CN112670510A - NaCrO2@ MFx/C composite material, preparation method thereof and application thereof in sodium-ion battery - Google Patents
NaCrO2@ MFx/C composite material, preparation method thereof and application thereof in sodium-ion battery Download PDFInfo
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Abstract
The invention relates to a NaCrO positive electrode material for a sodium-ion battery2The surface fluorination composite modification method is carried out. Taking a certain amount of NaCrO2Uniformly mixing the fluorine-containing organic compound and the metal salt, then carrying out high-temperature fluorination treatment reaction in an inert atmosphere resistance furnace, respectively carrying out sectional treatment at 350-450 ℃ and 550-750 ℃ for 2-6 hours, then naturally cooling to room temperature and taking out to obtain the fluoride and carbon composite modified NaCrO2A composite material. The experimental method has simple flow and easy operation, and the prepared composite material has excellent cycle performance and rate capability.
Description
Technical Field
The invention belongs to the technical field of sodium ions, and particularly relates to a surface modification technology of a positive electrode active material of a sodium ion battery.
Technical Field
In 2019, the royal academy of sciences in sweden awards the nobel chemical prize to john.b. goodenough, m.stanley Whittingham and Akira Yoshino to show the outstanding contributions they make in the field of lithium ion batteries, and create a chargeable world for human beings. However, it is important to develop a secondary battery system with wide resources and low cost due to the relative scarcity and uneven distribution of lithium resources. Compared with lithium, sodium which is located in the same main group and has similar chemical properties has wide resources and low price, and has the resource advantage and the cost advantage of replacing lithium ion batteries in partial fields. In sodium ion batteries, the layered transition metal oxide has high electrochemical activity and is of interest to the scientific community.
NaCrO as O3 phase sodium ion battery anode material2It has the advantages of good thermal stability, high safety performance and good rate capability. On one hand, the material is sensitive to moisture and air, has poor stability in the air and is easy to form residual alkali on the surface; on the other hand, the phase change of O3 → O '3 → P'3 occurs during the circulation process, the capacity attenuation is fast, the side reaction of the material and the electrolyte is more, and the circulation stability needs to be improved. ZHEN-WenFu et al first proposed the use of glucose on NaCrO2The capacity after circulating 40 cycles under the current density of 5mA/g is 110mAh/g, and the capacity retention rate is only 93.6% (Ding J, Zhou Y N, Sun Q, et al. cycle performance improvement of NaCrO2 carbon by coating for the sodium batteries [ J]Electrochemistry Communications,2012,22(none): 85-88). Seung-Taek Myung et al propose to adopt asphalt as carbon source for NaCrO2The surface modification is carried out, which not only contributes to enhancing the cycle performance of the material, but also enhances the conductivity of the material by the highly crystalline carbon, and the capacity retention rate after 50 cycles of the cycle under the current density of 20mA/g is 96 percent (Yu, C.Y.et al. NaCrO2 catalyst for high-rate sodium-ion battery)energy environ, Sci.8,2019-2026, doi:10.1039/c5ee00695c (2015), but the method adopts an emulsion drying method, and compared with the method, the method is more complicated in operation and more strict in experimental conditions. The experimental method has simple flow and easy operation, and the prepared composite material has excellent cycle performance and rate capability.
Disclosure of Invention
For NaCrO2The invention has the inherent defect of poor cycle performance of the material, and the first aim of the invention is to provide NaCrO2@ C @ MFx composite material (the invention is also called as composite material for short) and aims to solve the problem of NaCrO2The surface instability problem, and the rate and the cycle stability of the sodium ion battery are improved.
The second purpose of the invention is to provide the NaCrO2A preparation method of @ C @ MFx composite material, aiming at providing a composite material prepared from NaCrO2The solid phase synthesis method successfully coats the carbonaceous material in the oxide and solves the problem of phase transition of the material.
The third purpose of the invention is to provide the NaCrO2The application of the @ C @ MFx composite material in the sodium ion battery, and the obtained sodium ion battery and the positive electrode material thereof.
