CN109786715B - Method for preparing copper-based sodium-rich layered oxide material based on chalcopyrite - Google Patents
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Abstract
The invention discloses a method for preparing a copper-based sodium-rich layered oxide material based on chalcopyrite, which comprises the steps of placing chalcopyrite concentrate in an air atmosphere for calcination treatment, mixing a calcined product with manganese oxide and sodium salt through ball milling, and then placing in the air atmosphere for heat treatment to obtain the copper-based sodium-rich layered oxide material. The method uses chalcopyrite (with CuFeS as main ingredient) rich in natural resources2) The prepared copper-based sodium-rich layered oxide material has stable crystal structure and high purity, is used as an anode active substance of a sodium ion battery, and the obtained sodium ion secondary battery shows higher working voltage, excellent multiplying power and cycle performance.
Description
Technical Field
The invention relates to a preparation method of a copper-based sodium-rich layered oxide material, in particular to a method for preparing the copper-based sodium-rich layered oxide material for a sodium ion battery by using low-price chalcopyrite concentrate, belonging to the technical field of preparation of sodium ion battery materials.
Background
Fossil energy sources such as coal, oil and natural gas support the progress of human civilization and the development of economic society since the 19 th century. However, the non-regenerability of fossil energy and the huge consumption of fossil energy by human beings are gradually going to be exhausted, and the ecological environmental problems caused by fossil energy are becoming more severe. Under the background of the times, the development of renewable, sustainable and environment-friendly new energy has become a common consensus, and renewable energy sources such as solar energy, wind energy and the like are vigorously developed. However, due to the intermittent and unstable characteristics of the photovoltaic power generation and the wind power generation, smooth grid-connected power supply is difficult, so that large-scale energy storage equipment is required for regulation and control, the peak clipping and valley filling functions are exerted, the power supply efficiency and stability are improved, and the power supply cost is reduced. At present, the secondary batteries which can be selected mainly comprise nickel-hydrogen batteries, nickel-cadmium batteries, lead-acid storage batteries and lithium ion batteries. Among them, lithium ion batteries have been widely used in the fields of 3C products and electric vehicles because of their advantages of high specific energy, no memory effect, small self-discharge, long cycle life, and environmental friendliness, however, lithium resources are limited, and battery costs are high, and cannot meet the low-cost requirements of large-scale applications. The sodium in the same main group with lithium has physical and chemical properties similar to those of lithium, but has more abundant content and low cost. Therefore, the sodium ion secondary battery is considered as an ideal substitute for the lithium ion battery, and is expected to be applied to large-scale energy storage devices.
In recent years, the research on the electrode material of the sodium ion battery has become one of the research hotspots in the field of energy storage, and a large number of sodium ion positive and negative electrode materials are reported. The positive electrode material mainly comprises phosphate, fluorophosphate, Prussian blue and derivatives thereof, oxide, organic compounds and the like. Among them, the organic compound positive electrode material has poor conductivity and is decomposed at high voltage; prussian blue and derivatives thereof have higher working voltage but lower actual specific capacity, and the conventional liquid phase preparation method easily causes water molecules to enter crystal lattices to block Na+Transport and de-intercalation, resulting in rapid capacity fade. The phosphate anode material has outstanding thermal stability and structural stability, the fluorophosphate obtained by replacing phosphate ions with the fluoride ions enhances the anion induction effect and improves the platform voltage, however, the material has larger mass, so that the specific capacity of the material is lower, and the practical application is limited. Na having NASICON structure3V2(PO4)3Is a phosphate positive electrode which is successfully researched in recent yearsA material. The application of carbon-coating modification strategies in the brave plants and the like improves the platform capacity [ electrochem. Commun.,2012,14,86-89 ]; duck waves and the like prepared by solvent-assisted carbothermic method3V2(PO4)2F3Has a high voltage platform of 3.8V/4.2V and shows excellent multiplying power and cycle performance [ J.Power Sources,2014,1, 871-.
