CN114520323A - Double-strategy modified layered oxide sodium ion battery positive electrode material and preparation method and application thereof - Google Patents

Double-strategy modified layered oxide sodium ion battery positive electrode material and preparation method and application thereof Download PDF

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CN114520323A
CN114520323A CN202210291367.8A CN202210291367A CN114520323A CN 114520323 A CN114520323 A CN 114520323A CN 202210291367 A CN202210291367 A CN 202210291367A CN 114520323 A CN114520323 A CN 114520323A
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sodium
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章根强
万广林
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University of Science and Technology of China USTC
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Abstract

The invention provides a dual-strategy modified layered oxide sodium-ion battery anode material and a preparation method and application thereof, wherein the anode material is prepared by Mg2+Doped synergetic ZrO2Surface modified double-surfaceSlightly opposite to P2 type nickel manganese base layered transition metal oxide Na0.67Ni0.33Mn0.67O2Is modified to obtain the compound with the chemical formula of Na0.67Ni0.33‑xMgxMn0.67O2‑n％ZrO2，0<x<0.2, 0-3% of n%, where n% represents ZrO2Mass percent in the positive electrode material of the sodium-ion battery. The positive electrode material provided by the invention has the advantages of high working voltage, stable structure, good cycling stability, good rate capability under large current density and the like, and has good application prospect in the positive electrode material of the sodium-ion battery.

Description

Double-strategy modified layered oxide sodium ion battery positive electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a dual-strategy modified layered oxide sodium-ion battery positive electrode material, and a preparation method and application thereof.
Background
Energy has been a hot issue of people's attention as one of three major pillars for civilized development of human society. Due to exhaustion of traditional non-renewable fossil energy such as coal and petroleum, people pay more and more attention to renewable energy such as wind energy, solar energy and hydropower. Unfortunately, such renewable energy sources are characterized by locality and discontinuity, which cannot be directly incorporated into the grid, requiring storage with energy storage devices. In recent years, due to the high abundance of sodium and the similar working principle of the lithium ion battery, the demand for the sodium ion battery in the field of energy storage is higher and higher, and the sodium ion battery is considered as the most promising next-generation energy storage device behind the lithium ion battery. The layered oxide material is used as a very important positive electrode material in a sodium ion battery, and has an important position in scientific research and industry due to high voltage and specific capacity, simple synthesis process and good tap (compaction) density, but the cycling stability of the layered oxide material is still poor.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a Mg2+Doped synergetic ZrO2The surface-modified double-strategy-modified layered oxide sodium ion battery cathode material has the advantages of high working voltage, excellent cycling stability and good rate capability, and the preparation method is simple, high in yield and low in cost.
In order to realize the purpose, the invention adopts the following technical scheme:
the invention firstly provides a dual-strategy modified layered oxide positive electrode material of a sodium ion battery, which is prepared by Mg2+Doped synergetic ZrO2Surface modified double-strategy P2 type Ni-Mn based layered transition metal oxide Na0.67Ni0.33Mn0.67O2Is modified to obtain; the chemical formula of the positive electrode material of the sodium-ion battery is Na0.67Ni0.33- xMgxMn0.67O2-n％ZrO2，0<x<0.2, 0. ltoreq. N.ltoreq.3, N represents ZrO2Mass percent in the positive electrode material of the sodium-ion battery. Preferably 0<x<0.15, 0.5% to n% to 2%, more preferably 0.5% to n% to 2%<x<N is more than or equal to 0.1 and 1 percent and less than or equal to 2 percent. The positive electrode material of the sodium ion battery is ZrO2Surface modified Mg2+The doped layered oxide particle material is characterized in that the particle size of the particles is 2-5 mu m.
The invention also provides a preparation method of the sodium-ion battery positive electrode material, which is prepared by combining a sol-gel method with a wet chemical method and comprises the following steps:
A) dissolving a sodium source compound, a nickel source compound, a magnesium source compound and a manganese source compound with a chelating agent in water according to a molar ratio, and heating to volatilize a solvent to obtain a gel precursor;
B) drying the gel precursor and then grinding to obtain precursor powder;
C) calcining the precursor powder in two steps in sequence to obtain Mg2+Doped P2 type Ni-Mn based layered transition metal oxide Na0.67Ni0.33-xMgxMn0.67O2；
D) Dispersing the product obtained in the step C) in ethanol, then adding a zirconium source compound with a corresponding mass percentage, stirring and heating to volatilize the solvent to obtain mixture powder;
E) grinding the mixture powder, and then calcining the mixture powder to obtain ZrO2And carrying out surface modification to obtain the target product, namely the sodium-ion battery positive electrode material.