NaCrO2The sodium hydroxide is sensitive to moisture and air, has poor stability in the air and is easy to form residual alkali on the surface; moreover, the phase change of O3 → O '3 → P'3 occurs in the circulation process, the capacity attenuation is fast, and the side reaction of the material and the electrolyte is more; aiming at the technical problem, the invention provides the following solutions:
NaCrO2The @ MFx/C composite material comprises a base material and a coating material coated on the surface of the base material in situ, wherein the base material is NaCrO2(ii) a The coating material comprises a carbon material and metal fluoride MFx uniformly dispersed in the carbon material; the M comprises at least one of alkaline earth metal elements and rare earth metal elements; and x is the valence of the metal element.
The invention provides a novel material, which is prepared from NaCrO2Forming a carbon material in situ on the surface of the oxidic core material and depositing the carbon materialThe metal fluoride is embedded in situ in the matrix. The material can be based on the joint synergy of components and structures, and can effectively improve NaCrO2The stability of the material is reduced, the problem that the surface residual alkali and the phase are easy to change is solved, the structure and the phase stability of the material are effectively improved, and the capacity, the rate capability and the cycling stability of the material in a sodium ion battery are improved.
In the present invention, when M is an alkaline earth metal, the preferable valence thereof is +2 (that is, the MFx is MF2) (ii) a When M is a rare earth metal, the preferred valence is +3 (i.e., the MFx is MF)3)。
Preferably, M comprises at least one of Mg, Ca, Sr, Y, La and Ba.
Preferably, the carbon material is an amorphous carbon material; preferably a fluorine doped amorphous carbon material; further preferred is a carbon material obtained by pyrolysis of a fluoropolymer.
The coating material also comprises sodium fluoride formed by fluoridation of surface residual alkali sodium hydroxide or sodium carbonate, and the sodium fluoride is tightly combined on the surface of the substrate.
Preferably, the content of the metal fluoride in the composite material is 0.3-3 wt.%, and the content of the carbon is 0.5-5 wt.%.
The invention also provides the NaCrO2A preparation method of the @ metal fluoride/C composite material; adding NaCrO2Mixing with a fluorine carbon source and an M source, and then performing two-stage gradient sintering under a protective atmosphere to obtain the fluorine carbon source;
in the two-stage gradient sintering, the temperature of the first-stage sintering is 350-450 ℃; the temperature of the second-stage sintering is 550-750 ℃.
To solve the problem of NaCrO2The invention innovatively solves the technical problems of poor stability, residual alkali on the surface, easy phase transformation, easy impurity phase generation and high preparation difficulty2Combined with a fluorine carbon source and an M source and cooperated with the special two-stage gradient solid phase sintering mechanism, can synergistically solve the problem of NaCrO2Surface residual alkali and easy phase transformation, can successfully synthesize the material with the structure, and improves the prepared materialPhase stability, magnification and cycling stability of the material.
Preferably, the fluorine carbon source is a fluoropolymer. Researches show that the phase stability and electrochemical performance of the material can be further improved by adopting the preferred material and matching the metal source and the two-stage solid phase sintering mechanism.
Preferably, the fluoropolymer is at least one of polyvinyl fluoride (PVF), polyvinylidene fluoride (PVdF), Polytetrafluoroethylene (PTFE).
Preferably, the M source is at least one of hydroxide, carbonate, bicarbonate, nitrate and carboxylate of M metal.
Preferably, NaCrO2And the mass ratio of the fluorine carbon source to the M source is 1: 0.7% -7%: 0.3% -3%; further preferred ratios are 1: 0.8% -2%: 0.3 to 1.5 percent.
In the invention, the existing method and equipment can be adopted for NaCrO2Fluorine carbon source, M source are mixed, for example milled.
In the invention, in the two-stage gradient sintering process, the protective atmosphere is an oxygen-free atmosphere; preferably at least one of inert gas, nitrogen and hydrogen; further preferred are argon, nitrogen, an argon-hydrogen mixed gas, a nitrogen-hydrogen mixed gas;
preferably, the temperature of the first-stage sintering is 400-450 ℃.
Preferably, the time for the first stage sintering is 2-6 h.
Preferably, the temperature for the second stage sintering is 550-.
