CN116130621A - Polyanionic sodium ion battery positive electrode material, preparation and application thereof - Google Patents
Polyanionic sodium ion battery positive electrode material, preparation and application thereof Download PDFInfo
- Publication number
- CN116130621A CN116130621A CN202211557118.5A CN202211557118A CN116130621A CN 116130621 A CN116130621 A CN 116130621A CN 202211557118 A CN202211557118 A CN 202211557118A CN 116130621 A CN116130621 A CN 116130621A
- Authority
- CN
- China
- Prior art keywords
- sodium
- ion battery
- positive electrode
- electrode material
- sodium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a polyanion sodium ion battery positive electrode material, and preparation and application thereof, wherein the positive electrode material has a chemical formula of Na 4‑(n‑2)x Mn 1‑x VM x (PO 4 ) 3 @C, wherein M is a dopant ion comprising W 3+ 、Ga 3+ 、La 3+ 、Y 3+ 、Yb 3+ 、Sn 4+ 、Zr 4+ 、Nb 5+ 、Mo 6+ N is the valence of the doping ion, 0<x is less than or equal to 0.2. The invention adopts high valence and large radius ion to replace Mn position, which can adjust the local ion bond strength and electron-hole distribution state in the crystal lattice, reduce energy band gap, improve electron conductivity, expand sodium ion diffusion channel in the crystal lattice and increase sodium ion migration capacity; thereby improving the high rate performance of the material. Another partyThe doping of the surface element can reduce John-Teller effect, strengthen lattice stability of the material and improve cycling stability of the material. The material designed by the invention has good multiplying power performance and cycle life, and is suitable for industrialized amplification.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery anode materials, and particularly relates to a polyanion type sodium ion battery anode material, and preparation and application thereof.
Background
Rechargeable lithium ion batteries, which benefit from high energy density and long cycle life, have been widely used in electric vehicles and in the field of large-scale energy storage. However, the lithium resources are distributed unevenly, the supply capacity is insufficient, and in this case, the rapid expansion of the market leads to the price increase of the lithium ion battery, which severely limits the application of the lithium ion battery in large-scale power grid energy storage. In contrast, sodium Ion Batteries (SIBs), while having a gap from lithium ion batteries in electrochemical performance, have the significant advantages of abundant sodium element resources and low cost. In the face of trillion-level energy storage markets and energy storage strategic demands, the sodium ion battery can avoid the risk of market fluctuation of the lithium ion battery caused by shortage of lithium element resources to a great extent, and the lithium ion battery can be effectively supplemented in the lithium ion battery market. With the progressive refinement of sodium ion battery technology, the market of partial lead-acid batteries can be possibly replaced, or the technology of the large-scale distributed energy storage field in the future can be dominant, and the development of sodium ion batteries has been driven into a fast lane.
With sodium vanadium phosphate (Na) 3 V 2 (PO 4 ) 3 ) The representative sodium super-ion conductor type (NASICON) phosphate sodium ion battery anode material benefits from phosphate-oxygen ion bond (P-O) with stable phosphate radical in a lattice structure, has high crystal structure stability and thermal safety, can be compared with lithium iron phosphate in a lithium battery, and is a sodium ion battery anode material with market prospect. Since the V source is relatively expensive, partial V is replaced with inexpensive Mn to obtain Na 4 MnV(PO 4 ) 3 Has good application prospect. With Na and Na 3 V 2 (PO 4 ) 3 Same as Na 4 MnV(PO 4 ) 3 The positive electrode material also has a problem of poor intrinsic electron conductivity, resulting in a short plate in its electrochemical properties, particularly in the rate properties. To overcome this problem, as reported in inventions CN 106992298A and CN 112242525A, the improvement of the overall conductivity of the material, in particular the introduction of highly conductive carbon materials such as carbon nanotubes, graphene, acetylene black, etc., is a common means to solve the above problems, usually in a way that is supplemented with an external conductive agent. However, too much mixing of highly conductive carbon materials such as carbon nanotubes, graphene, acetylene black, etc. tends to significantly reduce the workability of the materialsAnd the tap density of the electrode material is reduced, and the volume energy density is weakened. The electron energy band structure and the lattice structure of the matrix material are adjusted through element doping, so that the intrinsic electron conductivity and the ion diffusion capacity of the material are improved, and the method has more practical value for developing the polyanion sodium-ion battery anode material with excellent comprehensive performance.
