CN114824216A - Multielement-doped sodium-ion battery positive electrode material and preparation method and application thereof - Google Patents

Multielement-doped sodium-ion battery positive electrode material and preparation method and application thereof Download PDF

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CN114824216A
CN114824216A CN202210461978.2A CN202210461978A CN114824216A CN 114824216 A CN114824216 A CN 114824216A CN 202210461978 A CN202210461978 A CN 202210461978A CN 114824216 A CN114824216 A CN 114824216A
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胡朴
汤傲
邹义琪
商超群
张占辉
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Wuhan Institute of Technology
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Abstract

The invention relates to the field of sodium ion battery electrode materials, and discloses a multielement-doped sodium ion battery anode material and a preparation method and application thereof. The composition of the positive electrode material is Na z Mn w V y M u (PO 4 ) 3‑x (SiO 4 ) x Wherein M is a transition metal, x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0.5 and less than or equal to 2, w is more than or equal to 0.01 and less than or equal to 1, u is more than or equal to 0 and less than or equal to 1, z is more than or equal to 3 and less than or equal to 4, x and u are not 0 at the same time, and the algebraic sum of the valence of each element is zero; the preparation process comprises the steps of preparing a precursor by a sol-gel method, grinding and sintering. The invention utilizes manganese, silicon and transition metal to Na with NASICON structure 3 V 2 (PO 4 ) 3 The doping modification is carried out, and the manganese is doped with a V site, the transition metal is doped with a V site, and the silicon is doped with a P site, so that the material has higher energy density, more excellent electrochemical performance and cycle performance while maintaining an excellent three-dimensional frame structure, and has good application prospects in sodium-ion batteries and energy storage.

Description

Multielement-doped sodium-ion battery positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the field of sodium ion battery electrode materials, in particular to a multielement doped sodium ion battery anode material and a preparation method and application thereof.
Background
With the continuous use of non-renewable energy sources, renewable energy sources (such as wind energy, tidal energy, solar energy and the like) are more and more emphasized due to the energy crisis, and because the renewable energy sources have the characteristics of uncontrollable and unadjustable, the stored energy plays a key role in the utilization process of the energy sources. With the development of several decades, lithium ion batteries have been widely used as representative energy storage technologies, making it possible to reduce the consumption of fossil fuels. However, because the lithium resource is very limited and the heavy metal elements such as cobalt and nickel, which are commonly used in lithium ion batteries, are also very rare, the application of the lithium ion batteries in large-scale energy storage is limited.
As is well known, the sodium element is relatively abundant in the earth crust and has a wide distribution area, and meanwhile, the physicochemical properties of sodium and lithium are similar and the de/intercalation mechanism is similar, so the research and development of the sodium-ion battery are expected to alleviate the problem of limited development of the energy storage battery caused by the shortage of lithium resources to a certain extent. Besides the advantages of abundant and easily available resources, low cost and wide distribution, compared with the lithium ion battery, the sodium ion battery has the advantage of safety, the thermal runaway temperature of the sodium battery is higher than that of the lithium battery, the passivation and oxidation are easier, and the inflammable phenomenon is not easily generated, which is the main defect of the lithium battery. Therefore, sodium ion batteries have a great potential for industrialization.
In the sodium ion battery, the positive electrode material is a bottleneck to increase its energy density and power output, and thus, there is a need to vigorously develop an advanced positive electrode material. Na of sodium super ion conductor (NASICON) structure 3 V 2 (PO 4 ) 3 The composite material has the advantages of excellent structural stability, higher oxidation-reduction potential, good thermal stability, larger theoretical energy density, open three-dimensional framework structure and the like. However, due to Na + Larger ionic radius and retarded diffusion kinetic rate to make the energy of the material denseThe degree, electrochemical performance and cycling performance are greatly restricted, limiting further practical applications, particularly in large-scale energy storage systems.
