CN111261870B - NASICON structure Na4CrMn(PO4)3Method for producing materials and use thereof - Google Patents
NASICON structure Na4CrMn(PO4)3Method for producing materials and use thereof Download PDFInfo
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- CN111261870B CN111261870B CN202010077442.1A CN202010077442A CN111261870B CN 111261870 B CN111261870 B CN 111261870B CN 202010077442 A CN202010077442 A CN 202010077442A CN 111261870 B CN111261870 B CN 111261870B
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a NASICON structure Na4CrMn(PO4)3Manufacture of materialsPreparation method and application thereof. With Cr (CH)3COO)3、Mn(CH3COO)2·4H2O、CH3COONa and NH4H2PO4Using a sol-gel method as raw materials, carrying out magnetic stirring and ultrasonic treatment on the raw materials by using an oil bath kettle at 78 ℃ to volatilize water to obtain dried gel, then placing the dried gel in a vacuum drying oven to be dried for 12 hours at 120 ℃ to obtain dried gel, fully grinding the dried gel to obtain powder, weighing 0.4 g of powder, pressing the powder into tablets by using a phi 10 mm mould, placing the tablets in a tubular furnace, and carrying out heat treatment for 6 hours at 800 ℃ under the argon atmosphere to obtain the NASICON structure Na4CrMn(PO4)3The material is applied to the positive electrode material of the sodium-ion battery. The invention has the characteristics of simple operation and high product purity, shows a higher voltage platform and a still available specific capacity when being used as the positive electrode material of the sodium-ion battery, and can provide reference significance for the development of the positive electrode material of the sodium-ion battery and the design of a commercial battery with high energy density.
Description
Technical Field
The invention belongs to the technical field of electrode materials and electrochemical energy storage devices, and particularly relates to Na with an NASICON structure4CrMn(PO4)3A method for preparing the material and application thereof.
Background
With the rapid progress of science and technology, environmental problems caused by the increasing demand of human beings on fossil fuels become a non-negligible factor, and the effective utilization of green renewable energy sources is urgently realized. Conventional renewable energy sources such as solar energy, wind energy and tidal energy are not supplied stably, and in order to sufficiently and effectively store and utilize the energy sources, development of a large-scale energy storage system becomes a hot spot of attention at present.
Sodium Ion Batteries (SIB) are increasingly used in large-scale energy storage devices due to the abundant, widespread and inexpensive storage of sodium resources in the earth's crust. NASICON (sodium super ion conductor) structural materials are considered as an attractive SIB electrode material by virtue of their stable three-dimensional framework and large sodium ion channels. Na (Na)3V2(PO4)3The material is a typical sodium super-ionic conductor structure material, has higher ionic conductivity and higher theoretical specific capacity, and has a discharge platform of about 3.4V. The invention uses Na3V2(PO4)3The material is a matrix, and the matrix is a porous material,by jointly replacing V element with Cr element and Mn element, Na as new material is formed under the condition of keeping original crystal structure unchanged and electric neutrality4CrMn(PO4)3When the material is used as a positive electrode material of a sodium-ion battery, the theoretical capacity can reach 111 mAh g within the voltage range of 2.5-4.5V-1The charging and discharging platform is as high as 4.3V.
Disclosure of Invention
The invention aims to provide a NASICON structure Na4CrMn(PO4)3A method for preparing the material and application thereof.
Preparation of NASICON Structure Na4CrMn(PO4)3The material comprises the following specific steps:
(1) placing the beaker filled with distilled water into an oil bath pan at 78 ℃, and then adding Na4CrMn(PO4)3Respectively weighing Cr (CH) according to the stoichiometric ratio3COO)3、Mn(CH3COO)2·4H2O、CH3COONa and NH4H2PO4Dissolving the raw materials in the distilled water, stirring for half an hour, taking out the beaker, putting the beaker into an ultrasonic cleaner for ultrasonic treatment for 10 minutes, and then continuing to carry out magnetic stirring at 78 ℃ to evaporate water to obtain dry gel.
(2) And (2) putting the xerogel prepared in the step (1) into a vacuum drying oven, drying for 12 hours at 120 ℃ to obtain dried gel, fully grinding the dried gel to obtain powder, weighing 0.4 g of the powder, and pressing the powder into tablets by using a phi 10 mm mould.
