CN108046231B - Sodium ion battery positive electrode material and preparation method thereof - Google Patents
Sodium ion battery positive electrode material and preparation method thereof Download PDFInfo
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention belongs to the field of positive electrode materials of sodium-ion batteries, and particularly discloses a phosphoric acid pyrophosphoric acid composite polyanion-type iron-based positive electrode material with a chemical formula of Na4Fe2M(PO4)2(P2O7) (ii) a Wherein M is at least one of Mn, Co and Ni. In addition, the invention also discloses a preparation method and application of the cathode material. The material provided by the invention has good electrical properties, and researches show that the material not only has a high-voltage platform of more than 3.5v, but also has obviously excellent thermal stability, multiplying power and cycle performance. The preparation method is simple, high in repeatability and low in cost, and has a great commercial application prospect.
Description
Technical Field
The invention relates to the field of sodium ion battery materials, in particular to a phosphoric acid pyrophosphoric acid composite polyanion-based iron-based positive electrode material.
Background
The lithium ion battery has high specific capacity and high energy density, so that the lithium ion battery is widely applied to portable electronic equipment and popularization and application of the ion battery in the field of large energy storage systems. Sodium ion batteries have become hot research at home and abroad as effective substitutes for lithium ion batteries. Sodium has similar physicochemical properties with lithium, and the sodium resource has considerable storage in the earth crust (the earth crust abundance of lithium is 0.006%, and the earth crust abundance of sodium is 2.64%), so that the sodium-ion battery has great advantages in cost, and the sodium-ion battery is the most potential battery system for large-scale energy storage commercial application.
In order to meet the requirements of practical application, high voltage and high energy density are development directions of positive electrode materials of sodium ion batteries. Compared with an oxide system and a Prussian blue analogue system, the polyanion type sodium-ion battery positive electrode material shows higher voltage due to the induction effect of polyanion. Meanwhile, the polyanion material has an open ion diffusion channel, and has high structural stability and thermal stability, so the polyanion material has a good application prospect. At present, phosphate, silicate, sulfate, pyrophosphate and fluorophosphate system cathode materials are continuously proposed. However, the voltage of the positive electrode material of a single polyanion group still needs to be increased. In order to develop a higher voltage and high capacity cathode material, a mixed polyanion type cathode material becomes a hot point of research. The iron-based polyanionic positive electrode material such as sodium iron phosphate, sodium iron pyrophosphate and the like has stable structure and low cost. But its voltage is generally low, reducing the energy density of the battery.
Disclosure of Invention
In order to solve the problems encountered in the prior art, the invention provides a sodium ion battery positive electrode material (phosphoric acid pyrophosphoric acid composite polyanion type iron-based positive electrode material) aiming at improving the electrical properties of the material.
The second purpose of the invention is to provide a preparation method of the cathode material, and the invention aims to provide a preparation method of the composite cathode material for the sodium-ion battery, which has the advantages of good repeatability, simple operation, low cost and industrial application prospect.
The third object of the present invention is to provide a positive electrode material using the above positive electrode material.
A positive electrode material (the invention is also called as positive electrode material for short) of sodium ion battery, the chemical formula is Na4Fe2M(PO4)2(P2O7) (ii) a Wherein M is at least one of Mn, Co and Ni.
The cathode material is a phosphoric acid pyrophosphoric acid composite polyanion type iron-based cathode material, and belongs to an orthorhombic system. The anode material provided by the invention has good electrical properties, and researches show that the material not only has a high-voltage platform of more than 3.5V (the voltage of a general iron-based material is about 3.0V), but also has obviously excellent thermal stability, multiplying power and cycle performance.
Preferably, the positive electrode material has a steric group Pn21a。
The anode material is a three-dimensional sheet porous material.
The positive electrode material of the invention has the stoichiometric ratio of Na to Fe to M to (PO)4)3-∶(P2O7)4-＝4∶2∶1∶2∶1。
The invention also provides a preparation method of the sodium-ion battery anode material, which comprises the steps of dissolving a sodium source, an iron source, an M source and a phosphorus source in water according to the proportion of Na, Fe, M and P elements in a chemical formula to obtain a mixed solution; adding a complexing agent into the mixed solution, heating and stirring to obtain gel; drying the gel to obtain a precursor; and calcining the precursor at 450-650 ℃ to obtain the cathode material.