Disclosure of Invention
The invention aims to overcome the defects of the existing method for improving the electrochemical performance of the polyanion type positive electrode material by adopting a large amount of carbon-based conductive agents, and provides the polyanion type sodium ion battery positive electrode material with high-rate charge-discharge performance and long-term cycle life and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme: a polyanion type sodium ion battery positive electrode material has a chemical formula of Na 4-(n-2)x Mn 1-x VM x (PO 4 ) 3 @C, wherein M is a dopant ion comprising W 3+ 、Ga 3+ 、La 3+ 、Y 3 + 、Yb 3+ 、Sn 4+ 、Zr 4+ 、Nb 5+ 、Mo 6+ N is the valence of the doping ion, 0<x≤0.2。
In the technical scheme of the invention, high-valence and large-radius cations are adopted to pertinently replace partial manganese atoms, regulate local ionic bonds and electronic energy bands and expand Na + And the migration channel space improves the intrinsic electron conductivity and the ion conductivity of the material and enhances the high-current charge and discharge capacity. By reducing the John-Teller effect of Mn-O octahedron, the lattice stability of the material is enhanced, the cycle life is prolonged, and the prepared positive electrode material has good sodium storage performance.
The second object of the invention is to provide a preparation method of the positive electrode material of the polyanion sodium ion battery, wherein the positive electrode material is a conventional carbon-coated polyanion sodium ion battery composite positive electrode material modified by substitution of manganese sites, and is prepared by a method of drying a precursor solution by a spray process and combining high-temperature carbothermic reduction, and the preparation method specifically comprises the following steps:
s1, mixing a sodium source, a vanadium source, a manganese source, a phosphorus source, a doped ion source, a conductive agent or a conductive agent precursor in a solvent, and heating and stirring to form a uniform precursor solution, wherein the heating and stirring temperature is 25-80 ℃ and the time is 0.5-10h; the solvent is a volatile solvent.
Molar ratio of sodium, manganese, vanadium to phosphorus element Na: mn: v: m: p is 3.95-4.05: 0.8 to 0.99:1.0 to 1.2:2.95 to 3.05, and the mole ratio of the doping ion M substituted by manganese position to vanadium is (0 to 0.2): 1.
In a more preferred scheme, the molar ratio of sodium, manganese, vanadium and phosphorus elements is 4.05:0.95:1:0.05:3.
in the technical scheme of the invention, the concentration of vanadium ions in the aqueous solution dissolved with a sodium source, a manganese source, a vanadium source and a phosphorus source is 0.1-0.5 mol/L, and more preferably 0.25mol/L;
the conductive agent is one or more of carbon black, carbon nano tube and graphene; the conductive agent precursor is one or more of glucose, sucrose, starch, polyethylene glycol, citric acid, sodium citrate and polyvinylpyrrolidone, and the molar ratio of the conductive agent or the conductive agent precursor to the sodium source is (0.5-1.8): 1.
S2, treating the precursor solution obtained in the step S1 through a spray drying process to obtain precursor powder, wherein the inlet temperature of spray drying is 170-240 ℃, and most preferably 220 ℃.
