CN107069012B - Hollow spherical Na4Fe3(PO4)2P2O7/C composite positive electrode material and preparation method thereof - Google Patents
Hollow spherical Na4Fe3(PO4)2P2O7/C composite positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hollow spherical Na4Fe3(PO4)2P2O7the/C composite cathode material and the preparation method thereof comprise the following steps: (1) dissolving a surfactant in a polar solvent to obtain a surfactant solution, adjusting the pH of the surfactant solution to 1-4, adding a sodium source, an iron source, a phosphorus source and a carbon source, and dispersing; (2) transferring the emulsion obtained in the step (1) to a culture dish, standing for 6-24 h at the temperature of 10-40 ℃, and then heating for 8-36 h at the temperature of 80-120 ℃ to obtain a precursor; (3) the precursor is placed in an inert atmosphere, calcined for 2 to 6 hours at the temperature of 250 to 350 ℃, then heated to 500 to 700 ℃, and continuously calcined for 6 to 12 hours. The composite anode material obtained by the invention can relieve the volume change caused by sodium ion de-intercalation during charging and discharging, and effectively improve Na4Fe3(PO4)2P2O7Conductivity and stability of (d).
Description
Technical Field
The invention belongs to the field of preparation of a sodium-ion battery anode material, and particularly relates to hollow spherical Na4Fe3(PO4)2P2O7a/C compound anode material and a preparation method thereof.
Background
Energy is an important material basis for survival and development of human society, but at present, the traditional fossil energy coal, petroleum, natural gas and the like still account for a large proportion in the global energy structure. The decreasing of fossil energy reserves and the serious environmental pollution caused in the utilization process thereof compel countries in the world to vigorously develop new energy systems and technology research. Renewable energy sources such as solar energy, wind energy and the like have the characteristics of rich resources, environmental friendliness and the like. However, due to the limitation of natural conditions, such clean energy sources are intermittent and unstable, and are difficult to be combined with the grid for power generation, so that a large-scale energy storage system must be used for peak clipping and valley filling to ensure the stability of a power grid and the continuity of power supply. The existing large-scale energy storage technologies comprise water pumping energy storage, compressed air energy storage, flywheel energy storage, electrochemical energy storage and the like. Compared with other energy storage technologies, the electrochemical energy storage has the characteristics of high conversion efficiency, long cycle life, low maintenance cost, flexible power and energy characteristics and the like.
There are many routes for large-scale electrochemical energy storage technologies, such as lead-acid batteries, flow batteries, high-temperature sodium-sulfur batteries, lithium ion batteries, and the like. However, lead-acid batteries, flow batteries, and high-temperature sodium-sulfur batteries all have fatal inherent defects, so that they are difficult to scale in energy storage systems. The lithium ion battery has high energy density, long cycle life, cleanness and high efficiency, and is the first choice of the energy storage system. However, in recent years, with the large consumption of lithium metal brought by the rapid development of the electric automobile market in China and the uneven distribution of lithium resources in the world (mainly distributed in south America countries), the development of the lithium ion battery industry in China in the future is inevitably limited by the shortage of upstream lithium ores. The sodium ion battery similar to the working principle of the lithium ion battery has the characteristics of low cost, high energy density and the like, and can be used in the field of large-scale energy storage.
Although the research of the sodium ion battery is started in the eighties of the last century, the development is not smooth, the maturity of the technology is far inferior to that of the lithium ion battery, and the main bottleneck for restricting the development of the sodium ion battery is the defectThe cathode material has long service life and can stably remove and insert sodium ions. At present, the positive electrode material of the sodium ion battery mainly comprises a layered oxide, a tunnel oxide, a prussian blue compound, a polyanion compound and the like. Layered oxide NaxMO2The electrochemical sodium storage material has excellent electrochemical sodium storage activity, simple preparation method and higher energy density, but the structural stability and the cycle performance of the material are poorer. Tunnel type oxide NaxMO2Has stable structure and cycle performance, but has low first-cycle charge capacity, resulting in very low practical specific energy of the battery. Prussian blue compound KMFe (CN)6The material has a three-dimensional open structure, high sodium storage activity, good circulation stability and rate capability and low cost, but the large-scale preparation process of the material has more problems to be solved urgently. Polyanionic compounds have many advantages such as an open framework structure, good structural and thermal stability, and a stable voltage plateau, and are therefore favored.
