CN115417393A - Spherical manganese zirconium sodium phosphate/carbon composite material, and preparation method and application thereof - Google Patents
Spherical manganese zirconium sodium phosphate/carbon composite material, and preparation method and application thereof Download PDFInfo
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Abstract
A spherical sodium zirconium manganese phosphate/carbon composite material, its preparation method and application are disclosed, the chemical formula of the material is Na 3 MnZr(PO 4 ) 3 The preparation method comprises the following steps: stirring and dispersing a sodium source, a phosphorus source, a manganese source, a zirconium source and a carbon source into a uniform solution according to a certain stoichiometric ratio to obtain a mixed solution; carrying out spray drying on the mixed solution to quickly evaporate water to obtain a precursor; roasting the precursor in a protective atmosphere to obtain a secondaryThe particle appearance is spherical manganese zirconium sodium phosphate/carbon composite material. The material is applied to the positive electrode material of the sodium-ion battery, and shows higher discharge voltage, discharge specific capacity and better cycling stability. The synthesis method is simple to operate and short in process flow.
Description
Technical Field
The invention relates to the technical field of preparation of a sodium-ion battery positive electrode material, in particular to a spherical manganese zirconium sodium phosphate/carbon composite material, and a preparation method and application thereof.
Background
The sodium ion battery has abundant use reservesSodium which is widely distributed is used as load ions, so that the method has outstanding advantages in the aspect of raw material price and is beneficial to reducing the electrochemical energy storage cost. The general molecular formula of the NASICON type phosphate anode material is Na 3 M 2 (PO 4 ) 3 Wherein M can be selected from divalent, trivalent and quadrivalent ions of V, fe, mn, ti, zr and the like. In this type of material, na 3 V 2 (PO 4 ) 3 Has higher discharge voltage and longer cycle life, but the vanadium has larger environmental pollution and is not beneficial to industrialization. Na (Na) 3 Fe 2 (PO 4 ) 3 The cost of the raw materials is lower, but the discharge voltage of the iron-based material is lower, and the iron-based material is in disadvantage in the competition of energy density. In contrast, manganese-based NASICON type phosphates Na 3 MnM(PO 4 ) 3 (M is a tetravalent transition metal ion), mn can realize two-electron transfer, namely Mn is used 2+ /Mn 4+ The redox couple reacts electrochemically, which makes it react with Na in capacity 3 V 2 (PO 4 ) 3 And the like, a higher discharge voltage can be obtained. The content of zirconium in the earth crust is 0.025% which is more than the total amount of common metals such as copper, lead, zinc and the like. From the resource perspective, na 3 MnZr(PO 4 ) 3 Has better development potential. However, na 3 MnZr(PO 4 ) 3 The electron conductance of (2) is relatively low, and a higher discharge voltage easily causes decomposition of the electrolyte, thus affecting the cycle stability of the material. Improvement of Na 3 MnZr(PO 4 ) 3 The electrochemical performance of the electrolyte needs to adopt a proper synthesis method to introduce conductive carbon to improve the electronic conductance, and simultaneously, the design of the secondary particle morphology inhibits the electrolyte from being Na under high voltage 3 MnZr(PO 4 ) 3 Decomposition of the surface.
Disclosure of Invention
In view of the above problems, the present invention provides a spherical manganese zirconium sodium phosphate/carbon composite material, and aims to obtain a manganese zirconium sodium phosphate/carbon composite positive electrode material with high charge and discharge capacity, good cycle stability and rate capability by a method with simple operation and short process flow.
In order to achieve the purpose, the technical scheme of the invention is as follows: the spherical manganese zirconium sodium phosphate/carbon composite material has the chemical formula: na (Na) 3 MnZr(PO 4 ) 3 /C。Na 3 MnZr(PO 4 ) 3 Has a rhombohedral NASICON-type crystal structure; the carbon in the composite material is amorphous carbon, and the carbon layer is coated with Na 3 MnZr(PO 4 ) 3 The surface of the primary particles; the shape of the secondary particles of the composite material is spherical.