Preferably: the sodium source compound is selected from one or more of sodium acetate, sodium nitrate, sodium oxalate and sodium citrate; the nickel source compound is selected from one or more of nickel acetate, nickel nitrate, nickel oxalate, nickel sulfate and nickel chloride; the magnesium source compound is selected from one or more of magnesium acetate, magnesium nitrate, magnesium oxalate, magnesium sulfate and magnesium chloride; the manganese source compound is selected from one or more of manganese acetate, manganese nitrate, manganese oxalate, manganese sulfate and manganese chloride; the zirconium source compound is selected from one or more of zirconium acetate, zirconium nitrate, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide and zirconium chloride; the chelating agent is selected from citric acid, oxalic acid, tartaric acid or ethylenediamine tetraacetic acid.
Preferably, in step C), the two-step calcination of the precursor powder is performed in an air atmosphere, and is divided into a first-step calcination and a second-step calcination; the heating rate of the first-step calcination is 1-10 ℃/min, the temperature is raised to 350-600 ℃, and the temperature is maintained until organic matters are fully decomposed; and the temperature rise rate of the second step of calcination is 1-10 ℃/min, the temperature is raised to 800-1000 ℃, and the temperature is kept for 10-24 h until a P2 phase structure without impurity phase is formed.
Preferably, in the step E), the one-step calcination of the mixture powder is carried out in an air atmosphere, the heating rate is 1-10 ℃/min, the temperature is increased to 400-600 ℃, and the temperature is kept for 6-10 h until ZrO is formed2A surface modification layer.
The invention also provides a positive plate of the sodium-ion battery, which is prepared from an active positive material, a conductive additive, a binder and a solvent, wherein the active positive material is selected from the dual-strategy modified layered oxide sodium-ion battery positive material. Wherein: the conductive additive can be selected from one or more of Super-P, carbon black and Ketjen black; the binder can be one or more of polyvinylidene fluoride or polyacrylic acid, sodium carboxymethylcellulose and sodium alginate; the solvent can be selected from one of N-methyl pyrrolidone or deionized water.
The invention also provides a preparation method of the sodium ion battery positive plate, which is prepared by mixing the positive material, the conductive additive, the binder and the solvent, smearing and drying. The present invention is not particularly limited to the specific methods for mixing, smearing and drying, and may be any method known to those skilled in the art.
The invention also provides a sodium ion battery, which consists of the positive plate, the diaphragm, the organic electrolyte and the negative metal sodium, wherein the positive plate is the sodium ion battery positive plate adopting the double-strategy modified layered oxide sodium ion battery positive material. The organic electrolyte is a carbonate electrolyte, and the concentration of the carbonate electrolyte is 0.1-2M, preferably 1M. In the organic electrolyte, the solvent can be at least one selected from diethyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate and fluorinated ethylene carbonate, and is preferably a mixed solvent of propylene carbonate and fluorinated ethylene carbonate; the solute is at least one selected from sodium hexafluorophosphate, sodium perchlorate and sodium bistrifluoromethylsulfonyl imide, and is preferably sodium perchlorate. The separator is preferably glass fiber.
The invention also provides application of the sodium ion battery in electric vehicles, solar energy and wind energy power generation, peak regulation of smart power grids, distributed power stations or large-scale energy storage devices of communication bases.
Compared with the prior art, the invention has the beneficial effects that:
1. na provided by the invention0.67Ni0.33-xMgxMn0.67O2-n％ZrO2The compound is used as a modified positive electrode material of the sodium-ion battery, and enriches the material system of the sodium-ion battery.
2. The positive electrode material provided by the invention has the advantages of high working voltage, stable structure, good cycling stability, good rate performance under large current density and the like, is obviously improved compared with the unmodified material, and has good application prospect in the positive electrode material of the sodium-ion battery.
3. The cathode material can be prepared by combining a simple sol-gel method and a wet chemical method, the process is simple and easy to control, mass production is easy to realize, the yield is high, the cost is low, the used raw materials are safe, non-toxic and environment-friendly, and the cathode material has good industrial production potential.
4. Preferred Na of the invention0.67Ni0.28Mg0.05Mn0.67O2-1％ZrO2The combination property is best at 1C (1C is 173mA g-1) The capacity retention rate is 81.5 percent after the cycle is carried out for 150 circles at the multiplying power, the multiplying power performance is excellent, 62.9 percent of initial capacity can be kept at the high multiplying power of 5C, and the method is suitable for large-scale energy storage equipment.