S3, performing two-step sintering treatment on the precursor powder obtained in the step S2 to obtain a manganese-site-substituted modified phosphate type sodium ion battery anode material, wherein the first step is performed with calcination at 300-550 ℃ for 1-5 hours to obtain a pre-decomposition intermediate product, and the pre-decomposition intermediate product obtained in the first step is ground and mixed and then subjected to second-step sintering, wherein the second-step sintering temperature is 500-800 ℃, preferably 700-750 ℃, and the sintering time is 4-15 hours, preferably 6-15 hours; more preferably 8-12 h, still more preferably the calcination is carried out at a process temperature increase rate of 1-10 ℃/min, most preferably 5 ℃/min. The protective gas used in the sintering is one or more of argon, nitrogen and hydrogen-argon mixed gas, and H in the mixed gas 2 The volume fraction is 3 to 20%, preferably 10%.
More preferred embodiments, the sodium source comprises one or more of an organic sodium salt or an inorganic sodium salt; specifically, the sodium source is one or more of sodium acetate, sodium oxalate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium nitrate, sodium carbonate and sodium bicarbonate, and preferably sodium acetate.
In a more preferred scheme, the manganese source is one or more of manganese acetate, manganese nitrate, manganese carbonate, manganese dioxide and manganese oxide, and is preferably manganese acetate.
More preferably, the vanadium source includes at least one of sodium metavanadate, ammonium metavanadate, vanadium pentoxide and vanadium trioxide. Preferred sources of vanadium are ammonium metavanadate, vanadium pentoxide, preferably ammonium metavanadate.
In a more preferred scheme, the phosphorus source is one or more of phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate and trisodium phosphate; preferably diammonium phosphate.
In a more preferred scheme, the carbon source precursor is one or more of glucose, sucrose, starch, polyethylene glycol, citric acid, sodium citrate and polyvinylpyrrolidone.
The invention also provides application of the manganese-site-substituted modified polyanion type sodium ion battery anode material, and the manganese-site-substituted modified polyanion type sodium ion battery anode material is applied as the anode material of a sodium ion battery.
In the technical scheme of the invention, other high-valence and large-radius cations are adopted to pertinently replace partial manganese atom positions, so that the distribution of local chemical bonds and electron clouds is regulated, the electronic and ionic conductivity is improved, and the lattice stability is enhanced, thereby ensuring that the material has more excellent sodium storage performance. Based on the full solution type precursor process, the raw material components are uniformly mixed on an atomic level, so that a pure-phase product with lower impurity content is obtained. The obtained material is applied to sodium ion batteries and has high discharge specific capacity, good cycle stability and rate capability.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a polyanion-type sodium ion battery composite positive electrode material which can solve the problems of low intrinsic conductivity, poor multiplying power performance and poor cycle stability of a manganese vanadium sodium phosphate positive electrode material.
2. The invention adopts other cations to replace partial manganese ions, and realizes the local charge rearrangement in the crystal and the beneficial transformation of the semiconductor energy band gap by controlling the distribution proportion of the number of manganese and vanadium atoms in the crystal lattice, thereby obviously improving the electronic conductivity and the ion conductivity in the crystal lattice of the material and essentially and effectively improving the electrochemical sodium storage performance of the material. The strategy for improving the intrinsic electronic conductivity of the material by a cation substitution mode has important significance for practical application of the material.
3. The invention adopts a high-efficiency and easy-to-operate spray drying process and a cheap conventional carbon source to realize that the uniform conductive carbon layer is coated on Na 4-(n-2)x Mn 1-x VM x (PO 4 ) 3 The composite structure of the active crystal particles can also have good electron/ion transmission characteristics under the condition of not using expensive conductive carbon materials such as graphene, carbon nanotubes and the like, and realize excellent electrochemical performance.
4. Na of the invention 4-(n-2)x Mn 1-x VM x (PO 4 ) 3 The preparation process of the @ C composite material is simple and feasible, and the full liquid phase mixing process can realize uniform mixing of raw material substances at the atomic level, and the adopted sodium source, phosphorus source, manganese source, carbon source, doped ion source and the like are wide in sources, low in cost and beneficial to large-scale production and industrial application.
5. Na of the invention 4-(n-2)x Mn 1-x VM x (PO 4 ) 3 When the @ C composite material is used as a positive electrode material of a sodium ion battery, the @ C composite material has excellent rate performance and cycle stability.