The spherical manganese zirconium sodium phosphate/carbon composite material is prepared by taking sodium salt, manganese salt, zirconium salt, phosphate and a carbon source as raw materials, wherein the sodium salt and the phosphate can be the same substance, and the preparation method of the spherical manganese zirconium sodium phosphate/carbon composite material comprises the following steps:
(1) Dissolving sodium salt, manganese salt, zirconium salt, phosphate and a carbon source in a stoichiometric ratio in a certain amount of water, and continuously stirring and dispersing to form a uniform mixed solution;
(2) Putting the obtained mixed solution into a spray drying tower for spray drying to quickly evaporate water to obtain a precursor;
(3) And (3) placing the precursor in a heating furnace, and roasting under the condition of introducing a protective gas to obtain the spherical manganese zirconium sodium phosphate/carbon composite material.
In the raw materials, the sodium salt is selected from one or a combination of several of sodium acetate, sodium dihydrogen phosphate and sodium citrate; the manganese salt is manganese acetate; the zirconium salt is selected from one or the combination of two of zirconium acetate, zirconium acetylacetonate, zirconium citrate, zirconium propionate and zirconium methacrylate; the phosphate is selected from one or a combination of more of sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate; the carbon source is one or a combination of several of citric acid, sucrose and glucose.
The temperature of the feed inlet of the spray drying tower is 120-300 ℃.
In the preparation method of the spherical manganese zirconium sodium phosphate/carbon composite material, the protective gas is one of nitrogen, argon, nitrogen-hydrogen mixed gas and argon-hydrogen mixed gas, the roasting temperature is 600-800 ℃, and the roasting time is 4-12h.
In the preparation method of the spherical sodium zirconium manganese phosphate/carbon composite material, the carbon content in the obtained spherical sodium zirconium manganese phosphate/carbon composite material can be regulated and controlled by changing the adding amount of the carbon source in the raw materials, and the carbon content in the composite material is 1-10wt%.
The spherical manganese zirconium sodium phosphate/carbon composite material is applied to a sodium ion battery as a positive electrode material.
The invention has the beneficial effects that:
1) A spherical compound of manganese zirconium sodium phosphate and carbon is formed by spray drying, which is beneficial to forming interconnected carbon coating layers on the surfaces of manganese zirconium sodium phosphate particles and improving the electronic conductance of the manganese zirconium sodium phosphate;
2) The compact spherical secondary particle morphology is beneficial to inhibiting the decomposition of the electrolyte under high voltage and is also beneficial to improving the compaction density of the material.
3) The preparation method has the advantages of simple operation, easily controlled reaction conditions and short process flow.
Drawings
FIG. 1 shows Na prepared in example 1 of the present invention 3 MnZr(PO 4 ) 3 An X-ray diffraction pattern of/C;
FIG. 2 shows Na prepared in example 1 of the present invention 3 MnZr(PO 4 ) 3 SEM picture of/C;
FIG. 3 shows Na prepared in example 1 of the present invention 3 MnZr(PO 4 ) 3 Charge-discharge curve of C under 0.1C multiplying power;
FIG. 4 shows Na prepared in example 1 of the present invention 3 MnZr(PO 4 ) 3 The long cycle performance of the sodium-ion half-cell under the multiplying power of 2C when the/C is used as a positive electrode material;
FIG. 5 shows Na prepared in example 2 of the present invention 3 MnZr(PO 4 ) 3 An X-ray diffraction pattern of/C;
FIG. 6 shows Na prepared in example 2 of the present invention 3 MnZr(PO 4 ) 3 SEM picture of/C;
FIG. 7 is the present inventionWhile Na prepared in example 2 3 MnZr(PO 4 ) 3 Charge-discharge curve of C under 0.1C multiplying power;
FIG. 8 shows Na prepared in example 2 of the present invention 3 MnZr(PO 4 ) 3 and/C is used as a positive electrode material, and the sodium-ion half cell has long cycle performance at the rate of 2C.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the following specific examples.
