CN114408892B - Preparation and application method of ion-doped phosphate anode material - Google Patents

Preparation and application method of ion-doped phosphate anode material Download PDF

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CN114408892B
CN114408892B CN202210024196.2A CN202210024196A CN114408892B CN 114408892 B CN114408892 B CN 114408892B CN 202210024196 A CN202210024196 A CN 202210024196A CN 114408892 B CN114408892 B CN 114408892B
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刘永畅
李捷
刘毓坤
曲选辉
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University of Science and Technology Beijing USTB
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Abstract

A process for preparing the ion doped phosphate as positive electrode includes such steps as introducing non-active element, stirring, evaporating solvent, drying, grinding, and high-temp calcining in inertial atmosphere to obtain modified Na (4‑a) Mn x Cr y M z (PO 4 ) 3 (ii) a Wherein: m is one or more of Mg, zr and Al; a is the variable of Na content after isovalent doping substitution; and x + y + z =2. The invention has the advantages that: the condition is controllable, the repetition is easy, and the doping modification effect is obvious. Doping element M selectively replaces manganese or chromium sites to form inactive MO 6 The octahedron can effectively pin a crystal structure and stabilize the material in the electrochemical circulation process; meanwhile, the electron/ion conductivity of the material can be improved by doping ions, and the two synergistically improve the cycling stability and rate capability of the high-specific-energy phosphate anode material in the sodium ion battery.

Description

Preparation and application method of ion-doped phosphate anode material
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a preparation method and an application method of an ion-doped phosphate anode material.
Background
Lithium ion batteries have been commercialized and have been successful in the fields of portable electronic devices, electric vehicles, and the like. However, the lithium resource in the crust is low in storage capacity and uneven in distribution, and as the lithium ion battery is further developed, the cost of the lithium ion battery is continuously increased, and the application of the lithium ion battery in the large-scale energy storage field is severely limited. Because the sodium resource is abundant, the distribution is wide, the price is low, and the sodium ion battery shows good application prospect in the fields of large-scale energy storage, low-speed electric vehicles and the like. However, the standard electrode potential of sodium is higher than that of lithium, the ion radius is large, the mass is heavy, the energy density of the sodium-ion battery is low, the reaction kinetics is slow, and the structure of an electrode material is unstable in the process of sodium extraction. The positive electrode material is responsible for providing active sodium ions and high potential reaction couples, and occupies the highest price ratio of the sodium ion battery. Therefore, the development of a positive electrode material with high specific energy, high rate and long service life is one of the key points for promoting the industrialization of the sodium-ion battery.
Among the currently studied positive electrode material systems for sodium ion batteries, sodium fast ion conductor (NASICON) type phosphate is considered to be one of the most promising positive electrode material systems with commercial prospect, because it can provide a fast and stable sodium ion migration channel by virtue of a unique three-dimensional framework structure. The most classical of these is vanadium sodium phosphate (Na) 3 V 2 (PO 4 ) 3 ) Positive electrode material having excellent electrochemical properties (based on V) 3+ /V 4+ Redox couple providing about 110mAh g -1 Specific capacity and operating voltage of about 3.4V). But the energy density is low, and the vanadium raw material is expensive and toxic, so that the commercialization process is slow.