Compared with the anode materials, the oxide has the advantages of small molecular weight, high specific capacity, good electrochemical activity, simple preparation process and the like. Structurally, oxide positive electrode materials can be classified into a tunnel type and a layer type. Tunnel type mainly means Na having S-type large channel0.44MnO2The structure is stable, and the circulating performance is excellent, but the sodium content is low, so that the provided capacity is small, and the practical application of the composite material is limited. The layered oxide can be classified into P2 type and O3 type according to the environment of sodium ion and the stacking mode of oxygen atom, and respectively corresponds to space groups P63/mm and R-3m [ Physical B ]&C,1980,99,81-85 ]. In the P2 type layered oxide, the space where sodium ions are located is large, the transmission energy barrier is low, the structure in the charging and discharging process is stable, and good cycle performance is shown, but the capacity of the P2 type layered oxide is limited to a certain extent due to the relatively low sodium content. Although the O3-type layered oxide has a high sodium content, the sodium ion transport energy barrier is relatively high, and a multi-phase transition process occurs during charge and discharge, resulting in poor cycle performance. In addition, most O3-type oxides are unstable in air and tend to shift to the low sodium phase. The copper-based layered oxide cathode material is prepared by the copper doping thought of the Huyong et al by taking oxides of copper, iron, manganese and sodium as raw materials [ adv.Sci.2015,2,1500031; adv.mater.2015,27,6928-6933 ]. The material has higher working voltage, shows excellent stability in air, and provides a feasible idea and reference for modification research of the layered oxide material. However, the method selects copper oxide, ferric oxide and manganese oxide as industrial products, which are high in price and increase the preparation cost of materials.
Disclosure of Invention
Aiming at the defects of raw materials and cost existing in the method for preparing the copper-based sodium-rich layered oxide material in the prior art, the invention aims to provide the method for preparing the high-purity phase copper-based sodium-rich layered oxide material, which has simple steps, low raw material cost and mild conditions.
In order to achieve the technical purpose, the invention provides a method for preparing a copper-based sodium-rich layered oxide material based on chalcopyrite.
The technical scheme of the invention is to use chalcopyrite (the main component is CuFeS)2) As a Cu source and an Fe source. Chalcopyrite is the primary chalcopyrite with the most abundant reserves in nature, the sources are wide, and the chalcopyrite concentrate with the purity of more than or equal to 99 percent can be easily obtained after the primary chalcopyrite is subjected to flotation by the existing process.
The technical scheme of the invention is that chalcopyrite is fully calcined in air atmosphere to obtain a mixture of copper ferrite and copper oxide, and the calcined product is directly used as a raw material to react with manganese oxide and a sodium source at a high temperature in a solid phase manner to obtain the copper-based sodium-rich layered oxide material in one step, which is unexpected.
The copper-based sodium-rich layered oxide material prepared by the technical scheme of the invention has the following chemical expression:
NaxCuaFebMny+ cO2+δ；
wherein, the Cu element is +2 valence, the Fe element is +3 valence, the Mn element valence is +4 valence or the mixed state of +3 valence and +4 valence, that is, y is more than 3 and less than or equal to 4;
x, a, b, c and delta are mole percentages of corresponding elements, and the x, a, b, c, y and delta satisfy the charge balance relation: x +2a +3b + yc ═ 2(2+ δ), and satisfies 0.4 < x ≦ 1 and a + b + c ≦ 1; a is more than or equal to 0.15 and less than or equal to 0.3, b is more than or equal to 0.15 and less than or equal to 0.3, c is more than or equal to 0.4 and less than or equal to 0.7, and delta is more than or equal to-0.02 and less than or equal to 0.02.
The copper-based sodium-rich layered oxide material has a layered oxide structure, and transition metal elements Cu, Fe and Mn respectively form MO with six nearest oxygen atoms6(M ═ Cu, Fe, Mn) octahedral structure, MO6Octahedron connected in common edge to form transition metal layer, alkali metal ion Na+Forming an alkali metal layer between the transition metal layers; when the sodium content x is less than 0.8, Na+Occupying the position of a triangular prism between transition metal layers, wherein the obtained layered oxide has a P2 type structure, and the corresponding space group is P63/mmc; when the sodium content is more than or equal to 0.8 and less than or equal to 1, Na+Occupies octahedral positions between transition metal layers, and the obtained layered oxide has an O3 type structure and a corresponding space group of R-3 m.
