 to 80 hours (more preferably 36 to 72 hours). The oxalate connects phosphate radical and vanadate radical to form a layered structure material, and finally a metal organic phosphate framework Material (MOPOF) is formed, which is a multi-dimensional space structure hybrid material formed by cross-linking simple organic ligands by transition metal phosphate, and the structure can correspondingly encapsulate various alkali metals (such as Li) between layers+、Na+And K+) Ions. 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 conductive agent is 2-20% (more preferably 5-15%) of the mass of the Na-MOF material.
Preferably, in the step (3), the grinding time is 20-60 min (more preferably 25-40 min).
The invention has the following beneficial effects:
(1) the layered metal organic phosphate framework sodium ion positive electrode material is assembled into a sodium ion battery, the first discharge gram capacity can reach 63.1mAh/g under the current density of 0.1C (11.6 mA/g) within the voltage range of 2.5-4.5V, the coulombic efficiency is stable, after 30 times of circulation, the discharge gram capacity can reach 60.6mAh/g, and the discharge gram capacity retention rate can reach 98.1%; the battery assembled by the layered metal organic phosphate framework sodium ion positive electrode material has better discharge capacity and excellent cycle stability;
(2) the layered metal organic phosphate framework sodium ion positive electrode material is assembled into a sodium ion battery, the first discharge gram capacity can reach 62.2mAh/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 0.3C, the discharge gram capacity can reach 52.0 mAh/g; under the current density of 0.5C, the discharge gram capacity can reach 48.5 mAh/g; under the current density of 1C, the discharge gram capacity can reach 42.1 mAh/g; under the current density of 2C, the discharge gram capacity can reach 36.0mAh/g, which shows that the battery assembled by the layered metal organic phosphate framework sodium ion positive electrode material 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 a schematic structural diagram of a layered metallo-organic phosphate framework sodium ion positive electrode material according to example 1 of the present invention;
FIG. 2 is an XRD fine-modification diagram of the layered metal organic phosphate framework sodium ion cathode material in example 1 of the present invention;
FIG. 3 is an IR diagram of a layered metallo-organophosphate framework sodium ion positive electrode material of example 1 of the present invention;
FIG. 4 is an SEM image of a layered metallo-organic phosphate framework sodium ion positive electrode material of example 1 of the present invention;
FIG. 5 is a TEM image of a layered metallo-organic phosphate framework sodium ion positive electrode material of example 1 of the present invention;
FIG. 6 is a graph of discharge cycle performance of the layered metallo-organophosphate framework sodium ion positive electrode material of example 1 of the present invention and the Na-MOF material obtained in comparative example 1;
FIG. 7 is a graph showing discharge rate performance of the layered metallo-organophosphate framework sodium ion positive electrode material of example 1 of the present invention and the Na-MOF 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 conductive agents, namely carbon nanotubes, graphene and conductive carbon black, used in the reference examples or the examples of the invention are all purchased from the company 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 conductive agent used in the embodiment of the invention is acidized before use, and the specific method comprises the following steps: adding 0.2g of carbon conductive agent 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 water washing solution is neutral, and finally performing vacuum drying at 90 ℃ to constant weight to obtain the acidified carbon conductive agent.
Layered metallo-organophosphate framework sodium ion positive electrode material example 1
The layered metallo-organic phosphateThe framework sodium ion positive electrode material is a layered material formed by doping acidified carbon nano tubes in a metal organic phosphate framework sodium ion positive electrode material; the single crystal molecular formula of the metal organic phosphate framework sodium ion anode material is as follows: c2H10Na2O16P2V2The molecular structure belongs to a monoclinic system structure with a space group being a chiral noncentral space group, and the unit cell volume of the single crystal molecule is 683.94982 Å3The grain size is 131.6 nm, and the crystallinity is 87.17%; the layered metal organic phosphate framework sodium ion positive electrode material is of a layered nanosheet structure, and the width of the nanosheet is 1-5 microns; the doping amount of the acidified carbon nano tube is 5% of the mass of the metal organic phosphate framework sodium ion anode material; the particle size of the acidified carbon nano tube doped in the nano sheet is 0.02-0.10 mu m. The structural schematic diagram of the layered metal organic phosphate framework sodium ion cathode material is shown in figure 1.