The characteristic of structural diversity of the NASICON material is utilized, the redox couple is regulated and controlled by coordinating the types and the proportions of transition metal elements, so that the working voltage is improved, the multi-electron reaction is realized, and the method is an effective way for obtaining the phosphate anode with high specific energy, and therefore, a large amount of research is conducted by researchers. Masquerier topic group reported Na 4 MnV(PO 4 ) 3 Positive electrode, by exciting Mn 2+ /Mn 3+ (3.6V) and portion V 4+ /V 5+ The (4.0V) couple reaction effectively increases the operating voltage, but the material can only achieve higher capacity in the first turn and quickly decay during subsequent cycles (F.Chen, V.M.Kovrugin, R.David, et al.A. NASICON-type positive electrode for Na batteries with high energy density: na) 4 MnV(PO 4 ) 3 Small Methods,2019 (3): 1800218). Na is reported in the Goodenough group of subjects 3 MnZr(PO 4 ) 3 Introduction of Zr 4+ The latter material is based on Mn 2+ /Mn 3+ The electricity pair realizes 500 cycles of stable circulation, but does not contain active Zr 4+ The presence of (a) limits its theoretical capacity to two-electron reactions (h.c.gao, i.d.seymour, s.xin, et al.na) 3 MnZr(PO 4 ) 3 A high-voltage cathode for sodium batteries, journal of the American Chemical Society,2018 (140): 18192-18199). Recently, manganese chromium sodium phosphate (Na) was reported by Liu Yongchang subject group 4 MnCr(PO 4 ) 3 ) Positive electrode material, success inExcitation of Mn 2+ /Mn 3+ ，Mn 3+ /Mn 4+ (4.2V) and Cr 3+ /Cr 4+ (4.5V) three-electron redox reaction, high voltage and high specific capacity are realized simultaneously, and the energy density reaches 566.5Wh kg -1 Can be compared with commercial lithium iron phosphate, and shows a certain application prospect (J.Zhang, Y.C.Liu, X.D.ZHao, et al.A novel NASICON-type Na) 4 MnCr(PO 4 ) 3 Purifying the energy dense records of phosphate-binders for sodium-ion batteries, advanced Materials,2020 (32): 1906348). However, due to the influence of the distortion of ginger-taylor in manganese-based materials and the decomposition of electrolytes under high voltage, the cycle life of the manganese-based materials cannot meet the actual requirements, and improvement is urgently needed.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method and an application method of an ion-doped phosphate anode material. A proper amount of inactive elements are introduced in the process of preparing the phosphate anode material by a sol-gel method, and the NASICON type phosphate anode material Na is obtained by stirring, evaporating a solvent, drying, grinding into powder and calcining at high temperature in an inert atmosphere (4-a) Mn x Cr y M z (PO 4 ) 3 (ii) a Wherein: m is one or more of Mg, zr and Al; a is the variable of Na content after heterovalent doping substitution; and x + y + z =2. Doping element M selectively replaces manganese or chromium sites to form inactive MO 6 The octahedron can effectively pin a crystal structure and stabilize the material in the electrochemical circulation process; meanwhile, the electron/ion conductivity of the material can be improved by doping ions, and the cycle life and rate capability of the high-specific-energy phosphate anode material in the sodium ion battery are synergistically improved by the doping ions.
Based on the purpose, the invention adopts the following technical scheme:
a preparation method of an ion-doped phosphate cathode material comprises the following steps:
1) Preparing a citric acid aqueous solution, wherein citric acid is used as a carbon source and a complexing agent; adding the transition metal manganese source, the chromium source and the doping element M into the raw materials according to the stoichiometric ratio, stirring for 0.5 hour to completely dissolve and fully complex the transition metal manganese source, the chromium source and the doping element M; then adding a sodium source, a phosphorus source and an additional carbon source, and continuously stirring for 0.5 hour to obtain a clear solution;
2) Stirring the solution in a hot water bath until a green gel is formed, then placing the gel in a forced air drying oven to be heated so as to completely remove moisture, and grinding the gel into powder to obtain a precursor;
3) Putting the precursor powder into a tube furnace, and calcining at high temperature under the protection of inert atmosphere to obtain a doped modified phosphate anode material Na (4-a) Mn x Cr y M z (PO 4 ) 3 。
Further, the stoichiometric ratio of citric acid to transition metal salt in step (1) is 3; the content z of the doping element M is 0.05-0.5; the manganese source comprises at least one of manganese acetate, manganese nitrate and manganese acetylacetonate; the chromium source comprises at least one of chromium nitrate, chromium acetate and chromium sesquioxide; the doping elements comprise one or more of Mg, zr and Al, and the raw materials comprise at least one of corresponding acetate, nitrate and oxide; the sodium source comprises at least one of sodium acetate, sodium carbonate, sodium bicarbonate and sodium hydroxide; the phosphorus source comprises at least one of phosphoric acid and ammonium dihydrogen phosphate; the additional carbon source comprises at least one of ascorbic acid, glucose, methylcellulose.
Further, the temperature of the hot water bath in the step (2) is 70-90 ℃; the temperature of the air-blast drying oven is 100-120 ℃, and the drying time is 3-8 hours.
Further, the inert atmosphere in the step (3) comprises one or more of argon and nitrogen; the calcining temperature is 700 ℃, and the heating rate is 4 ℃ for min -1 The calcination time is 8 hours, and then the mixture is cooled to room temperature along with the furnace and taken out; the molecular formula of the doped and modified phosphate anode material is Na (4-a) Mn x Cr y M z (PO 4 ) 3 Wherein a is a variable of Na content after isovalent doping substitution; and x + y + z =2.