Preferably, the time for the first stage sintering is 2-6 h.
The preparation method comprises the following steps: adding NaCrO2The fluorine-containing polymer and the metal M element are mixed in a mortar, and are sintered for 2 to 6 hours in a segmented manner at 350 to 450 ℃ and 550 to 750 ℃ under the inert atmosphere condition, wherein the NaCrO2@MFxa/C composite positive electrode material; the fluorine source is at least one of polyvinyl fluoride (PVF), polyvinylidene fluoride (PVdF) and Polytetrafluoroethylene (PTFE); the metal M element source is carbonate or hydroxide of alkaline earth or rare earthAt least one of the substance; the protective atmosphere is argon, nitrogen, argon-hydrogen mixed gas and nitrogen-hydrogen mixed gas.
The invention also provides the NaCrO2The application of the @ metal fluoride/C composite material is used as a positive electrode active material of a sodium ion battery.
The invention also provides a sodium ion battery anode material containing the NaCrO2@ metal fluoride/C composite; also comprises a conductive agent and a binder;
the conductive agent can be a material known in the field of sodium electricity, such as at least one of acetylene black and Super-P, CNT;
the binder may be a material known in the field of sodium electricity, such as at least one of PVdF, PVA, PTFE;
preferably, in the positive electrode material, the weight percentage of the conductive agent is 1-15%; the weight percentage content of the binder is 1-15%; the balance of NaCrO2@ metal fluoride/C composite.
The invention also provides a sodium ion battery comprising the NaCrO2@ metal fluoride/C composite.
Advantageous effects
1. The invention provides a brand new NaCrO2@ MFx/C composite. Researches show that the material composition and the structure can be used for effectively improving the NaCrO due to the synergy of the material composition and the structure2The stability of the material is improved, the problem that surface residual alkali and phase are easy to convert is reduced, the structure and phase stability of the material are improved, and the multiplying power and the cycling stability of the material in a sodium ion battery are improved.
2. The invention also innovatively provides NaCrO2The coating strategy is innovatively based on the coordination of a fluorine carbon source and an M source and the synergistic combination of the two-stage gradient sintering mechanism, and can effectively solve the problem of NaCrO2The method has the problems of residual alkali, easy phase transformation and the like, and is beneficial to preparing the material with a brand new structure and excellent multiplying power and cycling stability.
Drawings
FIG. 1 is a schematic view of an embodimentNaCrO product from example 12@LaF3FESEM image and XRD image magnified 20000 times for/C.
FIG. 2 shows NaCrO in example 12Composition cell and product NaCrO of example 12@LaF3Comparative cycle performance of the/C composition battery at 2C rate.
FIG. 3 is a graph of rate capability at 0.2C, 0.5C, 1C, 2C, 5C, 10C, 15C, 20C rates for the product of example 1.
Fig. 4 is a graph of the first charge and discharge at 2C rate of the product of example 2.
FIG. 5 is a graph of the cycle performance at 2C rate for the product of example 3.
FIG. 6 is a graph of rate performance at 0.2C, 0.5C, 1C, 2C, 5C, 10C, 15C, 20C rate for the product of example 3.
FIG. 7 is a graph of the cycle performance at 2C rate for the product of example 4.
FIG. 8 is a graph of rate capability at 0.5C, 1C, 2C, 5C, 10C, 15C, 20C, 0.1C rate for the product of example 5.
Fig. 9 is a graph of discharge capacity versus voltage at 2C rate for the 1 st, 10 th, 50 th and 100 th circles of the product of example 6.
FIG. 10 is a graph of the cycle performance at 2C rate for the product of comparative example 1.
FIG. 11 is a graph of the cycle performance at 2C rate for the product of comparative example 2.
FIG. 12 is a graph of the cycle performance at 2C rate for the product of comparative example 3.
Detailed Description
In the following cases, the atmosphere of the sintering process is Ar unless otherwise stated.