Drawings
FIG. 1 is an XRD spectrum of the target product obtained in example 1.
FIG. 2 is an SEM image of the target product obtained in example 1.
FIG. 3 is a TEM image of the objective product obtained in example 1.
FIG. 4 is a charge-discharge curve of the objective product obtained in example 1 at a current density of 0.1C.
FIG. 5 is a CV curve of the target product obtained in example 1 at a sweep rate of 0.1 mV/s.
FIG. 6 shows the target and Mg alone obtained in example 12+Doped, pure ZrO2Surface modified and unmodified samples cycling stability curves at 1C rate.
FIG. 7 is a graph of the cycling stability of the target product obtained in example 1 and the average voltage at 0.1C rate for an unmodified control.
FIG. 8 is a graph of rate capability of the target product obtained in example 1 and an unmodified control over the range of 0.1C to 5C.
FIG. 9 is the XRD spectrum of the target product obtained in example 2.
Fig. 10 is a charge-discharge curve of the target product obtained in example 2 at a magnification of 0.1C.
FIG. 11 is the XRD spectrum of the target product obtained in example 3.
FIG. 12 is a charge/discharge curve of the objective product obtained in example 3 at a magnification of 0.1C.
FIG. 13 is the XRD spectrum of the target product obtained in example 4.
Fig. 14 is a charge and discharge curve of the target product obtained in example 4 at a magnification of 0.1C.
FIG. 15 is an XRD spectrum of the objective product obtained in example 5.
Fig. 16 is a charge and discharge curve of the objective product obtained in example 5 at a 0.1C magnification.
Detailed Description
For further understanding of the present invention, the high performance layered oxide sodium ion battery positive electrode material provided by the present invention, the preparation method and the application thereof are described below with reference to the following examples, and the protection scope of the present invention is not limited by the following examples.
Example 1
Step 1, preparing Na by combining sol-gel method with wet chemical method0.67Ni0.28Mg0.05Mn0.67O2-1％ZrO2Positive electrode material
The synthesized target product is Na0.67Ni0.28Mg0.05Mn0.67O2-1％ZrO2The anode material is prepared from sodium acetate, nickel acetate, magnesium acetate and manganese acetate as synthetic raw materials, citric acid as a chelating agent and deionized water as a solvent.
Dissolving sodium acetate, nickel acetate, magnesium acetate and manganese acetate in deionized water according to the molar ratio of the target product to citric acid (the molar ratio of the total molar amount of sodium, nickel, magnesium and manganese metal ions to the citric acid is 1:1.6), and placing the solution in an oil bath kettle at the temperature of 80 ℃ to continuously stir and evaporate to dryness until gel is formed. The gel was dried in an oven at 150 ℃ for 6h and then put into a mortar to be ground to obtain a precursor powder. Putting the precursor powder into a muffle furnace, heating at the rate of 2 ℃/min in the air atmosphere, pre-sintering at 450 ℃ for 6h, and then calcining at 950 ℃ for 15h to obtain Na 0.67Ni0.28Mg0.05Mn0.67O2。
Then the obtained Na is added0.67Ni0.28Mg0.05Mn0.67O2Dispersing in ethanol, adding 1% by mass of zirconium nitrate, and continuously stirring until the ethanol is completely volatilized to obtain mixture powder; placing the mixture powder in a mortar for grinding uniformly, then placing the mixture powder in a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃/min, preserving heat for 6h, and cooling to obtain a target product Na0.67Ni0.28Mg0.05Mn0.67O2-1％ZrO2。
Step 2, preparation of Na0.67Ni0.28Mg0.05Mn0.67O2-1％ZrO2Positive plate
Mixing the prepared target product with Super P and a binding agent polyvinylidene fluoride according to the mass ratio of 7:2:1, adding a solvent N-methyl pyrrolidone, and performing pulping, smearing, drying and the like to obtain the positive plate containing the target product.
Step 3, assembling the target product Na0.67Ni0.28Mg0.05Mn0.67O2-1％ZrO2A sodium ion battery which is a positive electrode.
Assembling the prepared target product anode electrode plate and a metal sodium cathode into a sodium ion battery, wherein GF/F is a battery diaphragm, and the electrolyte is a carbonate electrolyte (1M NaClO)4The PC solution of (a) contains 5 vol% FEC).