As shown in FIG. 2, the layered metal organic phosphate framework sodium ion positive electrode material of the embodiment of the invention belongs to a monoclinic system structure with a space group of a chiral noncentral space group and is C2H10Na2O16P2V2Pure phase, detailed assay data are shown in table 1.
Table 1 crystal data and structure information table of layered metal organic phosphate framework sodium ion positive electrode material in example 1
Figure 171429DEST_PATH_IMAGE001
As shown in FIG. 3, in the layered metal organic phosphate framework sodium ion cathode material of the embodiment of the invention, the characteristic peaks related to V = O and V-O bonds appear at 973 cm-1And 484 cm-1And appears at 1093 cm-1、1041 cm-1And 1070cm-1The characteristic peak of (A) is HPO4 2-The antisymmetric tensile vibration mode of (a); oxalate group (C)2O4 2-) The antisymmetric and symmetric C = O stretching vibration band appears at 1689 cm-1And 1365cm-1Indicating the chelation of the oxalate ligandBidentate bridging coordination mode.
As shown in FIG. 4, the layered metal organic phosphate framework sodium ion cathode material in the embodiment of the invention is of a layered nanosheet structure as a whole, and the width of the nanosheet is 1-5 μm.
As shown in FIG. 5, carbon particles formed by grinding carbon nanotubes are doped and coated in nanosheets of the layered metal organic phosphate framework sodium ion positive electrode material in the embodiment of the invention, and the particle size is 0.02-0.10 μm.
Preparation method of layered metal organic phosphate framework sodium ion cathode material example 1
(1) Adding 595.9mg of vanadium pentoxide (3.27 mmol) into 10mL of deionized water, stirring and dispersing for 15min at a stirring speed of 120 r/min, then adding 4.1mL of phosphoric acid (66.64 mmol) and 824.1mg of oxalic acid dihydrate (6.54 mmol), stirring, adding 524.6 mg of sodium hydroxide (13.1 mmol), and carrying out ultrasonic treatment for 10min at 300W until the mixture is uniformly dispersed to obtain 15mL of mixed solution A;
(2) placing 15mL of the mixed solution A 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 wash and precipitate in a cross manner for 3 times, and drying for 12h at 180 ℃ to obtain 23.6g of Na-MOF material;
(3) and (3) mixing 0.03g of Na-MOF 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 layered metal organic phosphate framework sodium ion positive electrode material.
Assembling the battery: 0.03g of the layered metal organic phosphate framework sodium ion positive electrode material of the embodiment is respectively weighed as a positive electrode 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 positive electrode material and fully ground, 2mL of NMP is added into the ground mixture to be dispersed and mixed, after uniform size mixing, the positive electrode piece is prepared by pulling pulp on an aluminum foil with the thickness of 16 mu m, and the button cell of CR2025 is assembled by taking a metal sodium piece as a negative electrode, a glass fiber Whatman GF/D pcs model as a diaphragm and 1mol/L of sodium phosphate as an 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. 6, the assembled sodium ion battery has a reversible specific capacity of 63.1mAh/g in 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 60.5 mAh/g after 30 cycles, with a capacity retention ratio of 95.9%.
As shown in fig. 7, 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 0.3C, the discharge gram capacity can reach 52.0 mAh/g; under the current density of 0.5C, the discharge gram capacity can reach 48.5 mAh/g; under the current density of 1C, the discharge gram capacity can reach 42.1 mAh/g; under the current density of 2C, the discharge gram capacity can still reach 36.0mAh/g, which shows that the battery assembled by the layered metal organic phosphate framework sodium ion positive electrode material has better rate capability.
From the above, the battery assembled by the layered metal organic phosphate framework sodium ion positive electrode material obtained in the embodiment of the invention has good specific discharge capacity, rate capability and excellent cycling stability.
Layered metallo-organophosphate framework sodium ion positive electrode material example 2
The layered metal organic phosphate framework sodium ion positive electrode material is a layered material formed by doping acidified carbon nano tubes in the metal organic phosphate framework sodium ion positive electrode material; the single crystal molecular formula of the metal organic phosphate framework sodium ion anode material is as follows: c2H10Na2O16P2V2The molecular structure belongs to a monoclinic system structure with a space group being a chiral noncentral space group, and the unit cell volume of the single crystal molecule is 685.6 Å3The grain size is 121.5nm, and the crystallinity is 95%; the layered metal organic phosphate framework sodium ion positive electrode material is of a layered nanosheet structure, and the width of the nanosheet is 5-10 microns; the doping amount of the acidified carbon nano tube is 8% of the mass of the metal organic phosphate framework sodium ion positive electrode material; the particle size of the acidified carbon nano tube doped in the nano sheet is 0.10-0.15 mu m.