The testing process of the anode material comprises the following steps: the material is made into a CR2025 button cell for charge and discharge cycle test. Preparing an electrode by adopting a coating method, taking N-methyl-2-pyrrolidone (NMP) as a solvent, respectively weighing active substances, acetylene black and PVdF according to a mass ratio of 8:1:1, uniformly mixing, coating on a pretreated aluminum foil, and drying in a vacuum drying oven at 120 ℃ to obtain the positive plate. In a glove box filled with argon, a metal sodium sheet is taken as a negative electrode, and 1 mol.L-1NaClO4And (3) dissolving Propylene Carbonate (PC) and fluoroethylene carbonate (FEC) as electrolyte, and using GF/D glass fiber as a diaphragm to assemble the CR2025 button cell, finally sealing the cell by using a sealing machine, and performing electrochemical test on a Land electrochemical instrument, wherein the charge-discharge voltage is 2.3-3.6V, and the 1C is 120 mA/g.
Example 1
2g of NaCrO are taken20.0355g of PVdF and 0.0071g of La were added2(CO3)3Grinding uniformly, keeping the temperature at 400 ℃ for 2h, heating to 650 ℃ and sintering for 2h to obtain NaCrO2@LaF3the/C composite (FESEM see example FIG. 1). As can be seen from the FESEM image, the composite material after surface fluorination treatment has a coating compounded in situ on the surface, and the coating is carbon, La fluoride and NaCrO generated after pyrolysis2The surface residual alkali is fluorinated to form NaF complex. Examples shown in FIG. 2 are NaCrO2Comparing the performance of the fluorinated composite material with that of the fluorinated composite material at 100 cycles of 2C, the NaCrO can be seen2The retention after 100 cycles at 2C rate was 81.26%, while NaCrO2@LaF3The circulation retention rate of the/C composite material at 2C multiplying power of 100 circles is as high as 97.65 percent and is far higher than that of NaCrO2A material; shown in FIG. 3 is NaCrO2@LaF3The first discharge specific capacity of the/C composite material under 0.2C, 0.5C, 1C, 2C, 5C, 10C, 15C and 20C is 123.7mAh/g, 119mAh/g, 118.2mAh/g, 117.6mAh/g, 117mAh/g, 116.6mAh/g and 115.9mAh/g respectively, and the multiplying power performance is excellent.
Example 2
Taking 2g of NaCrO20.0374g PTFE and 0.0142g La were added2(CO3)3Grinding uniformly, keeping the temperature at 350 ℃ for 2h, heating to 600 ℃ and sintering for 2h to obtain NaCrO2@LaF3a/C composite material. The material has the first discharge capacity of 124.8mAh/g under 0.2C multiplying power, the first discharge capacity of 121.8mAh/g under 2C multiplying power (see figure 4), the discharge capacity of 112.5mAh/g after circulation for 100 circles under 2C multiplying power, the capacity retention rate of 92.36 percent, and the cycle performance is obviously improved compared with that of a bare material.
Example 3
Taking 2g of NaCrO20.0349g of PVdF and 0.1019g of SrCO were added3Grinding uniformly, keeping the temperature at 400 ℃ for 2h, heating to 600 ℃ and sintering for 4h to obtain NaCrO2@SrF2a/C composite material; in the embodiment, FIG. 5 shows that the material has a specific discharge capacity of 106.3mAh/g after 100 times of cycling under a 2C multiplying power, and the cycling retention rate is 90.24%; shown in FIG. 6 is NaCrO2@SrF2The first discharge curve of the/C composite material at 0.5C, 1C, 2C, 5C, 10C, 15C and 20C shows that the rate capability is excellent.
Example 4
Taking 2g of NaCrO20.0184g of PTFE and 0.1019g of SrCO were added3Grinding uniformly, keeping the temperature at 400 ℃ for 2h, heating to 650 ℃ and sintering for 2h to obtain NaCrO2@SrF2a/C composite material. In the embodiment, fig. 7 shows that the first discharge capacity of the material is 119.4mAh/g at a rate of 0.2C, the first discharge capacity is 117.5mAh/g at a rate of 2C, the discharge capacity is 108.1mAh/g after the material is cycled for 100 circles at a rate of 2C, the capacity retention rate is 92.00%, and the cycle performance is obviously improved compared with that of a bare material.