Disclosure of Invention
The invention aims to solve the technical problem of providing a multielement doped sodium ion battery anode material and a preparation method and application thereof aiming at the defects of the conventional sodium ion battery anode material, wherein Na of an NASICON structure is subjected to manganese, silicon and transition metal 3 V 2 (PO 4 ) 3 And doping modification is carried out, and the manganese is doped with a V site, the transition metal is doped with a V site, and the silicon is doped with a P site, so that the material has higher energy density, more excellent electrochemical performance and cycle performance while maintaining an excellent three-dimensional frame structure.
In order to solve the technical problems provided by the invention, the invention provides a multielement doped sodium-ion battery positive electrode material, and the composition of the material is Na z Mn w V y M u (PO 4 ) 3-x (SiO 4 ) x (ii) a Wherein M is transition metal, x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0.5 and less than or equal to 2, w is more than or equal to 0.01 and less than or equal to 1, u is more than or equal to 0 and less than or equal to 1, z is more than or equal to 3 and less than or equal to 4, x and u are not 0 at the same time, and the algebraic sum of the valence of each element is zero.
In the above scheme, the transition metal is Zr 4+ 、Nb 5+ 、La 3+ 、Ce 3+ 、Ti 4+ 、Cr 3+ 、Fe 3+ One kind of (1).
The invention also provides a preparation method of the multielement doped sodium ion battery anode material, which comprises the following steps:
(1) mixing: according to the weight ratio of sodium: vanadium: phosphorus: manganese: silicon: the mol ratio of the transition metal is z, y (3-x), w, x, u, sodium source, vanadium source, phosphorus source, manganese source, silicon source and transition metal source are weighed, and complexing agents are weighed and mixed together in water to prepare precursor liquid;
(2) and (3) drying: drying the precursor liquid for the first time until the precursor liquid forms a gel state, and then drying the gel product for the second time to obtain a precursor;
(3) grinding: grinding the precursor to prepare precursor powder;
(4) and (3) sintering: and pre-sintering the precursor powder under an inert protective atmosphere, and sintering to obtain the final product, namely the positive electrode material of the sodium-ion battery.
In the scheme, the sodium source is one or more of sodium acetate, sodium nitrate, sodium oxalate, sodium citrate, sodium carbonate, sodium bicarbonate and the like; the vanadium source is one or more of ammonium metavanadate, sodium metavanadate, vanadium acetylacetonate and the like; the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, etc.
In the scheme, the manganese source is one or more of manganese acetate, manganese nitrate, manganese oxalate dihydrate, manganese carbonate, manganese dihydrogen phosphate and the like; the silicon source is one or more of silicon acetate, hexamethylcyclotrisiloxane, tetraethyl orthosilicate and the like; the transition metal source is one or more of zirconium nitrate, zirconium acetate, zirconium acetylacetonate, niobium oxalate hydrate, sodium niobate, lanthanum nitrate, lanthanum oxalate, lanthanum acetate, lanthanum carbonate, cerium ammonium nitrate, cerium oxalate, cerium carbonate, tetrabutyl titanate, chromium acetate, chromium nitrate, ferric oxalate, ferric citrate, etc.
In the scheme, the complexing agent is one or more of oxalic acid, ascorbic acid, citric acid monohydrate, malic acid and the like.
In the scheme, the molar weight of the complexing agent in the precursor liquid is 1-2 times of the sum of the molar weights of vanadium, manganese and transition metal, and the mass fraction of the solute in the precursor liquid is 10-25%.
In the scheme, the first-stage drying and the second-stage drying are both normal-pressure drying; the drying temperature of the first-stage drying is 75-95 ℃, and the drying time is 3-4 h; the drying temperature of the second-stage drying is 120-180 ℃, and the drying time is 3-4 h.
In the scheme, the grinding time is 20-60min, and the precursor powder is ground to be uniform in particle size.
In the scheme, the temperature rise rate of the pre-sintering is 3-10 ℃/min, and the temperature is kept for 3-4h after the temperature is raised to 350-450 ℃; the temperature rise rate of sintering is 3-10 ℃/min, and after the temperature rises to 500-850 ℃, the temperature is kept for 5-15 h.
In the scheme, the inert protective atmosphere is one or more of argon, nitrogen, hydrogen argon, helium and the like.