Through detection, the layered metal organic phosphate framework sodium ion positive electrode of the embodiment of the inventionThe polar material belongs to a monoclinic system structure with a space group of chiral noncentral space group and is C2H10Na2O16P2V2Pure phase.
Through detection, V = O and V-O bonds and HPO exist in the layered metal organic phosphate framework sodium ion positive electrode material in the embodiment of the invention4 2-And C2O4 2-The group shows the chelating bidentate bridging coordination mode of the oxalate ligand.
Through detection, the whole layered metal organic phosphate framework sodium ion positive electrode material in the embodiment of the invention is in a layered nanosheet structure, and the width of the nanosheet is 5-10 μm.
Through detection, carbon particles formed by grinding carbon nanotubes and coated in nano sheets of the layered metal organic phosphate framework sodium ion positive electrode material are doped, and the particle size is 0.10-0.15 mu m.
Preparation method of layered metal organic phosphate framework sodium ion cathode material example 2
(1) Adding 298.0mg of vanadium pentoxide (1.64 mmol) into 10mL of deionized water, stirring and dispersing for 10min at a stirring speed of 110 r/min, then adding 2.2mL of phosphoric acid (35.76 mmol) and 413.48mg of oxalic acid dihydrate (3.28 mmol), stirring, then adding 262.3 mg of sodium hydroxide (6.56 mmol), and carrying out ultrasonic treatment for 30min at 350W until the solution is uniformly dispersed to obtain 13mL of mixed solution A;
(2) putting 13mL of the mixed solution A obtained in the step (1) into a 50mL closed reaction kettle, carrying out hydrothermal reaction for 54h at 100 ℃, filtering, using deionized water and ethanol to sequentially wash and precipitate in a cross manner for 3 times, and drying for 14h at 200 ℃ to obtain 22.21g of Na-MOF material;
(3) and (3) mixing 0.05g of Na-MOF material obtained in the step (2) with 0.004g of acidified carbon nano tubes, and grinding for 35min by using an agate mortar to obtain the layered metal organic phosphate framework sodium ion positive electrode 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.
Through detection, the first discharge reversible specific capacity of the assembled sodium-ion battery can reach 62.3mAh/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 60.6mAh/g after 30 cycles, and the capacity retention rate is 98.1%.
Through detection, the first discharge gram capacity of the assembled sodium-ion battery can reach 62.2mAh/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 0.3C, the discharge gram capacity can reach 49.6 mAh/g; under the current density of 0.5C, the discharge gram capacity can reach 47.3 mAh/g; under the current density of 1C, the discharge gram capacity can reach 40.1 mAh/g; under the current density of 2C, the specific discharge capacity can still reach 35.1mAh/g, which shows that the battery assembled by the layered metal organic phosphate framework sodium ion positive electrode material has better rate capability.
From the above, the battery assembled by the layered metal organic phosphate framework sodium ion positive electrode material obtained in the embodiment of the invention has good specific discharge capacity, rate capability and excellent cycling stability.
Layered metallo-organophosphate framework sodium ion positive electrode material example 3
The layered metal organic phosphate framework sodium ion positive electrode material is a layered material formed by doping acidified graphene in the metal organic phosphate framework sodium ion positive electrode material; the single crystal molecular formula of the metal organic phosphate framework sodium ion anode material is as follows: c2H10Na2O16P2V2The molecular structure belongs to a monoclinic system structure with a space group being a chiral noncentral space group, and the unit cell volume of the single crystal molecule is 647 Å3The grain size is 130.3nm, and the crystallinity is 92%; the layered metal organic phosphate framework sodium ion positive electrode material is of a layered nanosheet structure, and the width of the nanosheet is 5-15 microns; the doping amount of the acidified graphene is 10% of the mass of the metal organic phosphate framework sodium ion positive electrode material; the particle size of the acidified graphene doped in the nanosheet is 0.05-0.12 mu m.