Example 5
Taking 2g of NaCrO20.0195g of PVdF and 0.0283g Y were added2(CO3)3·3H2Grinding the mixture evenly, keeping the temperature at 450 ℃ for 4h, heating the mixture to 700 ℃ and sintering the mixture for 4h to obtain NaCrO2@YF3the/C composite, examples shown in FIG. 8 are NaCrO2@YF3The first discharge specific capacity of the/C composite material under the multiplying power of 0.5C, 1C, 2C, 5C, 10C, 15C, 20C and 0.1C is respectively 114.9mAh/g, 114.4mAh/g, 113.3mAh/g, 110.7mAh/g, 107.3mAh/g, 103.3mAh/g, 96.9mAh/g and 104.5mAh/g, and the multiplying power performance is better.
Example 6
Taking 2g of NaCrO20.0161g of PTFE and 0.0187g of Mg (OH) were added2Grinding uniformly, keeping the temperature at 450 ℃ for 2h, heating to 750 ℃ and sintering for 2h to obtain NaCrO2@MgF3a/C composite material. Example shown in FIG. 9 is NaCrO2@MgF2Discharge capacity-voltage diagram of the/C composite material at 1 st circle, 10 th circle, 50 th circle and 100 th circle under 2C multiplying power,the discharge capacities of the material at the 1 st circle, the 10 th circle, the 50 th circle and the 100 th circle are respectively 116.0mAh/g, 115.5mAh/g, 112.4mAh/g and 106.7mAh/g, the capacity retention rate at the 100 th circle is 91.98%, and the cycle performance is good.
Comparative example 1
NaCrO without surface treatment2The assembled CR2025 button cell is tested for cycle performance at 2C rate. FIG. 10 shows NaCrO2The circulation diagram of the bare material circulating 100 circles under the 2C multiplying power shows that the initial capacity of the bare material is 118.4mAh/g, and the capacity retention rate is only 81.26% when the capacity is attenuated to 100.6mAh/g after 100 circles of circulation.
Comparative example 2
Compared with the embodiment 1, the difference is that the metal fluoride is not embedded in the coating layer in situ, and specifically comprises the following components:
adding 0.01g of beta-cyclodextrin into 2g of NaCrO2, grinding uniformly, keeping the temperature at 450 ℃ for 2h in Ar atmosphere, heating to 750 ℃ and sintering for 2h to obtain NaCrO2/C1Composite material, shown in FIG. 11 is NaCrO2/C1The cycle diagram of 100 cycles of the cycle under the 2C multiplying power shows that the initial capacity of the bare material is 117.6mAh/g, and after 100 cycles of the cycle, the capacity is attenuated to 102.6mAh/g, the capacity retention rate is 87.24%, and because of the protection of the carbon layer, the occurrence of side reactions between the electrolyte and the active substance can be reduced, so that the cycle performance of the material is enhanced.
Comparative example 3
Compared with the embodiment 1, the difference is that the metal fluoride is not embedded in the coating layer in situ, and specifically comprises the following components: adding 0.01g of PVdF into 2g of NaCrO2, grinding uniformly, keeping the temperature at 450 ℃ for 2h, heating to 750 ℃ and sintering for 2h to obtain NaCrO2/C2Composite material, shown in FIG. 12 is NaCrO2The material obtained after the PVdF is independently added is circulated for 100 circles under the multiplying power of 2C, carbon generated by pyrolysis of the PVdF at high temperature is dispersed and distributed on the surface of the material to enhance the circulation performance, and reacts with surface residual alkali to generate NaF, partial residual alkali is eliminated, and NaCrO can be seen2/C2The retention rate after 100 cycles at 2C multiplying power is 90.33 percent, and the cycle is relative to NaCrO2And NaCrO2/C1Is improved but is less than NaCrO2@LaF3And C, material.
Claims (10)
1. NaCrO2@ MFx/C composite; the material is characterized by comprising a base material and a coating material coated on the surface of the base material in situ, wherein the base material is NaCrO2(ii) a The coating material comprises a carbon material and metal fluoride MFx uniformly dispersed in the carbon material; the M comprises at least one of alkaline earth metal elements and rare earth metal elements; and x is the valence of the metal element.
