CN111268746A - Layered positive electrode material of sodium-ion battery, preparation method and application thereof - Google Patents
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Abstract
Sodium-ion battery layered positive electrode material, preparation method and application thereof, wherein the sodium-ion battery layered positive electrode material is NaNi0.5‑x‑yBxCyMn0.5‑zAzO2The A is selected from one of Sn, Ti, Nb, Sb and Bi, and z is more than or equal to 0.02 and less than or equal to 0.08; b is selected from one of Cu or Li, and x is more than or equal to 0.05 and less than or equal to 0.15; c is selected from one of Mg, Ca and Ba, and y is more than or equal to 0.05 and less than or equal to 0.12. The anode material prepared by the invention is doped with metal with the same valence state or lower valence state and difficult to be oxidized again to replace the original metalThe Ni position is found to be replaced by the Ni position, so that the structural stability of the layered positive electrode material is better, and the prepared battery has excellent long-cycle performance and transmission dynamic performance. The anode material prepared by the invention has good rate performance and cycling stability. The preparation method of the anode material is simple, environment-friendly and pollution-free, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a layered positive electrode material of a sodium-ion battery, a preparation method and application thereof.
Background
The lithium ion battery is a new-generation green environment-friendly battery, and is widely used in the fields of mobile phones, computers, electric automobiles and the like at present, but the lithium element in the earth crust is less in storage amount and high in price, so that the lithium ion battery is rather embarrassing. Sodium is an element with similar physicochemical properties to lithium, is widely distributed (the abundance in the earth crust is 2.3-2.8% and is about 12500 times of that of lithium element), is low in price, and has greater natural advantages and sustainable development potential compared with two batteries.
Since 2010, most of the research on sodium ion batteries has focused on the research on positive electrode materials. The positive electrode material of the sodium ion battery is similar to that of the lithium ion battery, and plays a crucial role in the research of a sodium ion electrochemical system. Layered transition metal oxide NaAO2The material is the most researched positive electrode material of the sodium-ion battery, and has the advantages of high energy density, high specific capacity, high electronic conductivity, simple preparation method and the like, but the material is extremely unstable in the air in the practical application process, so that the cost is increased in the processes of material synthesis, transportation and battery assembly. In addition, because the difference between the radius of the sodium ions and the radius of the transition metal is large, the layered oxide is easy to generate the problems of phase structure change and the like in the charging and discharging processes, so that the structural stability and the electrochemical cycle performance of the anode material are poor, and the large-scale application of the anode material is greatly limited. Patent CN201610978502.0 discloses a sodium ion battery anode material, a preparation method thereof and a method for improving air stability, wherein the anode material is a trigonal system NaA1-x-yBxCyO2By means of doping. And metal B which has the same or lower valence state than two elements in A and is difficult to oxidize again and metal C which has an oxidation-reduction potential difference value of more than 1V with two metals in A in the cathode material are doped in the preparation process of the cathode material, so that the cathode material has better air stability. Wherein A is a compound having2 electrochemically active transition metals Ni and Mn; b is Cu; c is selected from Sn or Ti; the doping amount of the metal B is more than or equal to 0.05 and less than or equal to x and less than or equal to 0.25, the doping amount of the metal C is more than or equal to 0.1 and less than or equal to y and less than or equal to 0.3, and the positive electrode material NaA1-x-yBxCyO2Can be expressed as NaDzE1-x-y-zBxCyO2The patent significantly improves the NaAO by means of metal doping2Although the patent of air stability of positive electrode material solves the problem of air stability of positive electrode material, the problem of poor long cycle performance and poor transport kinetics due to the poor structural stability is particularly obvious, so that a technical scheme for improving the long cycle performance and the transport kinetics of the positive electrode material is needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and particularly provides NaNi0.5-x- yBxCyMn0.5-zAzO2The layered positive electrode material of the sodium-ion battery solves the problem that the long cycle performance and the transmission dynamic performance of the positive electrode material are poor.