In a preferred scheme, the calcining treatment temperature is 650-950 ℃, and the calcining time is 5-10 h. The complete conversion of the chalcopyrite can be ensured in the preferred temperature and time range, and impurity phases such as sodium sulfate and the like can be generated in the subsequent mixing heat treatment process of the manganese oxide and the sodium carbonate if the conversion is not complete.
In a preferred embodiment, the calcined product is a mixture of copper ferrite and copper oxide.
Preferably, the manganese oxide comprises manganese sesquioxide and/or manganese dioxide.
In a preferred embodiment, the sodium salt comprises sodium carbonate.
In a preferred embodiment, the molar ratio of the calcined product to the oxides of manganese and sodium salt is 1:3: (2-5); wherein the calcined product is measured in terms of the molar amount of iron or copper contained therein. The sodium carbonate is generally present in an excess of 2 to 5% by weight relative to the theoretical molar mass.
In a preferable scheme, the temperature of the heat treatment is 700-1100 ℃, and the time is 10-20 hours.
The ball milling process of the invention is wet ball milling. A proper amount of volatile organic solvent such as ethanol or acetone can be used as a ball milling medium, and is ball milled to prepare slurry, and then the slurry is dried at the temperature of 60-80 ℃ to obtain precursor powder. The raw materials can be fully and uniformly mixed by ball milling, which is beneficial to the high-temperature solid-phase reaction efficiency and the high-purity copper-based sodium-rich layered oxide material.
The copper-based sodium-rich layered oxide material is used as a positive active material for a sodium ion battery, and the obtained sodium ion secondary battery has higher working voltage, excellent multiplying power and cycle performance, can be applied to large-scale energy storage equipment such as solar power generation, wind power generation, distributed power stations, smart grid peak shaving, backup power sources or communication base stations, and has great commercial application prospect.
The copper-based sodium-rich layered oxide material is used as a positive electrode active substance, and is coated on a current collector with a conductive additive, an adhesive and the like by a coating method to prepare a positive electrode plate. Conductive additives and binders are materials common in the art.
The preparation method of the copper-based sodium-rich layered oxide material is a solid phase method, and comprises the following specific steps:
pre-burning selected chalcopyrite with required stoichiometry for 5-10 hours in air atmosphere at 650-950 ℃, and mixing with manganese dioxide (or manganese dioxide) and sodium carbonate with corresponding stoichiometry according to a molar ratio of 1:3: (2-5) mixing; wherein, the sodium carbonate is excessive by 2 to 5 weight percent;
preparing precursor slurry from precursor powder and a proper amount of volatile organic solvent such as ethanol or acetone, uniformly mixing the precursor slurry by using a ball milling method, and drying at 60-80 ℃ to obtain precursor powder;
and placing the precursor powder in a tubular heating furnace or a muffle furnace, and carrying out heat treatment for 10-20 hours at 700-1100 ℃ in an air atmosphere to obtain the layered oxide material.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the copper-based sodium-rich layered oxide material has simple preparation process, takes chalcopyrite concentrate, manganese oxide and sodium salt as raw materials, and is synthesized by two steps of solid phase synthesis.
The copper-based sodium-rich layered oxide material adopts the chalcopyrite concentrate as the raw material, the raw material is easy to obtain, and the production cost of the material is greatly reduced.
The copper-based sodium-rich layered oxide material has high purity, does not contain impurity phases and has a stable crystal structure.
The copper-based sodium-rich layered oxide material has high electrochemical activity, and shows high working voltage, excellent multiplying power and cycle performance when being used for a sodium ion secondary battery.
Drawings
FIG. 1 is a process flow diagram of a copper-based sodium-rich layered oxide material;
FIG. 2 is an XRD spectrum of chalcopyrite;
FIG. 3 is an SEM image of chalcopyrite;
FIG. 4 is an XRD spectrum of a chalcopyrite pre-sintering product;
FIG. 5 is an SEM image of a chalcopyrite pre-sintered product;
FIG. 6 is XRD patterns of copper-based sodium-rich layered oxide materials with different element mole percentages;
FIG. 7 shows a layered oxide Na in example 20.6Cu0.19Fe0.21Mn0.6O2SEM picture of (1);
FIG. 8 is a charge-discharge graph of the sodium ion half cell of example 2;
FIG. 9 is a charge-discharge graph of the sodium ion half cell of example 3;
FIG. 10 is a charge-discharge graph of the sodium ion half cell of example 4;
FIG. 11 is an XRD pattern of the final product of comparative example 1;
FIG. 12 is a graph showing the charge and discharge curves of the sodium-ion half cell in comparative example 1;
fig. 13 is an XRD pattern of the final product of comparative example 2.