2. NaCrO according to claim 12@ metal fluoride/C composite; characterized in that M comprises at least one of Mg, Ca, Sr, La, Y and Ba;
preferably, the carbon material is an amorphous carbon material; preferably a fluorine doped amorphous carbon material; further preferably a fluoropolymer pyrolyzed carbon material;
preferably, the content of the metal fluoride in the composite material is 0.3-3 wt.%, and the content of the carbon is 0.5-5 wt.%.
3. NaCrO according to claim 1 or 22A preparation method of the @ metal fluoride/C composite material; characterized in that NaCrO is added2Mixing with a fluorine carbon source and an M source, and then performing two-stage gradient sintering under a protective atmosphere to obtain the fluorine carbon source;
in the two-stage gradient sintering, the temperature of the first-stage sintering is 350-450 ℃; the temperature of the second-stage sintering is 550-750 ℃.
4. NaCrO according to claim 32A preparation method of the @ metal fluoride/C composite material; the method is characterized in that the fluorine carbon source is a fluorine-containing polymer;
preferably, the fluorine-containing polymer is at least one of polyvinyl fluoride, polyvinylidene fluoride and polytetrafluoroethylene.
5. As claimed in claim 3The NaCrO2A preparation method of the @ metal fluoride/C composite material; the M source is at least one of hydroxide, carbonate, bicarbonate, nitrate and carboxylate of M metal.
6. NaCrO according to claim 32A preparation method of the @ metal fluoride/C composite material; characterized in that NaCrO2And the mass ratio of the fluorine carbon source to the M source is 1: 0.7% -7%: 0.3 to 3 percent.
7. NaCrO according to claim 32A preparation method of the @ metal fluoride/C composite material; it is characterized in that in the two-stage gradient sintering process, the protective atmosphere is an oxygen-free atmosphere; preferably at least one of inert gas, nitrogen and hydrogen; further preferred are argon, nitrogen, an argon-hydrogen mixed gas, a nitrogen-hydrogen mixed gas;
preferably, the temperature of the first-stage sintering is 400-450 ℃;
preferably, the temperature of the second-stage sintering is 550-650 ℃.
8. NaCrO according to claim 1 or 22@ metal fluoride/C composite material or NaCrO prepared by preparation method of any one of claims 3 to 72Use of a @ metal fluoride/C composite material, characterized in that it is used as a positive electrode active material for a sodium ion battery.
9. A positive electrode material for sodium ion batteries, comprising the NaCrO according to any one of claims 1 to 22@ metal fluoride/C composite material or NaCrO prepared by preparation method of any one of claims 3 to 72@ metal fluoride/C composite; also comprises a conductive agent and a binder;
preferably, the conductive agent is at least one of acetylene black and Super-P, CNT;
preferably, the binder is at least one of PVdF, PVA, and PTFE;
preferably, n isIn the electrode material, the weight percentage content of the conductive agent is 1-15%; the weight percentage content of the binder is 1-15%; the balance of NaCrO2@ metal fluoride/C composite.
10. A sodium ion battery comprising the NaCrO according to any one of claims 1 to 22@ metal fluoride/C composite material or NaCrO prepared by preparation method of any one of claims 3 to 72@ metal fluoride/C composite;
preferably, the positive electrode material of the sodium-ion battery of claim 9 is contained.
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| CN114597389A (en) * | 2022-01-25 | 2022-06-07 | 中南大学 | NaCrO2@ fluorophosphate transition metal sodium/C composite material, preparation method thereof and application thereof in sodium-ion battery |
| WO2023151459A1 (en) * | 2022-02-10 | 2023-08-17 | 深圳市德方创域新能源科技有限公司 | Lithium-supplementing additive, and preparation method therefor and application thereof |
| CN114975847A (en) * | 2022-07-07 | 2022-08-30 | 中南大学 | Composite metal negative electrode with sandwich structure and preparation method and application thereof |
| CN114975847B (en) * | 2022-07-07 | 2024-02-27 | 中南大学 | Composite metal negative electrode with sandwich structure and preparation method and application thereof |
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