Example 1
This embodiment is an example of a method for preparing a spherical manganese zirconium sodium phosphate/carbon composite material according to the present invention, and includes the following steps:
2.340g of 0.015mol NaH 2 PO 4 ·2H 2 O, 1.225g of 0.005mol Mn (CH) 3 COO) 2 ·4H 2 O, 2.458g of 0.005mol Zr (C) 5 H 8 O 2 ) 4 And 1.801g of 0.010mol of C 6 H 12 O 6 Dissolving in 20mL of deionized water, and heating and stirring at normal temperature to obtain a uniform mixed solution. And (3) carrying out spray drying on the obtained mixed solution, and controlling the temperature of a feed inlet of a spray drying tower to be 160 ℃ to obtain a precursor. Roasting the precursor after spray drying in a tubular furnace filled with argon at 750 ℃ for 12h to obtain spherical Na 3 MnZr(PO 4 ) 3 a/C composite material. The obtained Na 3 MnZr(PO 4 ) 3 The XRD pattern of/C is shown in figure 1, and the diffraction peaks in figure 1 are all attributed to Na 3 MnZr(PO 4 ) 3 . The obtained Na 3 MnZr(PO 4 ) 3 The SEM image of/C is shown in FIG. 2, wherein the secondary particles of the material are formed by aggregating a plurality of primary particles, the secondary particles are spherical in shape and have the particle size of 1-4 μm.
Mixing Na 3 MnZr(PO 4 ) 3 The mass ratio of the/C to the acetylene black to the PVDF is 8:1:1 in N-methylpyrrolidone (NMP), the resulting slurry was coated on an aluminum foil having a diameter of 16mm, and the aluminum foil was then vacuum-dried at 80 ℃ to obtain a positive electrode sheet. In an argon atmosphere glove box, taking metallic sodium as a negative electrode, 1mol L -1 NaClO 4 Propylene Carbonate (PC): fluoroethylene carbonate (FEC) (volume ratio 95. FIG. 3 shows Na 3 MnZr(PO 4 ) 3 The first circle of charge-discharge specific capacity of the charge-discharge curve of the C under the current density of 0.1C is 102.4mAh g -1 And 98.7mAh g -1 . FIG. 4 shows Na 3 MnZr(PO 4 ) 3 Discharge specific capacity-cycle number diagram of/C under 2C multiplying power, and the discharge specific capacity of the first cycle is 77.0mAh g -1 And the capacity retention rate after 1000 cycles of the cycle was 86.4%.
Example 2
This embodiment is another example of the method for preparing a spherical sodium zirconium manganese phosphate/carbon composite material according to the present invention, and includes the following steps:
2.340g of 0.015mol NaH 2 PO 4 ·2H 2 O, 1.225g of 0.005mol Mn (CH) 3 COO) 2 ·4H 2 O, 1.637g of 0.005mol Zr (CH) 3 COO) 4 And 2.702g of 0.015mol C 6 H 12 O 6 Dissolving in 20mL deionized water, heating and stirring at normal temperature to obtain a uniform mixed solution. And (3) carrying out spray drying on the obtained mixed solution, and controlling the temperature of a feed inlet of a spray drying tower to be 200 ℃ to obtain a precursor. Roasting the precursor after spray drying for 8 hours at 750 ℃ in a tubular furnace filled with argon to obtain spherical Na 3 MnZr(PO 4 ) 3 a/C composite material. The obtained Na 3 MnZr(PO 4 ) 3 The XRD pattern of/C is shown in FIG. 5, wherein the diffraction peaks are all attributed to Na 3 MnZr(PO 4 ) 3 . The obtained Na 3 MnZr(PO 4 ) 3 The SEM image of/C is shown in FIG. 6, wherein the secondary particles of the material are formed by aggregating a plurality of primary particles, the secondary particles are spherical in shape and have a particle size of 1-4 μm.