Through detection, the layered metal organic phosphate framework sodium ion positive electrode material in the embodiment of the invention belongs to a space group which is a chiral noncentral space groupHas a monoclinic system structure of C2H10Na2O16P2V2Pure phase.
Through detection, V = O and V-O bonds and HPO exist in the layered metal organic phosphate framework sodium ion positive electrode material in the embodiment of the invention4 2-And C2O4 2-Group, indicating a bidentate chelate coordination pattern of the oxalate ligand.
Through detection, the whole layered metal organic phosphate framework sodium ion positive electrode material in the embodiment of the invention is in a layered nanosheet structure, and the width of the nanosheet is 5-15 μm.
Through detection, graphene is doped and wrapped in the nanosheets of the layered metal organic phosphate framework sodium ion positive electrode material in the embodiment of the invention, and the particle size is 0.05-0.12 μm.
Preparation method of layered metal organic phosphate framework sodium ion cathode material example 3
(1) Adding 447.0mg of vanadium pentoxide (2.46 mmol) into 10mL of deionized water, stirring and dispersing for 20min at a stirring speed of 200 r/min, then adding 3.3mL of phosphoric acid (53.64 mmol) and 1240.4mg of oxalic acid dihydrate (9.84 mmol), stirring, then adding 590.3 mg of sodium hydroxide (14.75 mmol), and carrying out ultrasonic treatment for 20min at 250W until the mixture is uniformly dispersed to obtain 14mL of mixed solution A;
(2) placing 14mL of the mixed solution A obtained in the step (1) in a 50mL closed reaction kettle, carrying out hydrothermal reaction for 66h at 110 ℃, filtering, using deionized water and ethanol to sequentially wash and precipitate in a cross manner for 3 times, and drying for 16h at 195 ℃ to obtain 24.03g of Na-MOF material;
(3) and (3) mixing 0.1g of Na-MOF material obtained in the step (2) with 0.01g of acidified graphene, and grinding for 25min by using an agate mortar to obtain the layered metal organic phosphate framework sodium ion positive electrode 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.
Through detection, the first discharge reversible specific capacity of the assembled sodium-ion battery can reach 61.0mAh/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 59.3mAh/g after 30 cycles, and the capacity retention rate is 92.8%.
Through detection, the first discharge gram capacity of the assembled sodium-ion battery can reach 60.7mAh/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 0.3C, the discharge gram capacity can reach 46.1 mAh/g; under the current density of 0.5C, the discharge gram capacity can reach 43.4 mAh/g; under the current density of 1C, the discharge gram capacity can reach 39.0 mAh/g; under the current density of 2C, the specific discharge capacity can still reach 29.7mAh/g, which shows that the battery assembled by the layered metal organic phosphate framework sodium ion positive electrode material has better rate capability.
From the above, the battery assembled by the layered metal organic phosphate framework sodium ion positive electrode material obtained in the embodiment of the invention has good specific discharge capacity, rate capability and excellent cycling stability.
Layered metallo-organophosphate framework sodium ion positive electrode material example 4
The layered metal organic phosphate framework sodium ion positive electrode material is a layered material formed by doping acidified conductive carbon black in the metal organic phosphate framework sodium ion positive electrode material; the single crystal molecular formula of the metal organic phosphate framework sodium ion anode material is as follows: c2H10Na2O16P2V2The molecular structure belongs to a monoclinic system structure with a space group being a chiral noncentral space group, and the unit cell volume of the single crystal molecule is 701.2 Å3The grain size is 129.8nm, and the crystallinity is 85%; the layered metal organic phosphate framework sodium ion positive electrode material is of a layered nanosheet structure, and the width of the nanosheet is 1-10 microns; the doping amount of the acidified conductive carbon black is 8% of the mass of the metal organic phosphate framework sodium ion positive electrode material; the particle size of the acidified conductive carbon black doped in the nanosheet is 0.10-0.20 mu m.
Through detection, the layered metal organic phosphate framework sodium ion cathode material in the embodiment of the invention belongs to a monoclinic system structure with a space group being a chiral noncentral space group and is C2H10Na2O16P2V2Pure phase.
Through detection, V = O and V-O bonds and HPO exist in the layered metal organic phosphate framework sodium ion positive electrode material in the embodiment of the invention4 2-And C2O4 2-The group shows the chelating bidentate bridging coordination mode of the oxalate ligand.