(3) Placing the sheet obtained in the step (2) in a tube furnace, and carrying out heat treatment at 800 ℃ for 6 hours in argon atmosphere to obtain NASICON structure Na4CrMn(PO4)3A material.
NASICON structure Na of the invention4CrMn(PO4)3The material is applied to the positive electrode material of the sodium-ion battery.
The invention uses transition metal Cr element and Mn element to completely replace Na3V2(PO4)3V element in (1) obtained by increasing Na content while maintaining electrical neutralityNa4CrMn(PO4)3Material in which Cr and Mn occupy the position of V together, Cr3+Ionic radius (0.69A) and Mn2+(0.8A) and V3+The crystal structure is similar to that of the crystal structure in 0.74A, and can still maintain the original crystal structure after completely replacing the V element, the structure belongs to a trigonal crystal system, and the space group is R-3C. Theoretically, the compound can perform reversible extraction of two units of Na ions in charge and discharge in a voltage range of 2.5-4.5V, and corresponds to Mn3+/Mn2+And Mn4+/Mn3+The valence state of the two redox pairs is changed, and the maximum specific capacity can reach 111 mAh g-1Above, the voltage plateau is about 4.3V, and higher voltage can sufficiently improve the capacity density of the sodium ion battery.
The method adopts a sol-gel process to prepare Na with an NASICON structure4CrMn(PO4)3The material is different from the traditional high-temperature solid-phase synthesis process, the sol-gel process can realize the uniform mixing of reactant molecules, the components can be more uniform, the particle size of the obtained product is relatively small, and the electrochemical performance is improved to a certain extent. The method is simple and easy to implement, has high synthesis speed, and has reference significance for synthesis of other electrode materials.
Drawings
FIG. 1 shows NASICON structure Na prepared in example of the present invention4CrMn(PO4)3XRD pattern of the material.
FIG. 2 shows NASICON structure Na prepared in example of the present invention4CrMn(PO4)3Scanning electron micrographs of the material.
FIG. 3 is a cyclic voltammogram of the electrode obtained in the example of the present invention, with a sweep rate of 0.2 mV/s and a voltage range of 2.5-4.5V.
Fig. 4 is a voltage-capacity curve of the electrode obtained in the example of the present invention at 0.1C magnification for the first three cycles.
Fig. 5 is a graph of the cycling performance of the resulting electrode at 0.1C magnification in the examples of the invention.
Detailed Description
Example (b):
the following is a detailed description of specific examples, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following examples.
Preparation of NASICON Structure Na4CrMn(PO4)3The material comprises the following specific steps:
(1) the beaker containing 70 mL of distilled water was placed in an oil bath pan at 78 ℃ and then heated as Na4CrMn(PO4)3Respectively weighing Cr (CH) according to the stoichiometric ratio3COO)3、Mn(CH3COO)2·4H2O、CH3COONa and NH4H2PO4Dissolving in distilled water, stirring for half an hour, taking out, putting into an ultrasonic cleaner, performing ultrasonic treatment for 10 minutes, and then performing magnetic stirring at 78 ℃ to evaporate water to obtain dry gel.
(2) And (2) putting the xerogel prepared in the step (1) into a vacuum drying oven, drying for 12 hours at 120 ℃ to obtain dried gel, fully grinding the dried gel to obtain powder, weighing 0.4 g of the powder, and pressing the powder into tablets by using a phi 10 mm mould.
(3) Placing the sheet obtained in the step (2) in a tube furnace, and carrying out heat treatment at 800 ℃ for 6 hours in argon atmosphere to obtain NASICON structure Na4CrMn(PO4)3A material.
From FIG. 1, it is shown that Na is used3V2(PO4)3The structure is a structural model, RwpAbout 5.6%, RpAbout 4.08%, RBraggAbout 0.52%, it can be seen that the synthesized material is a pure phase compound, having a NASICON structure.
As can be seen from FIG. 2, the morphology of the obtained material is in a fine block shape, the surface is smooth and flat, and the particle diameter is distributed between 800 nm and 3 μm.