Mixing Na 3 MnZr(PO 4 ) 3 The mass ratio of the/C to the acetylene black to the PVDF is 8:1:1 in N-methylpyrrolidone (NMP), the resulting slurry was coated on an aluminum foil 16mm in diameter, which was subsequently heated at 80 deg.CAnd drying in vacuum to obtain the positive plate. In an argon atmosphere glove box, metal sodium is used as a negative electrode, and 1mol/L NaClO 4 Propylene Carbonate (PC): fluoroethylene carbonate (FEC) (volume ratio 95. FIG. 7 shows Na 3 MnZr(PO 4 ) 3 The charge-discharge curve of the C under the current density of 0.1C, the charge-discharge specific capacity of the first circle of the material under the condition is 103.0mAh g respectively -1 And 99.2mAh g -1 . FIG. 8 shows Na 3 MnZr(PO 4 ) 3 Discharge specific capacity-cycle number diagram of/C under 2C multiplying power, wherein the discharge specific capacity of the first cycle is 76.5mAh g -1 And the capacity retention rate after 1000 cycles of the cycle was 84.4%.
Example 3
This embodiment is another example of the method for preparing a spherical manganese zirconium sodium phosphate/carbon composite material according to the present invention, and includes the following steps:
2.340g of 0.015mol NaH 2 PO 4 ·2H 2 O, 1.225g of 0.005mol Mn (CH) 3 COO) 2 ·4H 2 O, 1.918g of 0.005mol Zr (CH) 3 CH 2 COO) 4 And 0.007mol C of 2.396g 12 H 22 O 11 Dissolving in 20mL deionized water, heating and stirring at normal temperature to obtain a uniform mixed solution. And (3) carrying out spray drying on the obtained mixed solution, and controlling the temperature of a feed inlet of a spray drying tower to be 160 ℃ to obtain a precursor. Roasting the precursor after spray drying in a tubular furnace filled with argon at 700 ℃ for 10h to obtain spherical Na 3 MnZr(PO 4 ) 3 a/C composite material.
Mixing Na 3 MnZr(PO 4 ) 3 The mass ratio of the/C to the acetylene black to the PVDF is 8:1:1 in N-methylpyrrolidone (NMP), the resulting slurry was coated on an aluminum foil having a diameter of 16mm, and the aluminum foil was then vacuum-dried at 80 ℃ to obtain a positive electrode sheet. In an argon atmosphere glove box, taking metal sodium as a negative electrode, and 1mol L -1 NaClO 4 Propylene Carbonate (PC): fluoroethylene carbonate (FEC) (volume ratio 95The separator was assembled into a button cell (CR 2025). Na (Na) 3 MnZr(PO 4 ) 3 The first-circle charge-discharge specific capacities of the/C circuits under the current density of 0.1C are respectively 102.9mAh g -1 And 99.0mAh g -1 。Na 3 MnZr(PO 4 ) 3 The first-circle specific discharge capacity of the C is 76.8mAh g when the C is circulated under the 2C multiplying power -1 And the capacity retention rate after 1000 cycles of the cycle was 85.2%.
Example 4
This embodiment is a 4 th example of the method for preparing a spherical manganese zirconium sodium phosphate/carbon composite material according to the present invention, and includes the following steps:
2.340g of 0.015mol NaH 2 PO 4 ·2H 2 O, 1.225g of 0.005mol Mn (CH) 3 COO) 2 ·4H 2 O, 1.673g of 0.005mol Zr (CH) 3 COO) 4 And 3.074g of 14mmol C 6 H 8 O 7 Dissolving in 20mL deionized water, heating and stirring at normal temperature to obtain a uniform mixed solution. And (3) carrying out spray drying on the obtained mixed solution, and controlling the temperature of a feed inlet of a spray drying tower to be 180 ℃ to obtain a precursor. Roasting the spray-dried precursor in a tubular furnace filled with argon at 770 ℃ for 6h to obtain spherical Na 3 MnZr(PO 4 ) 3 a/C composite material.
Mixing Na 3 MnZr(PO 4 ) 3 The mass ratio of the/C to the acetylene black to the PVDF is 8:1:1 in N-methylpyrrolidone (NMP), the resulting slurry was coated on an aluminum foil having a diameter of 16mm, and the aluminum foil was then vacuum-dried at 80 ℃ to obtain a positive electrode sheet. In an argon atmosphere glove box, taking metal sodium as a negative electrode, and 1mol L -1 NaClO 4 Propylene Carbonate (PC): fluoroethylene carbonate (FEC) (volume ratio 95. Na (Na) 3 MnZr(PO 4 ) 3 The first-circle charge-discharge specific capacities of the/C under the current density of 0.1C are respectively 102.3mAh g -1 And 98.9mAh g -1 。Na 3 MnZr(PO 4 ) 3 The first-circle specific discharge capacity of the/C is 76.0mAh g when the/C is circulated under the 2C multiplying power -1 Capacity retention after 1000 cyclesThe ratio was 83.0%.