According to the invention, the anode material with brand new crystal morphology and excellent electrical properties can be prepared by a sol-gel method and a calcination process at the temperature according to the proportion; in addition, the preparation method has the advantages of good repeatability, simple operation and low cost.
The sodium source is preferably a compound that is soluble in aqueous solution and ionizable to release Na +.
The sodium source is at least one of sodium pyrophosphate, sodium acetate, sodium nitrate, sodium carbonate, sodium bicarbonate, sodium dihydrogen phosphate and disodium hydrogen phosphate.
The iron source is preferably soluble in aqueous solution and ionizable to release Fe2+/Fe3+The compound of (1).
The iron source is at least one of ferrous oxalate, ferric nitrate, ferric citrate and ferric ammonium citrate.
The M source is a water-soluble salt of M metal ions. The M source is preferably water-soluble salts of Mn, Co and Ni.
More preferably, the manganese source is one or more of manganese acetate, manganese nitrate and manganese oxalate; the cobalt source is one or more of cobalt acetate, cobalt nitrate and cobalt oxalate; the nickel source is one or more of nickel acetate, nickel carbonate and nickel oxalate.
The phosphorus source is one or more of ammonium dihydrogen phosphate, phosphoric acid, diammonium hydrogen phosphate, ammonium phosphate, disodium hydrogen phosphate, sodium pyrophosphate and sodium dihydrogen phosphate.
The complexing agent is at least one of tetraethylene glycol, ethylene glycol, citric acid, oxalic acid, glucose, sucrose, ascorbic acid, polyvinylpyrrolidone and polyvinyl alcohol.
A further preferred complexing agent is tetraethyleneglycol.
Preferably, the concentration of Fe in the mixed solution is 0.1-0.5 mol L-1. Researches find that the precursor formed after the gel formed under the optimal concentration is dried is fluffy, so that the particle size of the subsequently prepared material is small, the pore channels are rich, and the rapid charge and discharge performance is promoted.
In the present invention, the concentration of Fe is Fe element (for example, Fe exists in the solution) in the mixture system3+Or Fe2+) The molar concentration of (c).
Preferably, the mol ratio of Fe to the complexing agent is 1: 1-4. The complexing effect is better and is beneficial to further improving the material performance.
The mol ratio of Fe to the complexing agent is the mol ratio of the iron element and the complexing agent in the mixed system.
The heating temperature in the gel preparation process is 70-90 ℃. Preferably, the process of preparing the gel by heating and stirring is preferably carried out under the condition of water bath; for example, in the preparation process, the heating temperature of the water bath is controlled to be 70-90 ℃.
Stirring at the water bath heating temperature until a gel is obtained.
Drying the gel to obtain a precursor; the drying temperature is preferably 110-130 ℃.
In the invention, the precursor is calcined, and the calcination process is carried out in a protective atmosphere.
Preferably, the protective atmosphere is one or more of argon, nitrogen and hydrogen-argon mixed gas.
It was found that the combination of the above method for preparing a gel contributes to obtaining a positive electrode material having the crystal phase of the present invention in the above preferred temperature range. The purity, crystal form and the like of the material are easy to change due to over high temperature, and the electrical property of the material is obviously reduced.
Further preferably, the temperature of the calcination is 450 to 550 ℃. In the temperature range, the phosphoric acid pyrophosphoric acid composite polyanion-based iron-based cathode material with higher crystal phase purity can be prepared.
The preferable calcination time is 6-18 h.
The invention also provides application of the sodium ion battery anode material, which is used as an anode active material of a sodium ion battery to prepare the sodium ion battery anode.
For example, the Na is added4Fe2M(PO4)2(P2O7) The (M ═ Mn, Co, Ni) material was mixed with a conductive agent and a binder, and then coated on an aluminum foil to prepare a positive electrode for a sodium ion battery. The conductive agent and the binder used may be those known to those skilled in the art. The method for assembling and preparing the positive electrode material of the sodium-ion battery can also refer to the existing method.