Detailed Description
The following examples are intended to explain the invention in more detail and do not limit the scope of the invention as claimed.
Example 1
The embodiment provides a preparation method of a copper-based sodium-rich layered oxide material, specifically a solid-phase method, and the flow shown in fig. 1 comprises the following steps:
And 3, uniformly mixing the precursors by adopting a ball milling method to obtain precursor powder. Preparing precursor slurry from the precursor powder and a proper amount of volatile organic solvent such as ethanol or acetone, uniformly mixing the precursor slurry by using a ball milling method, and drying at 60-80 ℃ to obtain precursor powder.
And 4, placing the precursor powder in a tubular heating furnace or a muffle furnace, and carrying out heat treatment for 10-20 hours at 700-1100 ℃ in an air atmosphere.
And 5, fully grinding the precursor powder after heat treatment to obtain the copper-based sodium-rich layered oxide material.
The chemical general formula of the prepared copper-based sodium-rich layered oxide material is as follows: na (Na)xCuaFebMny+ cO2+δ；
Wherein, the Cu element is +2 valence, the Fe element is +3 valence, the Mn element valence is +4 valence or the mixed state of +3 valence and +4 valence, that is, y is more than 3 and less than or equal to 4; the x, a, b, c and delta are mole percentages of corresponding elements, and the x, a, b, c, y and delta satisfy a charge balance relation: x +2a +3b + yc ═ 2(2+ δ), and satisfies 0.4 < x ≦ 1 and a + b + c ≦ 1; wherein a is more than or equal to 0.15 and less than or equal to 0.3, b is more than or equal to 0.15 and less than or equal to 0.3, c is more than or equal to 0.4 and less than or equal to 0.7, and delta is more than or equal to-0.02 and less than or equal to 0.02;
in NaxCuaFebMny+ cO2+δIn the structure of (1), transition metal elements Cu, Fe, Mn form MO with six oxygen atoms nearest to each other6(M ═ Cu, Fe, Mn) octahedral structure, MO6Octahedron connected in common edge to form transition metal layer, alkali metal ion Na+And forming an alkali metal layer between the transition metal layers, wherein the transition metal layers and the alkali metal layers alternately form a layered structure.
The X-ray diffraction (XRD) patterns of the plurality of layered oxide materials with different mole percentages of the elements are given in fig. 6. According to an XRD (X-ray diffraction) pattern, when the sodium content x is less than 0.8, the obtained layered oxide has a P2 type structure, and the corresponding space group is P63/mmc; when the sodium content is more than or equal to 0.8 and less than or equal to 1, the obtained layered oxide has an O3 type structure, and the corresponding space group is R-3 m.
Example 2
In this example, the layered oxide material was prepared using the solid phase method described in example 1 above.
Pre-burning selected chalcopyrite (the purity is more than or equal to 95%) with required stoichiometric quantity in an air atmosphere at 850 ℃ for 5 hours; mixing the obtained pre-sintered chalcopyrite product with manganese oxide and sodium carbonate (5 wt% in excess) according to a molar ratio of 1:3:3.15, and uniformly mixing precursor powder by adopting a wet ball milling process; transferring the precursor powder into a corundum crucible, and treating for 15h at 900 ℃ in a tubular heating furnace in the air atmosphere to obtain layered oxide Na0.6Cu0.19Fe0.21Mn0.6O2(black powder), the XRD pattern of which is shown in FIG. 6, the XRD pattern indicates that the resulting layered oxide has a P2 type structure. The SEM image is shown in FIG. 7.