The invention also provides an application of the multielement doped sodium ion battery anode material in a sodium ion battery, and the specific method comprises the following steps:
the multielement-doped positive electrode material Na of the sodium-ion battery z Mn w V y M u (PO 4 ) 3-x (SiO 4 ) x The sodium ion button cell is manufactured by sequentially assembling a cathode shell, an anode, a diaphragm, electrolyte, an anode, a gasket, a spring plate and an anode shell into an anode, taking sodium metal as a cathode and glass fiber as a diaphragm.
In the scheme, the electrolyte is prepared by dissolving sodium salt and an additive in a solvent, the sodium salt is sodium perchlorate, the additive is fluoroethylene carbonate (FEC), the solvent is Ethylene Carbonate (EC) and Polycarbonate (PC) in a volume ratio of 1:1, the concentration of the sodium salt in the electrolyte is 1mol/L, and the additive is added in an amount of 5% of the total mass of the sodium salt and the solvent.
The invention is to Na 3 V 2 (PO 4 ) 3 Doping modification is carried out, and doping different elements has different functions: after V in the material is replaced by Mn, the main body structure of the material cannot be damaged, higher voltage and energy density can be obtained in an electrochemical reaction, and meanwhile, as V is a toxic rare metal, Mn is nontoxic and has far more abundant resources than V, the safety of the material is improved after V is replaced by Mn, and the cost of the material is obviously reduced; doping transition metal M with different valence states and radiuses at the V position is beneficial to supporting a crystal framework, and changing Mn-O bonds, M-O bonds, Mn-M bonds and the spatial configuration thereof through an inter-ion coulomb effect, so that the disorder degree of Mn-O6 is increased, ginger-Taylor distortion caused by Mn is inhibited, and the electrochemical performance and the cycle performance of the material are improved; introducing Si with larger ion radius at the P position, increasing the cell volume and the ion transmission bottleneck area, and improving Na through the space effect + Transport properties due to Si 4+ Substituted P 5+ Increase Na in the crystal lattice + The concentration reaches charge balance, so that the material obtains smaller particle size and better cycle performance.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention utilizes manganese, silicon and transition metal pair Na 3 V 2 (PO 4 ) 3 Doping modification is carried out, the energy density of the material is improved by doping the V site with manganese, the electrochemical performance and the cycle performance of the material are improved by doping the V site with transition metal, and the Na is improved by doping the P site with silicon + Transport performance and material circulation performance, and multielement doped positive electrode material Na of sodium ion battery z Mn w V y M u (PO 4 ) 3-x (SiO 4 ) x Has higher energy density and more excellent electrochemical performance and cycle performance, compared with the undoped Na-ion battery anode material Na 3 V 2 (PO 4 ) 3 The lithium ion battery has higher discharge specific capacity, longer cycle life and more stable high-rate performance, and has good application prospect in sodium ion batteries and energy storage.
(2) The preparation method has the advantages of short flow and easy operation, replaces partial vanadium source by the manganese source and the transition metal source in the preparation process, reduces the use of toxic metals, improves the safety of the material and reduces the cost at the same time, and the obtained Na z Mn w V y M u (PO 4 ) 3-x (SiO 4 ) x Still maintain Na 3 V 2 (PO 4 ) 3 The excellent three-dimensional frame structure has good structural stability, strengthens the stability of the frame in the charging and discharging process, and is suitable for large-scale industrial production.
Drawings
FIG. 1 shows Na obtained in comparative example 1 of the present invention 3 V 2 (PO 4 ) 3 XRD pattern of (a).
FIG. 2 shows Na obtained in comparative example 1 of the present invention 3 V 2 (PO 4 ) 3 Constant current cycle diagram.
FIG. 3 shows Na obtained in comparative example 1 of the present invention 3 V 2 (PO 4 ) 3 The rate performance graph of (1).
FIG. 4 shows Na obtained in example 1 of the present invention 3.3 Mn 0.1 V 1.9 (PO 4 ) 2.8 (SiO 4 ) 0.2 XRD pattern of (a).