The NASICON structure Na prepared in this example was used4CrMn(PO4)3The material is applied to a positive electrode material of a sodium-ion battery and adopts Na according to NASICON structure4CrMn(PO4)3The electrode is prepared from the superconducting carbon black and PVDF (binder) in a mass ratio of 7:2: 1. Firstly putting PVDF into a glass beaker with the capacity of 5 mL, adding N-methylpyrrolidone solution (NMP), magnetically stirring until the mixture is clear, and adding Na with the NASICON structure4CrMn(PO4)3Mixing the material and superconducting carbon black, grinding in a mortar for 60 min, taking out, placing in a glass beaker, stirring for 8 hr, uniformly coating on a current collector aluminum foil, drying in a vacuum drying oven at 120 deg.C for 12 hr, taking out, slicing to obtain a wafer with a wafer area of 1.13 cm2Then, the electrode sheet was compacted at a pressure of 4 MPa as a working electrode, a metal sodium sheet as a reference electrode, a glass fiber membrane (Whatman) as a separator, an organic solution of sodium perchlorate in Ethylene Carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1: 1) as an electrolyte, 5 wt% fluoroethylene carbonate (FEC) as an additive, NaClO (sodium chloride) as an electrolyte, and NaClO (sodium chloride)4The concentration of (2) is L mol/L, and the battery case is CR 2032. The CR2032 half-cell was assembled and sealed in an argon filled glove box with an oxygen content and a water content below 0.1 ppm, wherein the charge and discharge capacity was calculated on the mass of the active material.
FIG. 3 is a cyclic voltammogram of the first three times of the resulting electrode at a scan rate of 0.2 mV/s over a voltage range of 2.5 to 4.5V. As can be seen from the CV diagram, the charging and discharging voltage platform is concentrated between 4.2V and 4.5V, and the curves of the second circle and the third circle are coincided, which shows that the electrode material has better reversibility.
Fig. 4 is a voltage-capacity curve of the resulting electrode at 0.1C magnification for the first three cycles. It can be seen that the charging platform is about 4.3-4.4V, and the discharging platform is about 4.2-4.3V, slightly lower than the charging platform.
FIG. 5 is a graph of data obtained after the resulting electrode was cycled at 0.1C rate for 10 cycles, and it can be seen that the first charge specific capacity was 191 mAh g-1The first discharge specific capacity is 69 mAh g-1The corresponding coulombic efficiency is 36%, and the reason why the coulombic efficiency is not high is mainly that the rapid dissolution of Mn element is caused by the strong Jalln-Teller effect in the charging and discharging process, so that the irreversible phase change of the material causes the rapid attenuation of the specific capacity. Reversible ratio after 10 cyclesThe capacity is 53.8 mAh g-1The coulomb efficiency reaches 90%, and the capacity is kept stable.
Claims (2)
1. NASICON structure Na4CrMn(PO4)3The preparation method of the material is characterized by comprising the following specific steps:
(1) placing the beaker filled with distilled water into an oil bath pan at 78 ℃, and then adding Na4CrMn(PO4)3Respectively weighing Cr (CH) according to the stoichiometric ratio3COO)3、Mn(CH3COO)2·4H2O、CH3COONa and NH4H2PO4Dissolving the raw materials in the distilled water, stirring for half an hour, taking out the beaker, putting the beaker into an ultrasonic cleaning machine for ultrasonic treatment for 10 minutes, and then continuously carrying out magnetic stirring at 78 ℃ to evaporate water to obtain dry gel;
(2) putting the xerogel prepared in the step (1) into a vacuum drying oven, drying for 12 hours at 120 ℃ to obtain dried gel, then fully grinding the dried gel to obtain powder, weighing 0.4 g of the powder, and pressing the powder into tablets by a phi 10 mm mould;
(3) placing the sheet obtained in the step (2) in a tube furnace, and carrying out heat treatment at 800 ℃ for 6 hours in argon atmosphere to obtain NASICON structure Na4CrMn(PO4)3A material.
2. NASICON structure Na prepared by the preparation method of claim 14CrMn(PO4)3The application of the material is characterized in that: the NASICON structure Na4CrMn(PO4)3The material is applied to the positive electrode material of the sodium-ion battery.
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| CN114649520A (en) * | 2022-03-31 | 2022-06-21 | 河南大学 | Polyanion-type sodium-ion battery positive electrode material modified by double carbons and preparation method and application thereof |
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| RU2566085C1 (en) * | 2011-08-29 | 2015-10-20 | Тойота Дзидося Кабусики Кайся | Active material for sodium accumulator positive electrode and method of its manufacturing |
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