For example, the present invention produces Na4Fe2M(PO4)2(P2O7) Grinding (M ═ Mn, Co and Ni) material, conductive carbon black and PVDF binder according to the mass ratio of 8: 1, fully mixing, adding NMP to form uniform slurry, coating the uniform slurry on an aluminum foil to be used as a test electrode, using metal sodium as a counter electrode and using 1M NaClO as electrolyte 4100% PC, preparing a sodium half cell and testing the electrochemical performance of the sodium half cell.
The invention also discloses a method for preparing the positive electrode of the sodium-ion battery by using the positive electrode material and testing the electrochemical performance of the positive electrode material.
The invention has the beneficial effects that:
the invention provides Na4Fe2M(PO4)2(P2O7) The (M ═ Mn, Co and Ni) cathode material is prepared by matching two strategies of partial substitution of transition metal ions and polyanion complexing; the voltage platform is cooperatively improved. And due to the induction effect of the polyanion, the voltage of the material is further improved by compounding the polyanion. The voltage platform of the material is above 3.5V, and the capacity of the material under the multiplying power of 2C can be as high as 82 mAh/g; the capacity retention rate after 50 cycles reaches more than 90%; the multiplying power and the cycle performance are obviously excellent.
In addition, the invention also provides a preparation method which is simple, reliable, low in cost and good in industrial application prospect. The material is used for a sodium ion battery and has excellent electrochemical performance.
Drawings
FIG. 1 shows Na obtained in example 14Fe2Mn(PO4)2(P2O7) Scanning Electron Micrographs (SEM) of the positive electrode material;
FIG. 2 shows Na obtained in example 14Fe2Mn(PO4)2(P2O7) XRD pattern of the positive electrode material;
FIG. 3 shows that Na was obtained in example 14Fe2Mn(PO4)2(P2O7) A multiplying power performance diagram of the sodium ion battery assembled by the positive electrode material;
FIG. 4 shows the preparation of Na in example 14Fe2Mn(PO4)2(P2O7) 0.5 multiplying power cycle performance diagram of sodium ion battery assembled by positive electrode material
Detailed Description
The following examples are intended to illustrate the invention in further detail; and the scope of the claims of the present invention is not limited by the examples.
Example 1
Taking 0.01mol of sodium pyrophosphate, 0.02mol of ferrous oxalate, 0.01mol of manganese acetate and 0.02mol of dihydrogen phosphateDissolving ammonium in 80ml of deionized water by stirring, adding 0.05mol of tetraethylene glycol, heating in a water bath at 80 ℃ and stirring to form colloid, and drying in a drying oven at 120 ℃ to obtain precursor powder; calcining the precursor at 550 ℃ for 10h under inert atmosphere to obtain a product Na4Fe2Mn(PO4)2(P2O7)。
Prepared Na4Fe2Mn(PO4)2(P2O7) The morphology (SEM) of the material is shown in figure 1, and is a three-dimensional sheet-like porous material. The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and as can be seen from fig. 3, the material has excellent rate performance, and even under the rate of 2C, the material still has the capacity of 82 mAh/g. As can be seen from the multiplying power cycle diagram in FIG. 4, after the battery is cycled for 50 circles under 2C, the specific discharge capacity reaches 75mAh/g, and the capacity retention rate reaches more than 90%.
Example 2
Taking 0.01mol of sodium pyrophosphate, 0.02mol of ferrous oxalate, 0.01mol of manganese acetate and 0.02mol of ammonium dihydrogen phosphate, stirring and dissolving in 80ml of deionized water, adding 0.08mol of tetraethylene glycol, heating in a water bath at 80 ℃, stirring to form colloid, and drying in a drying oven at 120 ℃ to obtain precursor powder; calcining the precursor at 550 ℃ for 10h under inert atmosphere to obtain a product Na4Fe2Mn(PO4)2(P2O7). The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 73.2mAh/g under the multiplying power of 2C. The capacity retention rate was 88%.