The application method of the ion-doped phosphate cathode material prepared by the method is characterized in that the modified phosphate cathode material Na is doped (4-a) Mn x Cr y M z (PO 4 ) 3 Mixing conductive carbon black and a binder sodium carboxymethyl cellulose (CMC-Na) according to a mass ratio of 70.
Further, doping the modified phosphate cathode material Na (4-a) Mn x Cr y M z (PO 4 ) 3 An electrode slice prepared by mixing conductive carbon black and sodium carboxymethyl cellulose (CMC-Na) serving as a binder is used as a positive electrode of the sodium ion battery, metal sodium is used as a counter electrode, and the concentration is 1mol L -1 NaClO (sodium chloride) 4 5vol% fluoroethylene carbonate (FEC) is added into PC to serve as electrolyte, glass fiber serves as a diaphragm, and the high-purity argon glove box with water and oxygen content less than 0.01ppm is assembled into a CR2032 button cell.
Compared with the prior art, the invention has the advantages that:
(1) The invention has controllable reaction conditions, easy repetition and obvious doping modification effect. Doping element M selectively replaces manganese or chromium sites to form inactive MO 6 The octahedron can effectively pin a crystal structure and stabilize the material in the electrochemical circulation process; meanwhile, the electron/ion conductivity of the material can be improved by doping ions, and the cycle life and the rate capability of the manganese chromium sodium phosphate anode material are synergistically improved by the doping ions.
(2) The idea and the preparation method of ion doping modification provided by the invention can be widely applied to improving the structural stability of the high specific energy phosphate anode material, the process is simple, the cost is low, and the industrial application prospect of the material can be greatly improved.
Drawings
FIG. 1 shows Na obtained in examples 1 to 3 of the present invention (4-a) Mn x Cr y M z (PO 4 ) 3 An XRD spectrum of the anode material;
FIG. 2 shows Na obtained in example 1 of the present invention 4 Mn 0.9 Mg 0.1 Cr(PO 4 ) 3 SEM, TEM and SEM Mapping images of the positive electrode material;
FIG. 3 is a graph obtained in example 1 of the present inventionNa of (2) 4 Mn 0.9 Mg 0.1 Cr(PO 4 ) 3 The charge-discharge curve and the cycle performance chart of the cathode material in the sodium-ion battery.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1:
1) Taking 50mL of deionized water, adding 3mmol of anhydrous citric acid, and stirring until the citric acid is completely dissolved; adding 0.9mmol of anhydrous manganese acetate, 1mmol of chromium nitrate nonahydrate and 0.1mmol of magnesium nitrate hexahydrate into the citric acid solution, and stirring for 0.5 hour to completely dissolve the materials to obtain a clear solution; 4mmol sodium acetate, 205. Mu.L phosphoric acid (85 wt%), 0.2g ascorbic acid were then added and stirring was continued for 0.5 h to give a clear solution;
2) Stirring the solution in a water bath at 80 ℃ to evaporate water until green gel is formed, then placing the gel in a forced air drying oven, heating at 110 ℃ for 3 hours to completely remove the water, and grinding into powder to obtain a precursor;
3) Putting the precursor powder into a tube furnace, and calcining the precursor powder for 8 hours at 700 ℃ in an argon atmosphere to obtain Na 4 Mn 0.9 Mg 0.1 Cr(PO 4 ) 3 And (3) a positive electrode material.
Using Na from example 1 4 Mn 0.9 Mg 0.1 Cr(PO 4 ) 3 The positive electrode material was made into an electrode according to the following method:
mixing Na 4 Mn 0.9 Mg 0.1 Cr(PO 4 ) 3 The positive electrode material, the conductive carbon black and the binder sodium carboxymethyl cellulose (CMC-Na) are mixed according to the mass ratio of 70 -1 NaClO (NaClO) 4 5vol% fluoroethylene carbonate (FEC) is added into PC to serve as electrolyte, glass fiber serves as a diaphragm, and the high-purity argon glove box with water and oxygen content less than 0.01ppm is assembled into a CR2032 button cell.
FIG. 1 shows Na in examples 1 to 3 of the present invention 4 Mn 0.9 Mg 0.1 Cr(PO 4 ) 3 ，Na 3.9 MnCr 0.9 Zr 0.1 (PO 4 ) 3 And Na 4 MnCr 0.9 Al 0.1 (PO 4 ) 3 Compared with a standard diffraction card, the XRD pattern of the anode material is of an NASICON type rhombic hexagonal structure, and the space group is R-3c, so that the crystal structure of the manganese chromium sodium phosphate is not changed by doping a proper amount of inactive elements.