6. The method for preparing the high-performance phosphate type sodium ion battery anode material is simple in operation, quick and efficient, low in cost and capable of promoting large-scale production and commercial application.
Drawings
FIG. 1 is a schematic view of a composite positive electrode material Na of a polyanionic sodium ion battery prepared in example 1 3.95 Mn 0.95 VLa 0.05 (PO 4 ) 3 X-ray diffraction pattern (XRD) at C;
FIG. 2 is a schematic view of a composite positive electrode material Na of a polyanionic sodium ion battery prepared in example 1 3.95 Mn 0.95 VLa 0.05 (PO 4 ) 3 Scanning Electron Microscopy (SEM) of @ C;
FIG. 3 shows the Na-ion polymer composite positive electrode material of the sodium ion battery prepared in example 1 3.95 Mn 0.95 VLa 0.05 (PO 4 ) 3 Characteristic charge-discharge curve of @ C at 0.1C magnification;
FIG. 4 is an unmodified optimized polyanionic sodium ion battery positive electrode material Na prepared in comparative example 1 4 MnV(PO 4 ) 3 Charge-discharge curve at 1C magnification;
FIG. 5 shows Na obtained by the present invention 3.95 Mn 0.95 VLa 0.05 (PO 4 ) 3 Modified optimized Na @ C and comparative example 1 4 MnV(PO 4 ) 3 The cycle life retention of the @ C material at 1C magnification was compared.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
The invention aims at the manganese site substitution modified polyanion composite material to be used for preparing the positive electrode of the sodium ion battery and testing the electrochemical sodium storage performance of the sodium ion battery. For example, the polyanion composite material is mixed with a conductive agent and a binder, and then coated on an aluminum foil to form a film, so that the sodium ion battery positive plate is manufactured. The conductive agent and the binder may be materials known to those skilled in the art. The method for preparing the positive electrode material of the sodium ion battery by assembly can also refer to the existing method. For example, the positive electrode material of the polyanion sodium ion battery prepared by the invention is mixed with conductive carbon black and PVDF binder according to the mass ratio of 8:1:1, the obtained uniform slurry is coated on aluminum foil to be used as a test electrode, sodium metal is used as a counter electrode, and 1M NaPF is used as electrolyte 6 (PC-EMC-FEC) sodium half-cells were prepared in a glove box and tested for electrochemical performance.
Example 1
Firstly, 5mmol is takenCitric acid was dissolved in 50mL deionized water, then 2.5mmol ammonium metavanadate was added and heated in a 70 ℃ water bath for 40 minutes to give a clear solution. Then, after 2.375mmol of manganese acetate tetrahydrate and 0.125mmol of lanthanum nitrate were added to the solution again, stirring was continued for 20 minutes, and then 4.9375mmol of disodium hydrogen phosphate and 2.5625mmol of ammonium dihydrogen phosphate were added. Obtaining clear precursor solution, obtaining spheroid precursor powder through spray drying, and setting working parameters as follows: the inlet temperature was 220℃and the feed rate was 100mL/h. Heating the precursor to 400 ℃ at a heating rate of 4 ℃/min in a tube furnace under the protection of argon atmosphere, preserving heat for 3 hours, heating to 720 ℃ at a heating rate of 5 ℃/min, and preserving heat for 10 hours to obtain the spherical carbon-coated polyanion sodium-ion battery composite anode material Na 3.95 Mn 0.95 VLa 0.05 (PO 4 ) 3 @C。
The polyanionic sodium ion battery composite positive electrode material Na prepared by adopting the embodiment 3.95 Mn 0.95 VLa 0.05 (PO 4 ) 3 The XRD spectrum of @ C is shown in figure 1, and the material has definite R-3C space group characteristics, has high peak intensity and sharp peak, and has no other impurity peaks, so that the material is a pure-phase sodium vanadium manganese phosphate crystal structure with good crystallinity. As shown in FIG. 2, the material obtained by the process is spherical particles with the particle size of about 3-5 μm. Na (Na) 3.95 Mn 0.95 VLa 0.05 (PO 4 ) 3 Molecular composition of @ C and sodium vanadium phosphate (Na 3 V 2 (PO 4 ) 3 ) Compared with the method, the vanadium element consumption is only one half of that of the sodium vanadium phosphate, so that the manufacturing cost and toxic pollution are effectively reduced. Na (Na) 3.95 Mn 0.95 VLa 0.05 (PO 4 ) 3 The @ C and sodium sheet are assembled into a button half cell, as shown in figure 3, the capacity of the material reaches 104.9mAh g at 0.1C multiplying power -1 Near theoretical capacity (110 mAh g -1 ) The energy density can reach 347Wh kg -1 And the capacity retention rate reaches 97.1% after 100 circles of circulation.