FIG. 5 shows Na obtained in example 1 of the present invention 3.3 Mn 0.1 V 1.9 (PO 4 ) 2.8 (SiO 4 ) 0.2 The charge and discharge performance of (1).
FIG. 6 shows Na obtained in example 1 of the present invention 3.3 Mn 0.1 V 1.9 (PO 4 ) 2.8 (SiO 4 ) 0.2 Constant current cycle diagram.
FIG. 7 shows Na obtained in example 1 of the present invention 3.3 Mn 0.1 V 1.9 (PO 4 ) 2.8 (SiO 4 ) 0.2 The rate performance graph of (2).
FIG. 8 shows Na obtained in example 2 of the present invention 4 MnV 0.95 Zr 0.05 (PO 4 ) 2.95 (SiO 4 ) 0.05 XRD pattern of (a).
FIG. 9 shows Na obtained in example 2 of the present invention 4 MnV 0.95 Zr 0.05 (PO 4 ) 2.95 (SiO 4 ) 0.05 SEM image of (d).
FIG. 10 shows Na obtained in example 3 of the present invention 4 MnV 0.9 La 0.1 (PO 4 ) 3 XRD pattern of (a).
FIG. 11 shows Na obtained in example 4 of the present invention 4 MnV 0.8 La 0.2 (PO 4 ) 3 XRD pattern of (a).
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Comparative example 1
A positive electrode material for sodium-ion battery contains Na 3 V 2 (PO 4 ) 3 The preparation method comprises the following steps:
(1) mixing: 0.4972g of CH 3 COONa、0.4726g NH 4 VO 3 、0.6971g NH 4 H 2 PO4 and 1.6896g C 6 H 8 O 7 Mixing the components in 30mL of deionized water to prepare a precursor solution;
(2) and (3) drying: placing the precursor solution in a constant-temperature water bath, heating to 80 ℃ and drying for 3.5h to form blue gelatinous semisolid, then placing the gelatinous semisolid in a drying box, heating to 120 ℃ and drying for 4h to obtain light green fluffy porous solid, namely a precursor;
(3) grinding: grinding the precursor for 25min to prepare precursor powder with uniform particle size;
(4) and (3) sintering: placing the precursor powder in a muffle furnace, heating to 350 ℃ at a heating rate of 3 ℃/min under the protection of argon, preserving heat for 3h for presintering, heating to 850 ℃ at a heating rate of 3 ℃/min, preserving heat for sintering for 7h, and cooling to obtain a final product Na 3 V 2 (PO 4 ) 3 。
FIG. 1 shows Na obtained in this comparative example 3 V 2 (PO 4 ) 3 The XRD pattern of the material can be seen from the figure, each diffraction peak of the material is narrow and sharp, and the position and relative intensity of each diffraction peak are equal to that of Na 3 V 2 (PO 4 ) 3 The standard cards were essentially identical, indicating that the material was successfully prepared and had good crystallinity.
FIG. 2 shows Na obtained in this comparative example 3 V 2 (PO 4 ) 3 The constant current cycle chart shows that the first discharge specific capacity of the material under the current density of 0.2C is 88mAh/g, the discharge specific capacity is 51mAh/g after 40 cycles, and the capacity retention rate is only 57.9%.
FIG. 3 shows Na obtained in this comparative example 3 V 2 (PO 4 ) 3 The rate performance graph shows that the specific discharge capacity of the material is obviously reduced along with the increase of the current density under the current densities of 0.5C, 1C, 2C and 5C, and the high rate performance of the material is generally shown.