The invention provides a layered positive electrode material of a sodium-ion battery, which is characterized in that the layered positive electrode material of the sodium-ion battery is NaNi0.5-x-yBxCyMn0.5-zAzO2The A is selected from one of Sn, Ti, Nb, Sb and Bi, and z is more than or equal to 0.02 and less than or equal to 0.08; b is selected from one of Cu or Li, and x is more than or equal to 0.05 and less than or equal to 0.15; c is selected from one of Mg, Ca and Ba, and y is more than or equal to 0.05 and less than or equal to 0.12.
The cation order in the layered positive electrode material is mainly related to the radius of cations in the transition metal layer, and the closer the two kinds of ion radii are, the more the cations tend to be arranged in disorder. The charge order and the sodium vacancy order are mainly related to the Fermi level between cations or related to oxidation-reduction potential, so that the relationship between ion charge and radius is comprehensively considered.
The inventor unexpectedly discovers that the C element is doped in the layered cathode material NaNi0.5-x-yBxCyMn0.5-zAzO2The Ni position of the anode material can play a role in nail pricking, so that the stability of a laminated structure is improved, and the long cycle performance of the anode material is further improved.
Preferably 0.05. ltoreq. x.ltoreq.0.1, 0.05. ltoreq. y.ltoreq.0.1, 0.02. ltoreq. z.ltoreq.0.05.
Preferably, the C is Mg, the B is Li, and the A is one selected from Nb and Sb.
The Mg-doped magnesium source raw material is at least one selected from magnesium salts of organic acids, metal oxides of magnesium, hydroxides of magnesium and inorganic salts of magnesium.
Preferably, the magnesium salt of the organic acid is at least one selected from magnesium acetate, magnesium laurate and magnesium salicylate. The inventors have unexpectedly found that the use of a magnesium salt of an organic acid as a magnesium source doped with magnesium significantly improves the air stability of the positive electrode material and thus the long cycle stability of the assembled cell.
The anode material is blocky particles with the particle size of 5-10 mu m.
It is a second object of the present invention to provide a NaAO2The preparation method of the layered positive electrode material of the sodium-ion battery comprises the following steps:
mixing the raw material components according to a ratio, performing two-stage sintering of pre-sintering and high-temperature sintering, and cooling to room temperature to obtain the layered positive electrode material.
The mixing manner is not particularly limited, and includes manual mixing or mechanical mixing, and specifically at least one selected from mechanical ball milling, manual grinding, and mechanical grinding.
The sintering gas atmosphere is air or oxygen.
The two-stage sintering comprises presintering and high-temperature sintering, wherein the presintering adopts a heating rate of 2-10 ℃/min, a presintering temperature of 400-; the heating rate of the high-temperature sintering is 2-10 ℃/min, the temperature is 900-1200 ℃, and the heat preservation time is 10-15 h.
The step sintering is to ensure the full sintering of the precursor and prepare for the subsequent high-temperature sintering.
Preferably, the pre-sintering temperature is 450-550 ℃, and the heat preservation time is 6-8 h; the temperature of the high-temperature sintering is 950-.
The cooling mode is furnace cooling.
The invention also provides an application of the layered positive electrode material of the sodium-ion battery, and the layered positive electrode material of the sodium-ion battery is used as the positive electrode material of the battery to prepare a room-temperature liquid sodium-ion battery or a solid sodium-ion battery.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the anode material prepared by the invention is doped with metal which has the same valence state or lower valence state and is not easy to oxidize again to replace the original Ni position, the layered anode material with the replaced Ni position is found to have better stability, and the prepared anode material has excellent long-cycle performance and transmission dynamic performance.
The inventors unexpectedly found that by using a magnesium salt of an organic acid as a magnesium source doped with magnesium, the air stability of the battery of the obtained cathode material is significantly improved, and further, the cycle stability of the battery operation is significantly improved.
And thirdly, the battery prepared by the anode material prepared by the invention has good rate capability and cycling stability.
And fourthly, the preparation method of the cathode material is simple, environment-friendly and pollution-free, and is suitable for large-scale production.