FIG. 2 (a) shows Na in example 1 of the present invention 4 Mn 0.9 Mg 0.1 Cr(PO 4 ) 3 SEM topography of the positive electrode material: the material is uniformly dispersed nano particles, has the size of 200-400nm, has a larger specific surface area, and is beneficial to full infiltration of electrolyte and rapid transmission of sodium ions; the surface of the particles is uniformly coated with amorphous carbon, which is favorable for improving the electronic conductivity of the material. (b) Is Na in example 1 of the invention 4 Mn 0.9 Mg 0.1 Cr(PO 4 ) 3 The HRTEM of the cathode material clearly shows that the surface of the material has a carbon coating layer with a thickness of about 3nm, and the lattice spacing is measured to be 0.38nm and corresponds to the (113) crystal plane. (c) The distribution diagram is SEM Mapping element distribution diagram, and Na, mn, cr, mg, P, O and C elements are uniformly distributed in the material.
FIG. 3 (a) shows Na in example 1 of the present invention 4 Mn 0.9 Mg 0.1 Cr(PO 4 ) 3 The charge-discharge curve of the positive electrode material in the sodium ion battery is shown in the figure, and the charge-discharge curve of the positive electrode material is 1.4-4.5V (vs. Na) + Na) can reach the discharge capacity of 156.0mAh g under the current density of 0.1C within the voltage window -1 Shows Mn 2+ /Mn 3+ ，Mn 3+ /Mn 4+ And Cr 3+ /Cr 4+ The average working voltage of the three-electron redox reaction is 3.43V, and the energy density reaches 535.1Wh kg -1 . FIG. 3 (b) is Na 4 Mn 0.9 Mg 0.1 Cr(PO 4 ) 3 The cycle performance of the anode material under the multiplying power of 0.5C is 131.9mAh g -1 After 50 weeks of cycling, the capacity retention rate was still 84.76%. Compared with undoped manganese chromium sodium phosphate, the cycle stability is obviously improved, and the fact that the manganese chromium sodium phosphate anode can be improved by doping a proper amount of Mg is provedThe material has stable structure in the charging and discharging process.
Example 2:
1) Taking 50mL of deionized water, adding 3mmol of anhydrous citric acid, and stirring until the citric acid is completely dissolved; adding 1mmol of anhydrous manganese acetate, 0.9mmol of chromium nitrate nonahydrate and 0.1mmol of zirconium acetylacetonate into the citric acid solution, and stirring for 0.5 hour to completely dissolve the materials to obtain a clear solution; then 3.9mmol sodium acetate, 205. Mu.L phosphoric acid (85 wt%), 0.2g ascorbic acid were added and stirring was continued for 0.5 hour to obtain a clear solution;
2) Stirring the solution in a water bath at 80 ℃ to evaporate water until green gel is formed, then placing the gel in a forced air drying oven, heating at 110 ℃ for 3 hours to completely remove water, and grinding the gel into powder to obtain a precursor;
3) Putting the precursor powder into a tube furnace, and calcining the precursor powder for 8 hours at 700 ℃ in an argon atmosphere to obtain Na 3.9 MnCr 0.9 Zr 0.1 (PO 4 ) 3 And (3) a positive electrode material.
Using Na from example 2 3.9 MnCr 0.9 Zr 0.1 (PO 4 ) 3 The cathode material was assembled into a button cell type CR2032 according to the method of example 1, and the initial discharge capacity was 138.2mAh g at 0.5C rate -1 After 50 weeks of circulation, the capacity retention rate is 81.04%, and further, the electrochemical circulation stability of the manganese chromium sodium phosphate cathode material can be improved by doping a proper amount of Zr.
Example 3:
1) Taking 50mL of deionized water, adding 3mmol of anhydrous citric acid, and stirring until the citric acid is completely dissolved; adding 1mmol of anhydrous manganese acetate, 0.9mmol of chromium nitrate nonahydrate and 0.1mmol of aluminum nitrate nonahydrate into the citric acid solution, and stirring for 0.5 hour to completely dissolve to obtain a clear solution; 4mmol sodium acetate, 205. Mu.L phosphoric acid (85 wt%), 0.2g ascorbic acid were then added and stirring continued for 0.5 h to give a clear solution;
2) Stirring the solution in a water bath at 80 ℃ to evaporate water until green gel is formed, then placing the gel in a forced air drying oven, heating at 110 ℃ for 3 hours to completely remove the water, and grinding into powder to obtain a precursor;
3) Putting the precursor powder into a tube furnace, and calcining the precursor powder for 8 hours at 700 ℃ in an argon atmosphere to obtain Na 4 MnCr 0.9 Al 0.1 (PO 4 ) 3 And (3) a positive electrode material.