FIG. 1 is the XRD spectrum of the target product obtained in example 1, and it can be seen that the synthesized material has good crystallinity, and is P2 phase structure, P63/mmc space group.
FIG. 2 is an SEM image of the target product obtained in example 1, and it can be seen from the SEM image that the material has a disk-like morphology and the particle size of the particles is 2-5 μm.
FIG. 3 is a TEM image of the target product obtained in example 1, and it can be seen from the image that ZrO was successfully modified on the surface of the material2And (3) particles.
FIG. 4 shows the target product obtained in example 1 at 0.1C (1C 173 mAg)-1) The charging and discharging curve under the current density is shown in the figure, and the material has higher specific capacity of 121.9mAh g when being applied to the sodium ion battery-1And has a high average operating voltage of 3.68V.
FIG. 5 is a cyclic voltammogram of the target product obtained in example 1 at a sweep rate of 0.1mV/s, and it can be seen that the cyclic voltammogram corresponds well to the charge and discharge curves.
FIG. 6 shows the target product obtained in example 1 and Mg alone2+Doped control, pure ZrO2Cycling stability curves at 1C rate for the surface modified control as well as the unmodified control. As can be seen from the figure, the initial specific capacity of the target product obtained in the example is 115.2mAh g-1And the capacity retention rate after 150 cycles is 81.5%, which is obviously improved compared with other comparative samples. Wherein; mg alone2+The doped control sample is Na0.67Ni0.28Mg0.05Mn0.67O2Assembling a positive plate and a sodium ion battery; pure ZrO2The surface modified comparative sample is Na prepared without adding magnesium acetate raw material0.67Ni0.33Mn0.67O2Then ZrO again by the same method as above2Surface modification of the resulting Na0.67Ni0.33Mn0.67O2-1％ZrO2Assembling a positive plate and a sodium ion battery; the unmodified control was Na 0.67Ni0.33Mn0.67O2And assembling the positive plate and the sodium ion battery.
Fig. 7 is a cycle stability curve of the average working voltage of the target product obtained in example 1 and an unmodified comparative sample at a magnification of 0.1C, and it can be seen from the graph that the initial voltage is 3.68V, and the voltage retention ratio after 50 cycles is 97.2%, which is significantly improved compared with the unmodified comparative sample.
FIG. 8 is a graph of the rate performance of the target product of example 1 and an unmodified control over a range of 0.1C to 5C, showing an initial capacity of 121.8mAh g at 0.1C-1And the original capacity of 62.9 percent can be maintained under the high multiplying power of 5C, and is obviously improved compared with an unmodified comparison sample.
Example 2
The procedure is as in example 1, except that the starting material is Na0.67Ni0.28Mg0.05Mn0.67O2-0.5％ZrO2Is added in a stoichiometric ratio.
FIG. 9 is the XRD spectrum of the target product obtained in example 2, and it can be seen that the synthesized material has good crystallinity, and is P2 phase structure, P63/mmc space group.
FIG. 10 shows the target product obtained in example 2 at 0.1C (1C 173 mAg)-1) The charging and discharging curve under the current density is shown in the figure, and the material has higher specific capacity of 122.9mAh g when being applied to the sodium ion battery-1。
Example 3
The procedure is as in example 1, except that the starting material is Na 0.67Ni0.28Mg0.05Mn0.67O2-2％ZrO2Is added at a stoichiometric ratio of (c).
FIG. 11 is the XRD spectrum of the target product obtained in example 3, and it can be seen that the synthesized material has good crystallinity, and is P2 phase structure, P63/mmc space group.
FIG. 12 shows the target product obtained in example 3 at 0.1C (1C 173 mAg)-1) The charging and discharging curve under the current density is shown in the figure, and the material has higher specific capacity of 114.6mAh g when being applied to the sodium ion battery-1。
Example 4
The procedure is as in example 1, except that the starting material is Na0.67Ni0.23Mg0.10Mn0.67O2-1％ZrO2Is added in a stoichiometric ratio.
FIG. 13 is the XRD spectrum of the target product obtained in example 4, and it can be seen that the synthesized material has good crystallinity, and is P2 phase structure, P63/mmc space group.
FIG. 14 shows the target product obtained in example 4 at 0.1C (1C 173 mAg)-1) The charging and discharging curve under the current density is shown in the figure, the material has higher specific capacity of 111.9mAh g when being applied to the sodium ion battery-1。
Example 5
The procedure is as in example 1, except that the starting material is Na0.67Ni0.18Mg0.15Mn0.67O2-1％ZrO2Is added in a stoichiometric ratio.