Example 3
Taking 0.01mol of sodium pyrophosphate, 0.02mol of ferrous oxalate, 0.01mol of manganese acetate and 0.02mol of ammonium dihydrogen phosphate, stirring and dissolving in 40ml of deionized water, adding 0.05mol of tetraethylene glycol, heating in a water bath at 80 ℃, stirring to form colloid, and drying in a drying oven at 120 ℃ to obtain precursor powder; calcining the precursor at 550 ℃ for 10h under inert atmosphere to obtain a product Na4Fe2Mn(PO4)2(P2O7). The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button cell,under the multiplying power of 2C, the specific capacity is 72.8 mAh/g. The capacity retention rate was 88%.
Example 4
Taking 0.01mol of sodium pyrophosphate, 0.02mol of ferrous oxalate, 0.01mol of manganese acetate and 0.02mol of ammonium dihydrogen phosphate, stirring and dissolving in 80ml of deionized water, adding 0.05mol of tetraethylene glycol, heating in a water bath at 80 ℃, stirring to form colloid, and drying in a drying oven at 120 ℃ to obtain precursor powder; calcining the precursor at 650 ℃ for 18h under inert atmosphere to obtain a product Na4Fe2Mn(PO4)2(P2O7). The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 69.6mAh/g under the multiplying power of 2C. The capacity retention rate was 83.4%.
Example 5
Taking 0.01mol of sodium pyrophosphate, 0.02mol of ferrous oxalate, 0.01mol of manganese acetate and 0.02mol of ammonium dihydrogen phosphate, stirring and dissolving in 80ml of deionized water, adding 0.05mol of tetraethylene glycol, heating in a water bath at 80 ℃, stirring to form colloid, and drying in a drying oven at 120 ℃ to obtain precursor powder; calcining the precursor for 6h at 450 ℃ under inert atmosphere to obtain a product Na4Fe2Mn(PO4)2(P2O7). The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 70.8mAh/g under the multiplying power of 2C. The capacity retention rate was 84.7%.
Example 6
Taking 0.01mol of sodium pyrophosphate, 0.02mol of ferrous oxalate, 0.01mol of cobalt acetate and 0.02mol of ammonium dihydrogen phosphate, stirring and dissolving in 80ml of deionized water, adding 0.05mol of tetraethylene glycol, heating in a water bath at 80 ℃, stirring to form colloid, and drying in a drying oven at 120 ℃ to obtain precursor powder; calcining the precursor at 550 ℃ for 10h under inert atmosphere to obtain a product Na4Fe2Co(PO4)2(P2O7). The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 71.6mAh/g under the multiplying power of 2C. The capacity retention rate was 85.1%.
Example 7
Taking 0.01mol of sodium pyrophosphate, 0.02mol of ferrous oxalate, 0.01mol of nickel acetate and 0.02mol of ammonium dihydrogen phosphate, stirring and dissolving in 80ml of deionized water, adding 0.05mol of tetraethylene glycol, heating in a water bath at 80 ℃, stirring to form colloid, and drying in a drying oven at 120 ℃ to obtain precursor powder; calcining the precursor at 550 ℃ for 10h under inert atmosphere to obtain a product Na4Fe2Mn(PO4)2(P2O7). The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 69.4mAh/g under the multiplying power of 2C
Comparative example 1
Taking 0.01mol of sodium pyrophosphate, 0.02mol of ferrous oxalate, 0.01mol of manganese acetate and 0.02mol of ammonium dihydrogen phosphate, stirring and dissolving in 300ml of deionized water, adding 0.05mol of tetraethylene glycol, heating in a water bath at 80 ℃, stirring to form colloid, and drying in a drying oven at 120 ℃ to obtain precursor powder; calcining the precursor at 550 ℃ for 10h under inert atmosphere to obtain a product Na4Fe2Mn(PO4)2(P2O7). The sodium-ion battery composite positive electrode material prepared by the embodiment and a sodium sheet are assembled into a button battery, and the specific capacity is 23.7mAh/g under the multiplying power of 2C. In the mixed solution, the solubility of iron ions is too low, the expansion effect of the gel after drying is poor, three-dimensional pore channels of the prepared material are lost, and the rate capability is poor.