Using Na from example 3 4 MnCr 0.9 Al 0.1 (PO 4 ) 3 The cathode material was assembled as in example 1 to a coin cell type CR2032 with an initial discharge capacity of 141.2mAh g at 0.5C rate -1 And after 50 weeks of circulation, the capacity retention rate is 82.41%, and further confirmation is made that the electrochemical circulation stability of the manganese chromium sodium phosphate cathode material can be improved by proper amount of Al doping.
Finally, it is to be noted that the above examples are only given to aid understanding of the method of the present invention and its core concept. Without limiting the scope of the invention, it will be appreciated by those skilled in the art that various modifications may be made to the invention in order to optimize the present invention. Any modifications and variations that may be made without departing from the principles of the invention are intended to be included within the scope of the following claims.

Claims (6)

1. The preparation method of the ion-doped phosphate cathode material is characterized by comprising the following steps of:
1) Preparing a citric acid aqueous solution, wherein citric acid is used as a carbon source and a complexing agent; adding the transition metal manganese source, the chromium source and the doping element M into the mixture according to the stoichiometric ratio, stirring for 20-40 minutes to completely dissolve and fully complex the transition metal manganese source, the chromium source and the doping element M; then adding a sodium source, a phosphorus source and an additional carbon source, and continuously stirring for 20-40 minutes to obtain a clear solution;
the doping element M comprises one or more of Mg, zr and Al, and the raw material comprises at least one of corresponding acetate, nitrate and oxide;
2) Stirring the solution in a hot water bath until a green gel is formed, then placing the gel in a forced air drying oven to be heated so as to completely remove moisture, and grinding the gel into powder to obtain a precursor;
3) Placing the precursor powder in a tubeCalcining at high temperature in a formula furnace under the protection of inert atmosphere to obtain a doped modified phosphate cathode material Na (4-a) Mn x Cr y M z (PO 4 ) 3 Wherein a is a variable of Na content after isovalent doping substitution; and x + y + z =2;
the inert atmosphere in the step 3) comprises one or more of argon and nitrogen; the calcining temperature is 700 ℃, and the heating rate is 4 ℃ for min -1 The calcination time was 8 hours, and then the reaction mixture was taken out with cooling to room temperature.
2. The method for preparing an ion-doped phosphate cathode material according to claim 1, wherein the content z of the doping element M in step 1) is 0.05 to 0.5.
3. The method for preparing the ion-doped phosphate cathode material according to claim 1, wherein the manganese source in the step 1) comprises at least one of manganese acetate, manganese nitrate and manganese acetylacetonate; the chromium source comprises at least one of chromium nitrate, chromium acetate and chromium sesquioxide; the sodium source comprises at least one of sodium acetate, sodium carbonate, sodium bicarbonate and sodium hydroxide; the phosphorus source comprises at least one of phosphoric acid and ammonium dihydrogen phosphate; the additional carbon source comprises at least one of ascorbic acid, glucose, methylcellulose.
4. The method for preparing the ion-doped phosphate cathode material according to claim 1, wherein the temperature of the hot water bath in the step 2) is 70-90 ℃; the temperature of the air-blast drying oven is 100-120 ℃, and the drying time is 3-8 hours.
5. The application method of the ion-doped phosphate cathode material prepared by the method of claim 1 is characterized in that: doping the modified phosphate cathode material Na (4-a) Mn x Cr y M z (PO 4 ) 3 Mixing conductive carbon black and a binder sodium carboxymethyl cellulose (CMC-Na) according to a mass ratio of 70。
6. The method for using an ion-doped phosphate positive electrode material according to claim 5, wherein: doping the modified phosphate cathode material Na (4-a) Mn x Cr y M z (PO 4 ) 3 An electrode slice prepared by mixing conductive carbon black and sodium carboxymethyl cellulose (CMC-Na) as binder is used as the positive electrode of the sodium ion battery, metal sodium is used as a counter electrode, and the concentration is 1mol L -1 NaClO (NaClO) 4 Adding 5vol% fluoroethylene carbonate (FEC) into PC as electrolyte, taking glass fiber as a diaphragm, and assembling the mixture into a CR2032 button cell in a high-purity argon atmosphere glove box with water and oxygen contents of less than 0.01 ppm.
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