Example 1
A positive electrode material of sodium-ion battery contains Na 3.3 Mn 0.1 V 1.9 (PO 4 ) 2.8 (SiO 4 ) 0.2 The preparation method comprises the following steps:
(1) mixing: 1.0937g of CH 3 COONa、2.6736g C 15 H 21 O 6 V、1.2883g NH 4 H 2 PO 4 、0.1014g MnN 2 O 6 ·4H 2 O、0.17g C 8 H 12 O 4 Si and 2.1134g C 6 H 8 O 6 Mixing the components in 30mL of deionized water to prepare a precursor solution;
(2) and (3) drying: placing the precursor solution in a constant-temperature water bath, heating to 90 ℃ and drying for 3h to form blue gelatinous semisolid, then placing the gelatinous semisolid in a drying box, heating to 150 ℃ and drying for 3h to obtain light grayish yellow fluffy porous solid, namely a precursor;
(3) grinding: grinding the precursor for 30min to prepare precursor powder with uniform particle size;
(4) and (3) sintering: placing the precursor powder in a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving heat for 3.5h for presintering, heating to 550 ℃ at a heating rate of 5 ℃/min, preserving heat for sintering for 14h, and cooling to obtain a final product Na 3.3 Mn 0.1 V 1.9 (PO 4 ) 2.8 (SiO 4 ) 0.2 。
FIG. 4 shows Na obtained in this example 3.3 Mn 0.1 V 1.9 (PO 4 ) 2.8 (SiO 4 ) 0.2 The XRD pattern of the material is narrow and sharp in diffraction peaks, and the material has good crystallinity; position and relative intensity of each diffraction peak with Na 3 V 2 (PO 4 ) 3 After standard card comparison, the XRD pattern was shifted to a low angle after doping due to the incorporation of ionic Mn 2+ With Si 4+ Radius of greater than V 3+ And P 5+ The radius of (a) results from an increase in the unit cell volume of the material. As described above, Mn 2+ With Si 4+ The doping of (A) does not change the original NASICON structure, while Si does not change the original NASICON structure 4+ Successfully incorporate P 5+ The sites give good structural stability to the sample while strengthening the stability of the frame during charging and discharging.
FIG. 5 shows Na obtained in this example 3.3 Mn 0.1 V 1.9 (PO 4 ) 2.8 (SiO 4 ) 0.2 The first specific discharge capacity of the material under 0.5C, 1C, 2C and 5C is 83.4mAh/g, 82.8 mAh/g, 80.8mAh/g and 73.7mAh/g respectively, and the material has high initial specific discharge capacity under different multiplying powers.
FIG. 6 shows Na obtained in this example 3.3 Mn 0.1 V 1.9 (PO 4 ) 2.8 (SiO 4 ) 0.2 The constant current cycle diagram can show that the first discharge specific capacity of the material under the current density of 0.2C is 94.9mAh/g, after cycle for 40 times, the discharge specific capacity is 92.7mAh/g, the capacity retention rate is as high as 98.98 percent, and the material has high discharge specific capacity and good cycle stability.
FIG. 7 shows Na obtained in this example 3.3 Mn 0.1 V 1.9 (PO 4 ) 2.8 (SiO 4 ) 0.2 The rate performance graph shows that the specific discharge capacity of the material has no obvious difference under the current densities of 0.5C, 1C, 2C and 5C, and the material has ideal specific discharge capacity even under a larger current density, which shows that the material has good performance under high rate.
In conclusion, the multielement doped positive electrode material Na of the sodium-ion battery 3.3 Mn 0.1 V 1.9 (PO 4 ) 2.8 (SiO 4 ) 0.2 Less doped positive electrode material Na of sodium ion battery 3 V 2 (PO 4 ) 3 The material has higher specific discharge capacity, better cycle life and more stable high-rate performance, and shows that the doped material has higher energy density and more excellent electrochemical performance and cycle performance.