Example 2
Firstly, 5mmol of citric acid is dissolved in 50mL of deionized water, then 2.5mmol of ammonium metavanadate is added, and water bath is carried out at 70 DEG CHeating for 40 min to obtain clear solution. Then, 2.375mmol of manganese acetate tetrahydrate was added to the solution, and after 0.125mmol of zirconium nitrate was added with the aid of ultrasound, stirring was continued for 10 minutes, and then 4.875mmol of disodium hydrogen phosphate and 2.625mmol of ammonium dihydrogen phosphate were added. Obtaining clear precursor solution, obtaining spheroid precursor powder through spray drying, and setting working parameters as follows: the inlet temperature was 220℃and the feed rate was 100mL/h. Heating the precursor to 400 ℃ at a heating rate of 4 ℃/min in a tube furnace under the protection of argon atmosphere, preserving heat for 3 hours, heating to 730 ℃ at a heating rate of 5 ℃/min, and preserving heat for 10 hours to obtain the spherical carbon-coated polyanion sodium-ion battery composite anode material Na 3.9 Mn 0.95 VZr 0.05 (PO 4 ) 3 @C。
The polyanionic sodium ion battery composite positive electrode material Na prepared by adopting the embodiment 3.9 Mn 0.95 VZr 0.05 (PO 4 ) 3 The @ C and sodium sheet are assembled into a button half battery with a capacity of 103.1mAh g at 1C multiplying power -1 The capacity retention rate reaches 96.6% after 100 circles of circulation.
Example 3
5mmol of citric acid was first dissolved in 50mL of deionized water, then 2.5mmol of ammonium metavanadate was added and heated in a water bath at 70℃for 40 minutes to give a clear solution. Then, 2.375mmol of manganese acetate tetrahydrate was added to the solution, and after 0.125mmol of ammonium molybdate was added with the aid of ultrasound, stirring was continued for 5 minutes, and then 4.75mmol of disodium hydrogen phosphate and 2.75mmol of ammonium dihydrogen phosphate were added. Obtaining clear precursor solution, obtaining spheroid precursor powder through spray drying, and setting working parameters as follows: the inlet temperature was 220℃and the feed rate was 100mL/h. Heating the precursor to 400 ℃ at a heating rate of 4 ℃/min in a tube furnace under the protection of argon atmosphere, preserving heat for 3 hours, heating to 710 ℃ at a heating rate of 5 ℃/min, and preserving heat for 10 hours to obtain the spherical carbon-coated polyanion sodium-ion battery composite anode material Na 3.8 Mn 0.95 VMo 0.05 (PO 4 ) 3 @C。
The polyanionic sodium ion battery composite positive prepared by adopting the embodimentPolar material Na 3.8 Mn 0.95 VMo 0.05 (PO 4 ) 3 The @ C and sodium sheet are assembled into a button half battery, and the reversible discharge specific capacities of the button half battery are 104.2 mAh g and 101.8mAh g respectively under the charge-discharge multiplying power of 0.1C and 1C -1 。
Comparative example 1
5mmol of citric acid was first dissolved in 40mL of deionized water, then 2.5mmol of ammonium metavanadate was added and heated in a 70℃water bath for 40 minutes to give a clear solution. Then, 2.5mmol of manganese acetate tetrahydrate was added to the solution, stirring was continued for 20 minutes, and then 5mmol of disodium hydrogen phosphate and 2.5mmol of ammonium dihydrogen phosphate were added. Obtaining clear precursor solution, obtaining spheroid precursor powder through spray drying, and setting working parameters as follows: the inlet temperature was 220℃and the feed rate was 100mL/h. Heating the precursor to 400 ℃ at a heating rate of 4 ℃/min in a tube furnace under the protection of argon atmosphere, preserving heat for 3 hours, heating to 700 ℃ at a heating rate of 5 ℃/min, and preserving heat for 10 hours to obtain the spherical carbon-coated polyanion sodium-ion battery composite anode material Na 4 MnV(PO 4 ) 3 @C。