Among the numerous polyanionic compounds, Na4Fe3(PO4)2P2O7The theoretical specific capacity reaches 129mAh g-1The working voltage is 3.2V, the cost is low, and the excellent comprehensive performance is shown, so the method is widely concerned. However, Na4Fe3(PO4)2P2O7The electronic conductivity and the ionic conductivity of the composite material are extremely low, so that the actual specific capacity of the composite material is small, and the large-current discharge performance is poor.
Disclosure of Invention
The invention aims to provide hollow spherical Na4Fe3(PO4)2P2O7a/C compound anode material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one, hollow spherical Na4Fe3(PO4)2P2O7a/C composite positive electrode material in which carbon is mixed with Na4Fe3(PO4)2P2O7The mass ratio of (1): (1-49).
Two, hollow spherical Na4Fe3(PO4)2P2O7The preparation method of the/C composite cathode material comprises the following steps:
(1) dissolving a surfactant in a polar solvent to obtain a surfactant solution, adjusting the pH of the surfactant solution to 1-4, adding a sodium source, an iron source, a phosphorus source and a carbon source, and dispersing, wherein the molar ratio of sodium elements, iron elements and phosphorus elements in the sodium source, the iron source and the phosphorus source is 4: 3: 4;
(2) transferring the emulsion obtained in the step (1) to a culture dish, standing for 6-24 h at the temperature of 10-40 ℃, and then heating for 8-36 h at the temperature of 80-120 ℃ to obtain a precursor;
(3) putting the precursor in an inert atmosphere, calcining for 2-6 h at the temperature of 250-350 ℃, then heating to 500-700 ℃, and continuing calcining for 6-12 h to obtain a target compound, wherein carbon and Na in the target compound4Fe3(PO4)2P2O7The mass ratio of (1): (1-49);
the amount of the surfactant and Na in the target compound4Fe3(PO4)2P2O7In a molar ratio of 1: (1-15).
Further, the surfactant is one or more of fatty glyceride, sodium alkyl benzene sulfonate, polyoxyethylene-polyoxypropylene-polyoxyethylene.
Further, the polar solvent is one or more of water, methanol, ethanol, isopropanol and acetone.
Further, the sodium source is one or more of disodium hydrogen phosphate, sodium pyrophosphate, sodium acetate, sodium nitrate, sodium citrate and sodium oxalate.
Further, the iron source is one or more of ferric nitrate, ferric sulfate, ferric acetate, ferrous oxalate, ferrous sulfate and ferric chloride.
Further, the phosphorus source is one or more of phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium pyrophosphate and sodium pyrophosphate.
Further, the carbon source is one or more of starch, citric acid, sucrose, glucose and phenolic resin.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) adopting a surfactant as a growth template, forming a spherical structure by self-assembly, and forming a hollow structure after removing the surfactant, as shown in figure 1; the spherical structure has smooth surface and small specific surface area, and can reduce side reaction with electrolyte; the hollow structure is beneficial to relieving the volume change caused by sodium ion deintercalation during charging and discharging.
(2) Adopting oligomer or macromolecule as carbon source, forming three-dimensional network structure in self-assembly process, fixing cation on network skeleton, heat treating, and adding Na4Fe3(PO4)2P2O7The particle surface is coated with a carbon layer, as shown in figure 1, which is effective in increasing Na4Fe3(PO4)2P2O7Conductivity and stability of (d).
(3) The preparation process is stable and controllable, good in reproducibility and easy for batch production.
Drawings
FIG. 1 is a schematic diagram of the preparation of the present invention;
FIGS. 2 to 3 are SEM pictures of the target product obtained in example 1;
FIG. 4 is a charge-discharge curve of the objective product obtained in example 1;
FIG. 5 is a high current cycle curve of the target product obtained in example 1;
FIG. 6 is a charge-discharge curve of the objective product obtained in example 2;
FIG. 7 is a small current cycle curve of the objective product obtained in example 2;
FIG. 8 is a charge-discharge curve of the objective product obtained in example 3;
FIG. 9 is a small current cycle curve of the objective product obtained in example 3;
FIG. 10 is a charge-discharge curve of the objective product obtained in example 4;
FIG. 11 is a small current cycle curve of the objective product obtained in example 4.
Detailed Description
FIG. 1 is a schematic diagram of the preparation of the present invention, wherein firstly, a surfactant forms a normal phase micelle by self-assembly in a polar solvent. Subsequently, the sodium source compound, the iron source compound, the phosphorus source compound and the carbon source compound are linked to the hydrophilic group outside the micelle by hydrogen bonding. After heat treatment, the surfactant is pyrolyzed and removed to form a hollow spherical structure.