Example 2
A positive electrode material for sodium-ion battery contains Na 4 MnV 0.95 Zr 0.05 (PO 4 ) 2.95 (SiO 4 ) 0.05 The preparation method comprises the following steps:
(1) mixing: 1.3091g of CH 3 COONa、0.4633g NaVO 3 、1.3721g NH 4 H 2 PO 4 、0.4601g MnCO 3 、0.0425g C 8 H 12 O 4 Si、0.0864g Zr(NO 3 ) 4 ·5H 2 O and 0.7275g C 2 H 2 O 4 Mixing the components in 30mL of deionized water to prepare a precursor solution;
(2) and (3) drying: placing the precursor solution in a constant-temperature water bath, heating to 75 ℃ and drying for 4h to form blue gelatinous semisolid, then placing the gelatinous semisolid in a drying box, heating to 180 ℃ and drying for 3h to obtain light grayish yellow fluffy porous solid, namely a precursor;
(3) grinding: grinding the precursor for 40min to prepare precursor powder with uniform particle size;
(4) and (3) sintering: placing the precursor powder in a muffle furnace, heating to 350 ℃ at a heating rate of 8 ℃/min under the protection of argon, preserving heat for 4h for presintering, heating to 750 ℃ at a heating rate of 8 ℃/min, preserving heat for sintering for 11h, and cooling to obtain a final product Na 4 MnV 0.95 Zr 0.05 (PO 4 ) 2.95 (SiO 4 ) 0.05 。
FIG. 8 shows Na obtained in this example 4 MnV 0.95 Zr 0.05 (PO 4 ) 2.95 (SiO 4 ) 0.05 The XRD pattern of the material is narrow and sharp in diffraction peaks, and the material has good crystallinity; position and relative intensity of each diffraction peak with Na 4 MnV(PO 4 ) 3 After standard card comparison, the XRD pattern is shifted to a low angle after doping, the original NASICON structure of the material is not changed but the unit cell volume is increased, and Mn 2+ 、Zr 4+ And Si 4+ The structural stability of the material is further improved by the doping.
FIG. 9 shows Na obtained in this example 4 MnV 0.95 Zr 0.05 (PO 4 ) 2.95 (SiO 4 ) 0.05 As can be seen from the SEM image of (a), the material has good crystallinity, and the particle size is about 3 to 8 μm.
Example 3
A positive electrode material for sodium-ion battery contains Na 4 MnV 0.9 La 0.1 (PO 4 ) 3 The preparation method comprises the following steps:
(1) mixing: 0.3314g of CH 3 COONa、0.4261g NH 4 VO 3 、1.454g NaH 2 PO 4 、0.9906g(CH 3 COO) 2 Mn·4H 2 O、0.1739g La(NO 3 ) 3 ·6H 2 O and 1.6091g C 4 H 6 O 5 Mixing the components in 30mL of deionized water to prepare a precursor solution;
(2) and (3) drying: placing the precursor solution in a constant-temperature water bath, heating to 85 ℃ and drying for 4h to form blue gelatinous semisolid, then placing the gelatinous semisolid in a drying box, heating to 160 ℃ and drying for 3h to obtain light grayish yellow fluffy porous solid, namely a precursor;
(3) grinding: grinding the precursor for 25min to prepare precursor powder with uniform particle size;
(4) and (3) sintering: placing the precursor powder in a muffle furnace, heating to 350 ℃ at a heating rate of 5 ℃/min under the protection of hydrogen and argon, preserving heat for 3h for presintering, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat for sintering for 15h, and cooling to obtain a final product Na 4 MnV 0.9 La 0.1 (PO 4 ) 3 。
FIG. 10 shows Na obtained in this example 4 MnV 0.9 La 0.1 (PO 4 ) 3 The XRD pattern of the material is narrow and sharp in diffraction peaks, and the material has good crystallinity; position and relative intensity of each diffraction peak with Na 4 MnV(PO 4 ) 3 After standard card comparison, the XRD pattern is shifted to a low angle after doping, the original NASICON structure of the material is not changed but the unit cell volume is increased, and Mn 2+ And La 3+ The structural stability of the material is further improved by the doping.