The polyanionic sodium ion battery composite positive electrode material Na prepared by adopting the embodiment 4 MnV(PO 4 ) 3 The @ C and sodium sheet assembled into a button half cell, which was found to have a capacity of 88.6mAh g at 0.1C rate as seen in FIG. 4 -1 It can be seen from fig. 5 that the capacity retention after 100 cycles is only 81.4%. The result shows that the electrochemical performance of the manganese vanadium sodium phosphate material which is not subjected to heteroatom doping modification is difficult to be effectively exerted.
Claims (10)
1. A polyanionic sodium ion battery positive electrode material is characterized in that the chemical formula of the positive electrode material is Na 4-(n-2) x Mn 1-x VM x (PO 4 ) 3 @C, wherein M is a dopant ion comprising W 3+ 、Ga 3+ 、La 3+ 、Y 3+ 、Yb 3+ 、Sn 4+ 、Zr 4+ 、Nb 5+ 、Mo 6+ N is the valence of the doping ion, 0<x≤0.2。
2. The method for preparing the positive electrode material of the polyanionic sodium ion battery according to claim 1, comprising the following steps:
s1, mixing a sodium source, a vanadium source, a manganese source, a phosphorus source, a doped ion source, a conductive agent or a conductive agent precursor in a solvent, and heating and stirring to form a uniform precursor solution, wherein the heating and stirring temperature is 25-80 ℃ and the time is 0.5-10h;
wherein, the mole ratio of sodium, manganese, vanadium and phosphorus elements is 3.95-4.05: 0.8 to 0.99:1.0 to 1.2:2.95 to 3.05, the mole ratio of the doping ion M substituted by manganese position to vanadium is (0 to 0.2): 1;
s2, treating the precursor solution obtained in the step S1 through a spray drying process to obtain precursor powder;
s3, performing two-step sintering treatment on the precursor powder obtained in the step S2 to obtain a manganese-site-substituted modified phosphate type sodium ion battery anode material, wherein the first step is performed with calcination at 300-550 ℃ for 1-5 hours to obtain a pre-decomposition intermediate product, the pre-decomposition intermediate product obtained in the first step is ground and mixed and then subjected to second-step sintering, the sintering temperature of the second step is 500-800 ℃ and the sintering time is 4-15 hours, and the protective gas used in the sintering treatment is one or more of argon, nitrogen and hydrogen-argon mixed gas.
3. The method for preparing a positive electrode material of a polyanionic sodium ion battery according to claim 2, wherein the sodium source is one or more of sodium acetate, sodium oxalate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium nitrate, sodium carbonate, and sodium bicarbonate.
4. The method for preparing the positive electrode material of the polyanionic sodium ion battery according to claim 2, wherein the manganese source is one or more of manganese acetate, manganese nitrate, manganese carbonate, manganese dioxide, manganese oxide and manganous oxalate.