Through detection, the whole layered metal organic phosphate framework sodium ion positive electrode material in the embodiment of the invention is in a layered nanosheet structure, and the width of the nanosheet is 1-10 μm.
Through detection, conductive carbon black is doped and wrapped in the nanosheets of the layered metal organic phosphate framework sodium ion positive electrode material in the embodiment of the invention, and the particle size is 0.10-0.20 μm.
Preparation method of layered metal organic phosphate framework sodium ion cathode material example 4
(1) Adding 610.4mg of vanadium dioxide (7.36 mmol) into 10mL of deionized water, stirring and dispersing for 7min at the stirring speed of 150 r/min, then adding 5.38mL of phosphoric acid (87.45 mmol) and 1391.7mg of oxalic acid dihydrate (11.04 mmol), stirring, then adding 430.1mg of sodium chloride (7.36 mmol), and carrying out ultrasonic treatment for 5min at 500W until the solution is uniformly dispersed to obtain 16mL of mixed solution A;
(2) placing 16mL of the mixed solution A 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 wash and precipitate for 4 times in a cross way, and drying for 18h at 210 ℃ to obtain 23.89g of Na-MOF material;
(3) and (3) mixing 0.06g of Na-MOF material obtained in the step (2) with 0.0048g of acidified conductive carbon black, and grinding for 40min by using an agate mortar to obtain the layered metal organic phosphate framework sodium ion positive electrode 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.
Through detection, the first discharge reversible specific capacity of the assembled sodium-ion battery can reach 58.7mAh/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 57.2mAh/g after 30 cycles, and the capacity retention rate is 97.4%.
Through detection, the first discharge gram capacity of the assembled sodium-ion battery can reach 62.4mAh/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 0.3C, the discharge gram capacity can reach 43.3 mAh/g; under the current density of 0.5C, the discharge gram capacity can reach 39.3 mAh/g; under the current density of 1C, the discharge gram capacity can reach 34.8 mAh/g; under the current density of 2C, the specific discharge capacity can still reach 30.1mAh/g, which shows that the battery assembled by the layered metal organic phosphate framework sodium ion positive electrode material has better rate capability.
From the above, the battery assembled by the layered metal organic phosphate framework sodium ion positive electrode material obtained in the embodiment of the invention has good 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 Na-MOF 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 59.1 mAh/g in the voltage range of 2.5 to 4.5V and at the current density of 0.1C, and after 30 cycles, the discharge reversible specific capacity is only 19.3 mAh/g, and the capacity retention rate is only 32.7%, which indicates that the cycle performance is poor.
As shown in fig. 7, the initial discharge gram capacity of the assembled sodium-ion battery is 61.6mAh/g in the voltage range of 2.5-4.5V and at the current density of 0.1C; under the current density of 2C, the discharge specific capacity is reduced to 0.7mAh/g, which shows that the rate capability is very poor.
From the above, the addition of the carbon conductive agent can effectively improve the cycle and rate performance of the cathode material.

Claims (20)

1. The layered metal organic phosphate frame sodium ion battery positive electrode material is characterized by comprising metal organic phosphate frame sodiumThe anode material of the ion battery is a layered material formed by doping a carbon conductive agent; the molecular formula of the metal organic phosphate framework sodium-ion battery positive electrode material is C2H10Na2O16P2V2The molecular structure belongs to a monoclinic system structure with a space group being a chiral noncentral space group.
2. The positive electrode material of the layered metal organic phosphate framework sodium-ion battery as claimed in claim 1, wherein the unit cell volume of the positive electrode material is 620-720 Å3The grain size is 110-140 nm, and the crystallinity is 85-100%; the layered metal organic phosphate framework sodium ion battery positive electrode material is in a layered nanosheet structure, and the width of the nanosheet is 1-20 microns; the particle size of the carbon conductive agent doped in the nanosheet is 0.02-0.20 μm.