Example 4
A positive electrode material for sodium-ion battery contains Na 4 MnV 0.8 La 0.2 (PO 4 ) 3 The preparation method comprises the following steps:
(1) mixing: 0.3314g of CH 3 COONa、0.3781g NH 4 VO 3 、1.454g NaH 2 PO 4 、0.9906g(CH 3 COO) 2 Mn·4H 2 O、0.3464g La(NO 3 ) 3 ·6H 2 O and 1.6091g C 4 H 6 O 5 Mixing the components in 30mL of deionized water to prepare a precursor solution;
(2) and (3) drying: placing the precursor solution in a constant-temperature water bath, heating to 85 ℃ and drying for 4h to form blue gelatinous semisolid, then placing the gelatinous semisolid in a drying box, heating to 160 ℃ and drying for 3h to obtain light grayish yellow fluffy porous solid, namely a precursor;
(3) grinding: grinding the precursor for 25min to prepare precursor powder with uniform particle size;
(4) and (3) sintering: placing the precursor powder in a muffle furnace, heating to 350 ℃ at a heating rate of 5 ℃/min under the protection of hydrogen and argon, preserving heat for 3h for presintering, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat for sintering for 15h, and cooling to obtain a final product Na 4 MnV 0.8 La 0.2 (PO 4 ) 3 。
FIG. 11 shows Na obtained in this example 4 MnV 0.8 La 0.2 (PO 4 ) 3 The XRD pattern of the material is narrow and sharp in diffraction peaks, and the material has good crystallinity; position and relative intensity of each diffraction peak with Na 4 MnV(PO 4 ) 3 After standard card comparison, the XRD pattern is shifted to a low angle after doping, the original NASICON structure of the material is not changed but the unit cell volume is increased, and Mn 2+ And La 3+ The structural stability of the material is further improved by the doping.
Example 5
A positive electrode material for sodium-ion battery contains Na 4 MnV 0.9 Ce 0.1 (PO 4 ) 3 The preparation method comprises the following steps:
(1) mixing: 1.3135g of CH 3 COONa、0.4261g NH 4 VO 3 、1.5847g(NH 4 ) 2 HPO 4 、0.991g(CH 3 COO) 2 Mn·4H 2 O、0.1753g Ce(NO 3 ) 3 ·6H 2 O and 2.5273g C 6 H 8 O 7 Mixing the components in 30mL of deionized water to prepare a precursor solution;
(2) and (3) drying: placing the precursor solution in a constant-temperature water bath, heating to 80 ℃ and drying for 3.5h to form blue gelatinous semisolid, then placing the gelatinous semisolid in a drying box, heating to 150 ℃ and drying for 3.5h to obtain light grayish yellow fluffy porous solid, namely a precursor;
(3) grinding: grinding the precursor for 20min to prepare precursor powder with uniform particle size;
(4) and (3) sintering: placing the precursor powder in a muffle furnace, heating to 450 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, preserving heat for 4h for presintering, heating to 650 ℃ at a heating rate of 3 ℃/min, preserving heat for sintering for 12h, and cooling to obtain a final product Na 4 MnV 0.9 Ce 0.1 (PO 4 ) 3 。
Example 6
A positive electrode material for sodium-ion battery contains Na 3.8 MnV 0.9 Nb 0.1 (PO 4 ) 3 The preparation method comprises the following steps:
(1) mixing: 1.2268g of CH 3 COONa、1.2925g C 15 H 21 O 6 V、0.4647g NH 4 H 2 PO 4 、1.1513g MnH 4 P 2 O 8 ·2H 2 O、0.0659g NaNbO 3 And 1.6091g C 4 H 6 O 5 Mixing the components in 30mL of deionized water to prepare a precursor solution;
(2) and (3) drying: placing the precursor solution in a constant-temperature water bath, heating to 90 ℃ and drying for 3h to form blue gelatinous semisolid, then placing the gelatinous semisolid in a drying box, heating to 120 ℃ and drying for 4h to obtain light grayish yellow fluffy porous solid, namely a precursor;
(3) grinding: grinding the precursor for 30min to prepare precursor powder with uniform particle size;
(4) and (3) sintering: placing the precursor powder in a muffle furnace, heating to 400 ℃ at a heating rate of 6 ℃/min under the protection of helium, preserving heat for 3.5h for presintering, heating to 800 ℃ at a heating rate of 3 ℃/min, preserving heat for sintering for 8h, and cooling to obtain a final product Na 3.8 MnV 0.9 Nb 0.1 (PO 4 ) 3 。
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessarily exhaustive of all embodiments, and are therefore intended to be within the scope of the invention.