Drawings
Fig. 1 is a charge and discharge curve of a battery prepared in application example 1;
FIG. 2 is a graph showing rate performance of a battery prepared in application example 1;
fig. 3 is a charge-discharge curve of the battery prepared in application example 1 at different rates;
FIG. 4 is a cyclic voltammogram at different scan rates for the cell prepared in application example 1;
FIG. 5 is a linear fit plot for different scan rates for the cell prepared in application example 1;
fig. 6 is a graph of high rate cycle performance of the battery prepared in application example 1;
FIG. 7 shows NaNi prepared in example 10.3Li0.1Mg0.1Mn0.45Nb0.05O2SEM picture of the positive electrode material.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the descriptions in the following. All reagents used are commercially available in the art.
Example 1
Firstly, preparing anode material NaNi0.3Li0.1Mg0.1Mn0.45Nb0.05O2
Accurately weighing raw material Na with purity of more than 99 percent in corresponding proportion2CO3、NiO、Mn2O3、LiOH、(CH3COOH)2Mg、Nb2O5Adding the mixture into a ball mill, mechanically milling for 24 hours, pressing the obtained powder into a wafer with the diameter of 14mm under the pressure of 10MPa, and presintering the wafer at the early stage by adopting the temperature rise rate of 5 ℃/min, the presintering temperature of 500 ℃ and the heat preservation time of 8 hours; and then, carrying out post-sintering on the wafer at the heating rate of 3 ℃/min, the temperature of 1000 ℃ and the heat preservation time of 12h, and finally cooling to room temperature along with the furnace to obtain the black powdery anode material.
(II) preparation of NaNi0.3Li0.1Mg0.1Mn0.45Nb0.05O2Composite positive electrode
And (2) mixing the positive electrode material prepared in the step (I), Super P and a binding agent polyvinylidene fluoride according to the mass ratio of 0.7:0.2:0.1, adding a solvent N-methyl pyrrolidone, and carrying out pulping, smearing, drying and other process flows to obtain the composite positive electrode.
(III) assembling the sodium-ion battery
The compound prepared in the step (two)The positive electrode and the metal sodium negative electrode are assembled into a sodium ion battery, and the electrolyte contains NaClO4The concentration of the composite material is 1mol/L, the solvent is a mixed solvent of Propylene Carbonate (PC) and fluoroethylene carbonate (FEC) with the volume ratio of 95:5, a porous glass fiber diaphragm (whatman, GF/D) is adopted as the diaphragm, and a button cell is assembled in an argon glove box with the water oxygen value lower than 0.1ppm and electrochemical test is carried out.
Example 2
The rest is the same as the example 1, except that the doping amount of magnesium of the cathode material prepared in the step (I) is 5 percent, 5 percent refers to the mole percentage of magnesium element in the total transition metal elements, and the prepared cathode material is NaNi0.35Li0.1Mg0.05Mn0.45Nb0.05O2。
Example 3
The rest is the same as the example 1, except that the lithium doping amount of the cathode material prepared in the step (I) is 5%, and the prepared cathode material is NaNi0.35Li0.05Mg0.1Mn0.45Nb0.05O2。
Example 4
The rest is the same as the example 1, except that the doping amount of the niobium of the cathode material prepared in the step (I) is 2 percent, and the prepared cathode material is NaNi0.3Li0.1Mg0.1Mn0.48Nb0.02O2。
Example 5
The rest is the same as the example 1, except that the magnesium doping amount of the cathode material prepared in the step (I) is 12 percent, and the prepared cathode material is NaNi0.28Li0.1Mg0.12Mn0.45Nb0.05O2。
Example 6
The rest is the same as the example 1, except that the lithium doping amount of the cathode material prepared in the step (I) is 15%, and the prepared cathode material is NaNi0.25Li0.15Mg0.1Mn0.45Nb0.05O2。
Example 7
The rest is the same as the example 1, except that the doping amount of the niobium of the cathode material prepared in the step (I) is 8 percent, and the prepared cathode material is NaNi0.3Li0.1Mg0.1Mn0.42Nb0.08O2。
Example 8
The same as example 1 except that Sb was used as a raw material2O3Replacing Nb2O5The prepared anode material is NaNi0.3Li0.1Mg0.1Mn0.45Sb0.05O2。
Example 9