Mixing the above prepared Na0.47Cu0.19Fe0.21Mn0.6O2The material is used as the positive active substance of the sodium ion secondary battery to prepare the positive pole piece. The concrete mode is as follows: the obtained Na0.6Cu0.19Fe0.21Mn0.6O2Mixing the powder with acetylene black and polyvinylidene fluoride (PVDF, adhesive) according to a mass ratio of 70:20:10, dropwise adding a proper amount of N-methylpyrrolidone (NMP) solution serving as a dispersing agent, and grinding for 10 minutes to prepare slurry; the slurry is then coated on an aluminum foil current collector, 12Vacuum drying at 0 deg.C for 8h, and transferring to Ar atmosphere glove box for use.
The half-cells were assembled in an Ar atmosphere glove box. Using metal sodium as counter electrode and NaClO4A/ethylene carbonate (EC: DMC: DEC ═ 1:1:1) solution was used as an electrolyte and assembled into a CR2016 type button cell. A charge-discharge test was carried out at a current density of C/10(10mA/g) using a constant current charge-discharge mode, with a charge cut-off voltage set at 4.2V and a discharge cut-off voltage set at 2.5V. The charge and discharge curves for the first three weeks are shown in fig. 8, and the specific discharge capacities for the first three weeks are 67.6, 68.6 and 69 ma-hr/g, respectively.
Example 3
The specific preparation method and steps of this example are the same as those of example 2, but the raw material ratios are different, specifically, the chalcopyrite pre-sintered product: manganese sesquioxide: sodium carbonate 1:3: 3.675 (molar ratio, 5% excess sodium carbonate) of which the resulting layered oxide was Na0.68Cu0.26Fe0.17Mn0.57O2(black powder), the XRD pattern of which is shown in FIG. 1. The XRD pattern showed that the resulting layered oxide was of the P2 type structure. Prepared Na0.68Cu0.26Fe0.17Mn0.57O2The material is used as the positive active substance of the sodium ion secondary battery to prepare a positive pole piece and assemble the sodium ion half battery. A charge-discharge test was carried out at a current density of C/10(10mA/g) using a constant current charge-discharge mode, with a charge cut-off voltage set at 4.2V and a discharge cut-off voltage set at 2.5V. The charge and discharge curves for the first three weeks are shown in fig. 9, with specific discharge capacities of 75.8, 75.2 and 73.2 ma-hrs/g for the first three weeks, respectively.
Example 4
The specific preparation method and procedure of this example are essentially the same as in example 2, except that: (1) the raw material mixture ratio is different, specifically, the chalcopyrite presintering product: manganese sesquioxide: sodium carbonate 1:3: 4.6 (molar ratio, 2% sodium carbonate excess); (2) the heat treatment temperature is changed to 850 ℃ and the heat treatment is carried out for 10h under the air atmosphere. The obtained product is Na0.92Cu0.26Fe0.18Mn0.56O2Referring to fig. 6, the XRD pattern shows that the resulting layered oxide has an O3 type structure. To be preparedNa0.92Cu0.26Fe0.18Mn0.56O2The material is used as the positive active substance of the sodium ion secondary battery to prepare a positive pole piece and assemble the sodium ion half battery. A charge-discharge test was carried out at a current density of C/10(10mA/g) using a constant current charge-discharge mode, with a charge cut-off voltage set at 4.2V and a discharge cut-off voltage set at 2.5V. The charge and discharge curves for the first three weeks are shown in fig. 10, with the specific discharge capacities for the first three weeks being 85.5, 84.5 and 84.6 ma-hrs/g, respectively.
Comparative example 1
The specific preparation method and the raw material ratio of the comparative example are basically the same as those of the example 2, and the differences are as follows: in order to compare the influence of the mixing mode on the product components and structure, the precursor powder is mixed by adopting a grinding method in the embodiment. The XRD pattern of the finally obtained layered oxide is shown in figure 11, and the XRD pattern shows that the obtained layered oxide has a P2 type structure. However, elemental analysis showed that the product component was Na0.47Cu0.19Fe0.21Mn0.57O2The difference of the components of the layered oxide prepared by the ball milling method is obvious, which shows that compared with the ball milling method, the powder is not mixed uniformly enough and the particles are not contacted sufficiently, so that the deviation of the components of the product occurs. Prepared Na0.47Cu0.19Fe0.21Mn0.57O2The material is used as the positive active substance of the sodium ion secondary battery to prepare a positive pole piece and assemble the sodium ion half battery. A charge-discharge test was carried out at a current density of C/10(10mA/g) using a constant current charge-discharge mode, with a charge cut-off voltage set at 4.2V and a discharge cut-off voltage set at 2.5V. The charge and discharge curves for the first three weeks are shown in fig. 12, and the specific discharge capacities for the first three weeks are 60.2, 60.5 and 60.6 ma-hr/g, respectively.