Claims (10)

1. The multielement doped positive electrode material of the sodium-ion battery is characterized in that the positive electrode material consists of Na z Mn w V y M u (PO 4 ) 3-x (SiO 4 ) x (ii) a Wherein M is transition metal, x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0.5 and less than or equal to 2, w is more than or equal to 0.01 and less than or equal to 1, u is more than or equal to 0 and less than or equal to 1, z is more than or equal to 3 and less than or equal to 4, x and u are not 0 at the same time, and the algebraic sum of the valence of each element is zero.
2. The multi-element doped sodium ion battery positive electrode material of claim 1, wherein the transition metal is Zr 4+ 、Nb 5+ 、La 3+ 、Ce 3+ 、Ti 4+ 、Cr 3+ 、Fe 3+ One kind of (1).
3. A method of preparing the multielement doped positive electrode material of a sodium ion battery as claimed in claim 1, comprising the steps of:
(1) mixing: weighing a sodium source, a vanadium source, a phosphorus source, a manganese source, a silicon source and a transition metal source according to the molar ratio of sodium, vanadium, phosphorus, manganese, silicon and transition metal z to y (3-x) and w to x to u, weighing a complexing agent, and mixing the sodium source, the vanadium source, the phosphorus source, the manganese source, the silicon source and the transition metal source in water to prepare a precursor solution;
(2) and (3) drying: drying the precursor liquid for the first time until the precursor liquid forms a gel state, and then drying the gel product for the second time to obtain a precursor;
(3) grinding: grinding the precursor to prepare precursor powder;
(4) and (3) sintering: and pre-sintering the precursor powder under an inert protective atmosphere, and sintering to obtain the final product, namely the positive electrode material of the sodium-ion battery.
4. The method for preparing the multielement doped sodium ion battery positive electrode material according to claim 3, wherein the sodium source is one or more of sodium acetate, sodium nitrate, sodium oxalate, sodium citrate, sodium carbonate and sodium bicarbonate; the vanadium source is one or more of ammonium metavanadate, sodium metavanadate and vanadium acetylacetonate; the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and sodium phosphate; the manganese source is one or more of manganese acetate, manganese nitrate, manganese oxalate dihydrate, manganese carbonate and manganese dihydrogen phosphate; the silicon source is one or more of silicon acetate, hexamethylcyclotrisiloxane and tetraethyl orthosilicate; the transition metal source is one or more of zirconium nitrate, zirconium acetate, zirconium acetylacetonate, niobium oxalate hydrate, sodium niobate, lanthanum nitrate, lanthanum oxalate, lanthanum acetate, lanthanum carbonate, cerium ammonium nitrate, cerium oxalate, cerium carbonate, tetrabutyl titanate, chromium acetate, chromium nitrate, ferric oxalate and ferric citrate.
5. The method for preparing the multielement doped sodium ion battery positive electrode material according to claim 3, wherein the complexing agent is one or more of oxalic acid, ascorbic acid, citric acid monohydrate and malic acid.
6. The method according to claim 3, wherein the molar amount of the complexing agent in the precursor solution is 1-2 times the sum of the molar amounts of vanadium, manganese and transition metal, and the mass fraction of the solute in the precursor solution is 10-25%.
7. The method for preparing the multi-element doped sodium-ion battery cathode material according to claim 3, wherein the primary drying and the secondary drying are both normal-pressure drying; the drying temperature of the first-stage drying is 75-95 ℃, and the drying time is 3-4 h; the drying temperature of the second-stage drying is 120-180 ℃, and the drying time is 3-4 h.
8. The method for preparing the multielement doped sodium ion battery positive electrode material as claimed in claim 3, wherein the temperature rise rate of the pre-sintering is 3-10 ℃/min, and the temperature is maintained for 3-4h after the temperature is raised to 350-450 ℃; the temperature rise rate of sintering is 3-10 ℃/min, and after the temperature rises to 500-850 ℃, the temperature is kept for 5-15 h.
9. The method for preparing the multi-element doped sodium-ion battery cathode material according to claim 3, wherein the inert protective atmosphere is one or more of argon, nitrogen, hydrogen argon and helium.
10. Use of a multielement doped positive electrode material of a sodium ion battery as described in any of the claims 1-9 in a sodium ion battery.
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