The same as example 1 except that the raw material was CaO instead of magnesium acetate, and that a cathode material was NaNi0.3Li0.1Ca0.1Mn0.45Sb0.05O2。
Example 10
The same as example 1 except that magnesium acetate was replaced with magnesium laurate as a raw material, and a cathode material prepared using the same was NaNi0.3Li0.1Ca0.1Mn0.45Sb0.05O2。
Example 11
The other steps are the same as example 1, except that magnesium acetate is replaced by magnesium salicylate, and the prepared cathode material is NaNi0.3Li0.1Ca0.1Mn0.45Sb0.05O2。
Example 12
The same as example 1 except that MgO was used in place of magnesium acetate to prepare a cathode material of NaNi0.3Li0.1Ca0.1Mn0.45Sb0.05O2。
Example 13
The same as example 1 except that magnesium acetate was replaced with magnesium hydroxide, and a cathode material prepared was NaNi0.3Li0.1Ca0.1Mn0.45Sb0.05O2。
Example 14
The same as example 1 except that magnesium acetate was replaced with magnesium carbonate, and a cathode material prepared was NaNi0.3Li0.1Ca0.1Mn0.45Sb0.05O2。
Comparative example 1
The same as example 1 except that magnesium acetate was not contained in the raw material, and that NaNi was used as the positive electrode material0.4Li0.1Mn0.45Nb0.05O2。
Comparative example 2
The same as example 1 except that Nb was not contained in the raw material2O5The prepared anode material is NaNi0.3Li0.1Mg0.1Mn0.5O2。
Application example
The sodium ion batteries prepared in the above examples and comparative examples were subjected to the following performance tests:
1. the test voltage was between 2 and 4V and the charge and discharge performance was measured at a current of 0.2C (1C 120mA/g), and the results are shown in fig. 1.
2. Different multiplying power charge-discharge performance
The test voltage is between 2 and 4V, and the current is 0.2C (1C 120mA/g), the charge and discharge performance under 0.3C, 0.5C, 1C, 2C, 3C, 5C and 10C, and the results are shown in figure 2, figure 3 and table 1.
3. Dynamic performance test of sodium ion
The test voltage is between 2 and 4V, the cyclic voltammetry is performed under the conditions of 0.2mV/s, 0.4mV/s, 0.5mV/s, 0.8mV/s and 1mV/s scanning rate, a linear fitting point line graph is obtained according to the peak current vs of the polar peak and the square root of the scanning rate, and then the sodium ion diffusion coefficient is obtained by calculation, and the result is shown in Table 1.
4. Stability of charge and discharge cycle
The cycle life curve in 5C charge, 5C discharge mode, discharge capacity retention after 1000 cycles, results are shown in fig. 6 and table 1.
TABLE 1
Capacity retention rateaThe air stability of the anode material is tested, and specifically the capacity retention rate of the prepared anode material tested after the anode material is placed in the air for 2 days
Fig. 1 is a charge-discharge test curve of a battery prepared by the cathode material prepared in example 1 of the present invention at a voltage of 2 to 4V and with a current of 0.2C, which shows that the cathode material prepared in the present invention has good charge-discharge performance and high specific discharge capacity, the specific discharge capacity of example 1 is up to 132.1mA h/g, and the coulombic efficiency is up to 98.26%.
Fig. 6 is a cycle life curve of the battery prepared from the cathode material prepared in example 1 in the 5C charging and 5C discharging mode, and it can be seen from the data in table 1 and fig. 6 that the battery prepared in the example of the present invention has excellent long cycle stability at a high rate, and the capacity retention rate of the battery is high and the coulombic efficiency is very stable after 1000 cycles compared with the comparative example.
Fig. 2 and 3 show the battery cycle performance of the positive electrode material prepared in example 1 of the present invention at different rates, specifically, 5 times of cycle charging and discharging at rates of 0.2C, 0.3C, 0.5C, 1C, 2C, 3C, 5C, and 10C, respectively. The discharge specific capacities are 129.7mA h/g, 121.2mA h/g, 116.1mA h/g, 109.2mA h/g, 106.2mA h/g, 104.0mA h/g, 101.2mA h/g and 95.4mA h/g respectively, the capacity retention rate of 10C relative to 0.2C is 73.55%, and the excellent rate performance is shown.