FIG. 15 is the XRD spectrum of the target product obtained in example 5, and it can be seen that the synthesized material has good crystallinity, and is P2 phase structure, P63/mmc space group.
FIG. 16 shows the target product obtained in example 5 at 0.1C (1C 173 mAg)-1) The charging and discharging curve under the current density is shown in the figure, and the material has higher specific capacity of 90.8mAh g when being applied to the sodium ion battery-1。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. A dual-strategy modified layered oxide sodium-ion battery positive electrode material is characterized in that: the positive electrode material of the sodium-ion battery is prepared by Mg2+Doped synergetic ZrO2Surface modified double-strategy P2 type Ni-Mn based layered transition metal oxide Na0.67Ni0.33Mn0.67O2Is modified to obtain; the chemical formula of the positive electrode material of the sodium-ion battery is Na0.67Ni0.33- xMgxMn0.67O2-n％ZrO2，0<x<0.2, 0-3% of n%, where n% represents ZrO2Mass percent in the positive electrode material of the sodium-ion battery.
2. The method for preparing the positive electrode material of the sodium-ion battery according to claim 1, wherein the preparation is carried out by combining a sol-gel method and a wet chemical method, and the method comprises the following steps:
A) dissolving a sodium source compound, a nickel source compound, a magnesium source compound and a manganese source compound with a chelating agent in water according to a molar ratio, and heating to volatilize a solvent to obtain a gel precursor;
B) Drying the gel precursor and then grinding to obtain precursor powder;
C) calcining the precursor powder in two steps in sequence to obtain Mg2+Doped P2 type Ni-Mn-based layered transition metal oxide Na0.67Ni0.33-xMgxMn0.67O2；
D) Dispersing the product obtained in the step C) in ethanol, then adding a zirconium source compound with a corresponding mass percentage, stirring and heating to volatilize the solvent to obtain mixture powder;
E) the mixture powder is ground and then subjected to one-step calcination to complete ZrO2And carrying out surface modification to obtain the target product, namely the sodium-ion battery positive electrode material.
3. The method of claim 2, wherein:
the sodium source compound is selected from one or more of sodium acetate, sodium nitrate, sodium oxalate and sodium citrate;
the nickel source compound is selected from one or more of nickel acetate, nickel nitrate, nickel oxalate, nickel sulfate and nickel chloride;
the magnesium source compound is selected from one or more of magnesium acetate, magnesium nitrate, magnesium oxalate, magnesium sulfate and magnesium chloride;
the manganese source compound is selected from one or more of manganese acetate, manganese nitrate, manganese oxalate, manganese sulfate and manganese chloride;
the zirconium source compound is selected from one or more of zirconium acetate, zirconium nitrate, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide and zirconium chloride;
The chelating agent is selected from citric acid, oxalic acid, tartaric acid or ethylenediamine tetraacetic acid.
4. The production method according to claim 2, characterized in that: in the step C), the two-step calcination of the precursor powder is carried out in an air atmosphere and is divided into a first-step calcination and a second-step calcination; the heating rate of the first-step calcination is 1-10 ℃/min, the temperature is raised to 350-600 ℃, and the temperature is maintained until organic matters are fully decomposed; and the temperature rise rate of the second step of calcination is 1-10 ℃/min, the temperature is raised to 800-1000 ℃, and the temperature is kept for 10-24 h until a P2 phase structure without impurity phase is formed.
5. The method of claim 2, wherein: in the step E), the one-step calcination of the mixture powder is carried out in the air atmosphere, the heating rate is 1-10 ℃/min, the temperature is increased to 400-600 ℃, and the temperature is kept for 6-10 h until ZrO is formed2A surface modification layer.
6. A positive plate of a sodium-ion battery is characterized by being prepared from an active positive material, a conductive additive, a binder and a solvent, wherein the active positive material is selected from the positive material in claim 1.
7. A sodium ion battery is characterized by comprising a positive plate, a diaphragm, an organic electrolyte and negative metal sodium, wherein the positive plate is the positive plate of the sodium ion battery according to claim 6.
8. Use of the sodium ion battery of claim 7 in large scale energy storage devices for electric vehicles, solar and wind power generation, smart grid peak shaving, distributed power stations or communication bases.
CN202210291367.8A 2022-03-23 2022-03-23 Double-strategy modified layered oxide sodium ion battery positive electrode material and preparation method and application thereof Pending CN114520323A (en)

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