Comparative example 2
0.01mol of sodium pyrophosphate, 0.02mol of ferrous oxalate, 0.01mol of manganese acetate and 0.02mol of ammonium dihydrogen phosphate are taken to be stirred and dissolved in 80ml of deionized water, 0.01mol of tetraethylene glycol is added, and the mixture is heated and stirred in a water bath at 80 ℃, so that the material can not normally form gel.
Comparative example 3
Taking 0.01mol of sodium pyrophosphate, 0.02mol of ferrous oxalate, 0.01mol of manganese acetate and 0.02mol of ammonium dihydrogen phosphate, stirring and dissolving in 80ml of deionized water, adding 0.05mol of tetraethylene glycol, heating in a water bath at 80 ℃, stirring to form colloid, and drying in a drying oven at 120 ℃ to obtain precursor powder; and calcining the precursor at 400 ℃ for 10h under an inert atmosphere, wherein XRD (X-ray diffraction) of the obtained product shows that the corresponding crystalline phase of the target material is not contained.
Comparative example 4
Taking 0.01mol of sodium pyrophosphate, 0.02mol of ferrous oxalate, 0.01mol of manganese acetate and 0.02mol of ammonium dihydrogen phosphate, stirring and dissolving in 80ml of deionized water, adding 0.05mol of tetraethylene glycol, heating in a water bath at 80 ℃, stirring to form colloid, and drying in a drying oven at 120 ℃ to obtain precursor powder; and calcining the precursor at 800 ℃ for 10h under an inert atmosphere, wherein XRD (X-ray diffraction) of the obtained product shows that the corresponding crystalline phase of the target material does not exist.
Claims (7)
1. The positive electrode material of the sodium-ion battery is characterized in that the chemical formula is Na4Fe2M(PO4)2(P2O7) (ii) a Wherein M is at least one of Mn, Co and Ni;
is orthorhombic; space group Pn21a；
The positive electrode material of the sodium-ion battery is a three-dimensional sheet-shaped porous material.
2. The preparation method of the positive electrode material of the sodium-ion battery of claim 1, characterized by dissolving a sodium source, an iron source, an M source and a phosphorus source in water according to the proportion of Na, Fe, M and P elements in a chemical formula to obtain a mixed solution; adding a complexing agent into the mixed solution, stirring and heating to obtain gel; drying the gel to obtain a precursor; calcining the precursor at 450-650 ℃ to obtain the anode material;
the concentration of Fe in the mixed solution is 0.1-0.5 mol L-1；
The complexing agent is tetraethylene glycol;
the mol ratio of Fe to the complexing agent is 1: 1 to 4.
3. The method for producing a positive electrode material for a sodium-ion battery according to claim 2, wherein the concentration of Fe in the mixed solution is 0.25mol L-1。
4. The method for preparing the positive electrode material of the sodium-ion battery according to claim 3, wherein the molar ratio of Fe to the complexing agent is 1: 2.5.
5. the method for producing a positive electrode material for a sodium-ion battery according to claim 2, wherein the sodium source is at least one of sodium pyrophosphate, sodium acetate, sodium nitrate, sodium carbonate, sodium bicarbonate, sodium dihydrogen phosphate, and disodium hydrogen phosphate;
the iron source is at least one of ferrous oxalate, ferric nitrate, ferric citrate and ferric ammonium citrate;
the M source is water-soluble salt of M metal ions;
the phosphorus source is one or more of ammonium dihydrogen phosphate, phosphoric acid, diammonium hydrogen phosphate, ammonium phosphate, disodium hydrogen phosphate, sodium pyrophosphate and sodium dihydrogen phosphate.
6. The method for preparing the positive electrode material of the sodium-ion battery according to claim 2, wherein the heating temperature in the gel preparation process is 70-90 ℃.
7. The use of the positive electrode material for sodium-ion batteries according to claim 1, as a positive active material for sodium-ion batteries, for the preparation of positive electrodes for sodium-ion batteries.
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