3. The layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 1 or 2, characterized in that: the doping amount of the carbon conductive agent is 2-20% of the mass of the anode material of the metal organic phosphate framework sodium ion battery; the carbon conductive agent is one or more of carbon nano tube, graphene or conductive carbon black; the carbon conductive agent is subjected to acidification treatment before use, and the specific method comprises the following steps: adding a carbon 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 operation until the water washing solution is neutral, and finally performing vacuum drying to constant weight to obtain an acidified carbon conductive agent; the mixed acid is formed by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 2-4: 1; the mass-volume ratio of the carbon conductive agent to the mixed acid is 0.1-0.3: 100, and the unit of the mass-volume ratio is g/mL; the power of the ultrasonic dispersion is 100-600W, and the time is 3-5 h; the volume of the water for dilution is 3-5 times of the volume of the mixed acid; the aperture of the microporous filter membrane is 0.4-0.5 mu m; the temperature of vacuum drying is 80-100 ℃.
4. A preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
(1) adding a vanadium source into water, stirring and dispersing, then adding phosphoric acid and oxalic acid dihydrate, stirring, adding a sodium source, and carrying out ultrasonic treatment until the mixture is uniformly dispersed to obtain a mixed solution A;
(2) placing the mixed solution A obtained in the step (1) in a closed reaction kettle for hydrothermal reaction, filtering, washing the precipitate, and drying to obtain a Na-MOF material;
(3) and (3) mixing the Na-MOF material obtained in the step (2) with a carbon conductive agent, and grinding to obtain the layered metal organic phosphate framework sodium-ion battery positive electrode material.
5. The preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 4, characterized in that: in the step (1), the molar volume ratio of vanadium element to water in the vanadium source is 0.2-1.0: 1, and the unit of the molar volume ratio is mmol/mL; the vanadium source 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 preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 4 or 5, characterized in that: in the step (1), the molar ratio of the phosphoric acid, the oxalic acid dihydrate and the vanadium element in the vanadium source is 5-50: 0.5-5.0: 1; the molar ratio of sodium element in the sodium source to vanadium element in the vanadium source is 0.1-4.0: 1; the sodium source is one or more of sodium hydroxide, sodium bicarbonate or sodium chloride.
7. The preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 4 or 5, characterized in that: in the step (1), the power of the ultrasound is 100-600W, and the time of the ultrasound is 1-100 min.
8. The preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 6, characterized in that: in the step (1), the power of the ultrasound is 100-600W, and the time of the ultrasound is 1-100 min.
9. The preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 4 or 5, characterized in that: in the step (2), the volume of the mixed solution A accounts for 20-70% of the volume of the closed reaction kettle; the temperature of the hydrothermal reaction is 90-180 ℃, and the time of the hydrothermal reaction is 24-80 h.
10. The preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 6, characterized in that: in the step (2), the volume of the mixed solution A accounts for 20-70% of the volume of the closed reaction kettle; the temperature of the hydrothermal reaction is 90-180 ℃, and the time of the hydrothermal reaction is 24-80 h.
11. The preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 7, characterized in that: in the step (2), the volume of the mixed solution A accounts for 20-70% of the volume of the closed reaction kettle; the temperature of the hydrothermal reaction is 90-180 ℃, and the time of the hydrothermal reaction is 24-80 h.
12. The preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 4 or 5, characterized in that: 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.
13. The preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 6, characterized in that: 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.
14. The preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 7, characterized in that: 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.
15. The method for preparing the layered metal organic phosphate framework sodium-ion battery cathode material according to claim 9, characterized in that: 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.
16. The preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 4 or 5, characterized in that: in the step (3), the amount of the carbon conductive agent is 2-20% of the mass of the Na-MOF material; the grinding time is 20-60 min.
17. The preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 6, characterized in that: in the step (3), the amount of the carbon conductive agent is 2-20% of the mass of the Na-MOF material; the grinding time is 20-60 min.
18. The preparation method of the layered metal organic phosphate framework sodium-ion battery positive electrode material according to claim 7, characterized in that: in the step (3), the amount of the carbon conductive agent is 2-20% of the mass of the Na-MOF material; the grinding time is 20-60 min.
19. The method for preparing the layered metal organic phosphate framework sodium-ion battery cathode material according to claim 9, characterized in that: in the step (3), the amount of the carbon conductive agent is 2-20% of the mass of the Na-MOF material; the grinding time is 20-60 min.
20. The method for preparing the layered metal organic phosphate framework sodium-ion battery cathode material according to claim 12, wherein the method comprises the following steps: in the step (3), the amount of the carbon conductive agent is 2-20% of the mass of the Na-MOF material; the grinding time is 20-60 min.
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