Comparative example 2
In the comparative example, the copper-based layered oxide material is prepared by directly mixing and thermally treating the non-presintered chalcopyrite concentrate with manganese oxide and sodium carbonate. The specific method comprises the following steps: mixing chalcopyrite concentrate, manganese oxide and sodium carbonate according to the proportion of 1: 1.5: 1.575, and uniformly mixing precursor powder by adopting a wet ball milling process; transfer precursor powder to rigidAnd (3) treating the mixture in a jade crucible for 15 hours at 850 ℃ in an air atmosphere in a tubular heating furnace to obtain a product, wherein an XRD (X-ray diffraction) pattern of the product is shown in figure 13. The XRD spectrum shows that the obtained product is copper ferrite (CuFe)2O4) With sodium sulfate (Na)2SO4) The mixture of (1) shows that, in the case where the chalcopyrite is directly subjected to the mixing heat treatment with manganese sesquioxide and sodium carbonate without pre-burning, chalcopyrite decomposition occurs because sulfur dioxide is easily reacted with high-temperature molten sodium carbonate to obtain sodium sulfate which is difficult to decompose, and generation of a layered oxide is inhibited. Therefore, in the solid phase method described in example 1, the pre-sintering treatment of the chalcopyrite raw material is one of the key steps in the preparation of the copper-based layered oxide material in the present invention, and the degree of pre-sintering (desulfurization) has a significant influence on the product phase.
Claims (3)
1. A method for preparing a copper-based sodium-rich layered oxide material based on chalcopyrite is characterized by comprising the following steps: placing the chalcopyrite concentrate in an air atmosphere for calcination treatment, mixing the calcined product with manganese oxide and sodium salt through ball milling, and then placing in the air atmosphere for heat treatment to obtain the chalcopyrite;
the molar ratio of the calcined product to the manganese oxide and the sodium salt is 1:3: (2-5);
the calcining treatment temperature is 650-950 ℃, and the calcining time is 5-10 h;
the calcined product is a mixture of copper ferrite and copper oxide;
the temperature of the heat treatment is 700-1100 ℃, and the time is 10-20 hours.
2. The method for preparing the copper-based sodium-rich layered oxide material based on the chalcopyrite according to the claim 1, wherein the method comprises the following steps: the manganese oxide comprises manganese sesquioxide and/or manganese dioxide.
3. The method for preparing the copper-based sodium-rich layered oxide material based on the chalcopyrite according to the claim 1, wherein the method comprises the following steps: the sodium salt comprises sodium carbonate.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104638260A (en) * | 2015-02-12 | 2015-05-20 | 陕西理工学院 | Process for preparing electrode material of multi-element doped sodium-ion battery by use of sodium jarosite |
| CN104795552A (en) * | 2014-10-16 | 2015-07-22 | 中国科学院物理研究所 | Layered oxide material, preparation method, pole piece, secondary cell and application |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104795552A (en) * | 2014-10-16 | 2015-07-22 | 中国科学院物理研究所 | Layered oxide material, preparation method, pole piece, secondary cell and application |
| CN104638260A (en) * | 2015-02-12 | 2015-05-20 | 陕西理工学院 | Process for preparing electrode material of multi-element doped sodium-ion battery by use of sodium jarosite |
Non-Patent Citations (1)
| Title |
|---|
| Exploration and Size Engineering from Natural Chalcopyrite to High-Performance Electrode Materials for Lithium-Ion Batteries;Yang Zhang等;《ACS Appl. Mater. Interfaces》;20190115;第11卷;第6154-6165页 * |
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