The technical solution of the present invention is further described in detail below with reference to the accompanying drawings and embodiments. But do not limit the invention to the scope of the described embodiments.
Example 1
In this embodiment, the raw material includes F127 and Na4P2O7、Fe(NO3)3、NH4H2PO4And phenolic resin, wherein F127 is a surfactant and Na4P2O7Being both a sodium and a phosphorus source, Fe (NO)3)3Is a source of iron, NH4H2PO4Is a phosphorus source and phenolic resin is a carbon source. F127 and Na in target product4Fe3(PO4)2P2O7In a molar ratio of 1:1, Na4P2O7、Fe(NO3)3、NH4H2PO4In a molar ratio of 1: 3: 2.
and (3) taking water as a polar solvent, transferring the obtained emulsion to a culture dish, standing for 6h at 40 ℃, and then heating for 8h at 80 ℃ to obtain a precursor. And putting the precursor in an argon atmosphere, calcining for 6h at the temperature of 250 ℃, subsequently heating to 500 ℃, and continuing calcining for 12h to obtain the target product. The obtained target product contains carbon and Na4Fe3(PO4)2P2O7In a mass ratio of 1: 49.
The SEM pictures of the target product of the present embodiment are shown in FIGS. 2-3, and as can be seen from FIG. 2, the target product has a spherical structure, and the spherical particle size is 20 nm-100 nm. As can be seen from FIG. 3, it has a hollow structure with a pore diameter of 10nm to 80 nm.
FIG. 4 is a charge-discharge curve of the target product of this example, from which it can be seen that the target product of this example has a plurality of discharge plateaus and a discharge capacity of 90mAh g-1. FIG. 5 is a graph showing the large current cycle curve of the target product of this example at 200mA g-1Initial capacity at current density of 66mAh g-1The capacity retention rate after 500 cycles was 68%.
Example 2
In this example, the raw materials include sodium dodecylbenzenesulfonate and Na2HPO4、FeSO4、NH4H2PO4And sucrose, wherein sodium dodecyl benzene sulfonate is used as a surfactant and Na2HPO4Is both a sodium source and a phosphorus source, NH4H2PO4As a source of phosphorus, FeSO4Is an iron source and sucrose is a carbon source. Sodium dodecyl benzene sulfonate and Na in target product4Fe3(PO4)2P2O7In a molar ratio of 1: 5, Na2HPO4、FeSO4、NH4H2PO4In a molar ratio of 2: 3: 2.
and (2) taking ethanol as a polar solvent, transferring the obtained emulsion to a culture dish, standing for 8h at 20 ℃, and then heating for 10h at 90 ℃ to obtain a precursor. And putting the precursor in an argon atmosphere, calcining for 5 hours at the temperature of 280 ℃, then heating to 550 ℃, and continuing calcining for 10 hours to obtain the target product. The obtained target product contains carbon and Na4Fe3(PO4)2P2O7In a mass ratio of 1: 19.
FIG. 6 is a charge-discharge curve of the target product of this example, from which it can be seen that the target product of this example has a plurality of discharge plateaus and a discharge capacity of 95mAh g-1. FIG. 7 is a high current cycle curve of the target product of this example at 10mA g-1Initial capacity at current density 89mAh g-1The 90 cycle capacity remained essentially unchanged.
Example 3
In this example, the raw materials include F127, P123, Na4P2O7、FeC2O4Phosphoric acid and glucose, wherein F127 and P123 are surfactants, Na4P2O7Is both a sodium source and a phosphorus source, FeC2O4Is an iron source and phosphoric acid is a phosphorus source. Na in surfactant and target product4Fe3(PO4)2P2O7In a molar ratio of 1:10, Na4P2O7、FeC2O4、H3PO4In a molar ratio of 1: 3: 2.
And (2) taking ethanol as a polar solvent, transferring the obtained emulsion to a culture dish, standing for 12h at the temperature of 30 ℃, and then heating for 16h at the temperature of 90 ℃ to obtain a precursor. And putting the precursor in an argon atmosphere, calcining for 4 hours at the temperature of 300 ℃, subsequently heating to 600 ℃, and continuously calcining for 8 hours to obtain the target product. The obtained target product contains carbon and Na4Fe3(PO4)2P2O7The mass ratio of (A) to (B) is 1: 1.