TABLE 1 spherical Na prepared under different technical conditions 3 MnZr(PO 4 ) 3 Electrochemical performance of/C material
As can be seen from the composition and electrochemical performance data of the spherical sodium zirconium manganese phosphate/carbon composite material under different technical conditions in Table 1, na can be adjusted by changing the types and molar ratios of the raw materials 3 MnZr(PO 4 ) 3 In the/C composite material, the percentage content of carbon (C) is increased, so that the discharge capacity of the material under the condition of low-rate charge and discharge is reduced, but the Na content is favorably increased 3 MnZr(PO 4 ) 3 Discharge capacity and cycling stability under high rate charge and discharge conditions.
Claims (8)
1. The spherical sodium zirconium phosphate/carbon composite material is characterized in that the chemical formula of the sodium zirconium phosphate/carbon composite material is Na 3 MnZr(PO 4 ) 3 /C；Na 3 MnZr(PO 4 ) 3 Has a rhombohedral NASICON-type crystal structure; the carbon in the composite material is amorphous carbon, and the carbon layer is coated with Na 3 MnZr(PO 4 ) 3 The surface of the primary particles; the shape of the secondary particles of the composite material is spherical.
2. The spherical manganese zirconium sodium phosphate/carbon composite material according to claim 1, characterized in that the material is prepared by using sodium, salt, manganese salt, zirconium salt, phosphate and carbon source as raw materials, wherein the sodium salt and the phosphate are selected from the same substance.
3. The spherical sodium zirconium manganese phosphate/carbon composite material according to claim 1, wherein the sodium salt is selected from one or a combination of sodium acetate, sodium dihydrogen phosphate and sodium citrate; the manganese salt is manganese acetate; the zirconium salt is selected from one or the combination of two of zirconium acetate, zirconium acetylacetonate, zirconium citrate, zirconium propionate and zirconium methacrylate; the phosphate is selected from one or a combination of more of sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate; the carbon source is one or a combination of several of citric acid, sucrose and glucose.
4. The method for preparing the spherical sodium zirconium manganese phosphate/carbon composite material according to claim 1, characterized by comprising the following steps:
(1) Adding sodium salt, manganese salt, zirconium salt, phosphate and a carbon source into a certain amount of water according to the stoichiometric ratio of the chemical formula, and continuously stirring and dispersing the mixture into a uniform solution to obtain a mixed solution;
(2) Carrying out spray drying on the obtained mixed solution to quickly evaporate water to obtain a precursor;
(3) And roasting the obtained precursor in a heating furnace filled with protective gas to obtain the spherical manganese zirconium sodium phosphate/carbon composite material.
5. The method of claim 4, wherein the spray-dried spray-drying tower has a feed inlet temperature of 120 to 300 ℃.
6. The method of claim 4, wherein the protective gas is one of nitrogen, argon, a mixture of nitrogen and hydrogen, and a mixture of argon and hydrogen, the calcination temperature is 600-800 ℃, and the calcination time is 4-12h.
7. The preparation method according to claim 4, wherein the carbon content in the obtained spherical sodium zirconium manganese phosphate/carbon composite material can be regulated and controlled by changing the adding amount of the carbon source in the raw materials, and the carbon content in the composite material is 1-10wt%.
8. The use of a spherical sodium zirconium manganese phosphate/carbon composite material according to claim 1 in a sodium ion battery, wherein the spherical sodium zirconium manganese phosphate/carbon composite material is used as a positive electrode material for a sodium ion battery.
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| CN114373922A (en) * | 2022-01-07 | 2022-04-19 | 北京理工大学 | Manganese-based NASICON type sodium ion positive electrode material and preparation method and application thereof |
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