With reference to fig. 4, fig. 5 and table 1, it can be seen that the positive electrode material prepared by the present invention has a high sodium ion diffusion coefficient, and particularly, the sodium ion diffusion coefficient of example 1 is as high as 1.578 × 10-11cm2·s-1The higher diffusion coefficient of sodium ions further proves the conclusion that the rate performance of the battery prepared from the cathode material prepared by the invention is good.
Fig. 7 is an SEM image of a battery prepared by preparing the cathode material according to example 1 of the present invention, and it can be observed that the cathode material is in the form of bulk particles with a size distribution of 5-10 μm.
In conclusion, the anode material prepared by the invention has the advantages that the original position of Ni is replaced by the metal which is doped with the same valence state or lower valence state and is not easy to be oxidized again, the composite layered anode material which replaces Ni has good stability, and the long cycle performance and the transmission dynamic performance of the anode material are further improved.
The preparation method of the cathode material is simple, environment-friendly and pollution-free, and is suitable for large-scale production.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (10)
1. The layered positive electrode material of the sodium-ion battery is characterized by being NaNi0.5-x-yBxCyMn0.5-zAzO2The A is selected from one of Sn, Ti, Nb, Sb and Bi, and z is more than or equal to 0.02 and less than or equal to 0.08; b is selected from one of Cu or Li, and x is more than or equal to 0.05 and less than or equal to 0.15; c is selected from one of Mg, Ca and Ba, and y is more than or equal to 0.05 and less than or equal to 0.12.
2. The layered positive electrode material according to claim 1, wherein x is 0.05. ltoreq. x.ltoreq.0.1, y is 0.05. ltoreq. y.ltoreq.0.1, and z is 0.02. ltoreq. z.ltoreq.0.05.
3. The layered positive electrode material according to claim 1, wherein C is Mg, B is Li, and A is one selected from Nb and Sb.
4. The layered positive electrode material according to claim 1, wherein the Mg is at least one of a magnesium salt of an organic acid, a metal oxide of magnesium, a hydroxide of magnesium, and an inorganic salt of magnesium as a raw material.
5. The layered positive electrode material according to claim 4, wherein the Mg-doped magnesium material is a magnesium salt of an organic acid, specifically at least one selected from the group consisting of magnesium acetate, magnesium laurate and magnesium salicylate.
6. The layered positive electrode material according to claim 1, wherein the positive electrode material is a bulk particle having a particle diameter of 5 μm to 10 μm.
7. The method for preparing the layered positive electrode material of the sodium-ion battery as claimed in any one of claims 1 to 6, comprising the steps of: mixing the raw material components according to a ratio, performing two-stage sintering of pre-sintering and high-temperature sintering, and cooling to room temperature to obtain the layered positive electrode material.
8. The preparation method according to claim 7, wherein the pre-sintering is performed at a temperature rise rate of 2-10 ℃/min, a pre-sintering temperature of 400-; the heating rate of the high-temperature sintering is 2-10 ℃/min, the temperature is 900-1200 ℃, and the heat preservation time is 10-15 h.
9. The method as claimed in claim 8, wherein the pre-sintering temperature is 450-550 ℃, and the holding time is 6-8 h; the temperature of the high-temperature sintering is 950-.
10. The application of the layered positive electrode material of the sodium-ion battery as claimed in any one of claims 1 to 6, wherein the layered positive electrode material of the sodium-ion battery is used as a positive electrode material of the battery to prepare a room-temperature liquid sodium-ion battery or a solid sodium-ion battery.
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| CN113113589A (en) * | 2021-04-09 | 2021-07-13 | 福建师范大学 | Method for improving superlattice structure of sodium ion layered positive electrode material |
| CN113540440A (en) * | 2021-06-29 | 2021-10-22 | 福建师范大学 | Method for improving air stability of sodium-electricity layered metal oxide ordered structure |
| CN115043441A (en) * | 2022-07-28 | 2022-09-13 | 温州大学碳中和技术创新研究院 | Preparation method of layered oxide positive electrode material based on three-phase heterogeneous symbiotic structure and sodium ion battery |
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