FIG. 8 is a charge/discharge curve of the target product of this example, from which it can be seen that the target product of this example has a plurality of discharge plateaus and a discharge capacity of 59mAh g-1. FIG. 9 is a graph showing the large current cycle curve of the target product of this example at 20mA g-1Initial capacity at current density of 61mAh g-134 cycles after the capacity fade of 53mAh g-1。
Example 4
In this example, the raw materials include P123 and CH3COONa、FeC2O4、NH4H2PO4、(NH4)4P2O7And citric acid, wherein P123 is surfactant and CH3COONa as a sodium source, FeC2O4Is a source of iron, NH4H2PO4And (NH)4)4P2O7Is a phosphorus source compound, and citric acid is a carbon source. P123 and Na4Fe3(PO4)2P2O7In a molar ratio of 1:15, CH3COONa、 NH4H2PO4、(NH4)4P2O7、FeC2O4In a molar ratio of 4:2:1: 3.
And (3) taking acetone as a polar solvent, transferring the obtained emulsion to a culture dish, standing for 24h at 10 ℃, and then heating for 36h at 120 ℃ to obtain a precursor. And putting the precursor in an argon atmosphere, calcining for 2h at the temperature of 350 ℃, then heating to 700 ℃, and continuing calcining for 6h to obtain the target product. The obtained target product contains carbon and Na4Fe3(PO4)2P2O7The mass ratio of (A) to (B) is 1: 9.
FIG. 10 is a charge-discharge curve of the target product of this example, from which it can be seen that the target product of this example has a plurality of discharge plateaus and a discharge capacity of 102mAh g-1. FIG. 11 is a graph showing the large current cycle curve of the target product of this example at 10mA g-1Initial capacity at current density of 98mAh g-1The capacity remained essentially unchanged after 100 cycles.
Claims (6)
1. Hollow spherical Na4Fe3(PO4)2P2O7The preparation method of the/C composite cathode material is characterized by comprising the following steps:
(1) dissolving a surfactant in a polar solvent to obtain a surfactant solution, adjusting the pH of the surfactant solution to 1-4, adding a sodium source, an iron source, a phosphorus source and a carbon source, and dispersing, wherein the molar ratio of sodium elements, iron elements and phosphorus elements in the sodium source, the iron source and the phosphorus source is 4: 3: 4;
(2) transferring the emulsion obtained in the step (1) to a culture dish, standing for 6-24 h at the temperature of 10-40 ℃, and then heating for 8-36 h at the temperature of 80-120 ℃ to obtain a precursor;
(3) putting the precursor in an inert atmosphere, calcining for 2-6 h at the temperature of 250-350 ℃, then heating to 500-700 ℃, and continuing calcining for 6-12 h to obtain a target compound, wherein carbon and Na in the target compound4Fe3(PO4)2P2O7The mass ratio of (1): (1-49);
the amount of the surfactant and Na in the target compound4Fe3(PO4)2P2O7In a molar ratio of 1: (1-15);
the surfactant is one or more of fatty glyceride, sodium alkyl benzene sulfonate and polyoxyethylene-polyoxypropylene-polyoxyethylene.
2. The hollow spherical Na of claim 14Fe3(PO4)2P2O7The preparation method of the/C composite cathode material is characterized by comprising the following steps:
the polar solvent is one or more of water, methanol, ethanol, isopropanol and acetone.
3. The hollow spherical Na of claim 14Fe3(PO4)2P2O7The preparation method of the/C composite cathode material is characterized by comprising the following steps:
the sodium source is one or more of disodium hydrogen phosphate, sodium pyrophosphate, sodium acetate, sodium nitrate, sodium citrate and sodium oxalate.
4. The hollow spherical Na of claim 14Fe3(PO4)2P2O7The preparation method of the/C composite cathode material is characterized by comprising the following steps:
the iron source is one or more of ferric nitrate, ferric sulfate, ferric acetate, ferrous oxalate, ferrous sulfate and ferric chloride.
5. The hollow spherical Na of claim 14Fe3(PO4)2P2O7The preparation method of the/C composite cathode material is characterized by comprising the following steps:
the phosphorus source is one or more of phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium pyrophosphate and sodium pyrophosphate.
6. The hollow spherical Na of claim 14Fe3(PO4)2P2O7The preparation method of the/C composite cathode material is characterized by comprising the following steps:
the carbon source is one or more of starch, citric acid, sucrose, glucose and phenolic resin.
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