5. The method for preparing the positive electrode material of the polyanionic sodium ion battery according to claim 2, wherein the vanadium source is one or more of ammonium metavanadate, sodium metavanadate, vanadium pentoxide, vanadyl oxalate, vanadyl acetylacetonate and vanadyl trioxide.
6. The method for preparing a positive electrode material of a polyanionic sodium ion battery according to claim 2, wherein the doping ions include W 3+ 、Ga 3+ 、La 3+ 、Y 3+ 、Yb 3+ 、Sn 4+ 、Zr 4+ 、Nb 5+ 、Mo 6+ The source of the doping ions is at least one of nano oxide, oxalate, acetate, nitrate or carbonate containing target doping elements.
7. The method for preparing a positive electrode material of a polyanionic sodium ion battery according to claim 2, wherein the phosphorus source is one or more of phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate and trisodium phosphate.
8. The method for preparing the positive electrode material of the polyanionic sodium ion battery according to claim 2, wherein the conductive agent is one or more of carbon black, carbon nanotubes and graphene.
9. The method for preparing the positive electrode material of the polyanionic sodium ion battery according to claim 2, wherein the conductive agent precursor is one or more of glucose, sucrose, starch, polyethylene glycol, citric acid, sodium citrate and polyvinylpyrrolidone.
10. Use of the positive electrode material of a polyanionic sodium ion battery according to claim 1, wherein the positive electrode material of a polyanionic sodium ion battery is applied to a sodium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211557118.5A CN116130621A (en) | 2022-12-06 | 2022-12-06 | Polyanionic sodium ion battery positive electrode material, preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211557118.5A CN116130621A (en) | 2022-12-06 | 2022-12-06 | Polyanionic sodium ion battery positive electrode material, preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116130621A true CN116130621A (en) | 2023-05-16 |
Family
ID=86307045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211557118.5A Pending CN116130621A (en) | 2022-12-06 | 2022-12-06 | Polyanionic sodium ion battery positive electrode material, preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116130621A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117727885A (en) * | 2023-11-28 | 2024-03-19 | 湖北三峡实验室 | Preparation method of sodium-rich sodium vanadium phosphate/hard carbon composite positive electrode material |
| CN117766743A (en) * | 2024-02-22 | 2024-03-26 | 中南大学 | Polyanion type positive electrode composite material and preparation method and application thereof |
| CN118231668A (en) * | 2024-05-23 | 2024-06-21 | 宁波容百新能源科技股份有限公司 | Positive electrode material, preparation method and application thereof |
| CN118380583A (en) * | 2024-06-24 | 2024-07-23 | 湖南裕能新能源电池材料股份有限公司 | Polyanion type positive electrode material of sodium ion battery, preparation method and application thereof, electrode and sodium ion battery |
-
2022
- 2022-12-06 CN CN202211557118.5A patent/CN116130621A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117727885A (en) * | 2023-11-28 | 2024-03-19 | 湖北三峡实验室 | Preparation method of sodium-rich sodium vanadium phosphate/hard carbon composite positive electrode material |
| CN117766743A (en) * | 2024-02-22 | 2024-03-26 | 中南大学 | Polyanion type positive electrode composite material and preparation method and application thereof |
| CN118231668A (en) * | 2024-05-23 | 2024-06-21 | 宁波容百新能源科技股份有限公司 | Positive electrode material, preparation method and application thereof |
| CN118380583A (en) * | 2024-06-24 | 2024-07-23 | 湖南裕能新能源电池材料股份有限公司 | Polyanion type positive electrode material of sodium ion battery, preparation method and application thereof, electrode and sodium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109336193B (en) | Multi-element in-situ co-doped ternary material precursor and preparation method and application thereof | |
| CN116130621A (en) | Polyanionic sodium ion battery positive electrode material, preparation and application thereof | |
| CN106602044B (en) | Preparation of doped modified LiVPO4Method for preparing cathode material of F lithium ion battery | |
| CA2623636A1 (en) | Method of producing positive electrode active material and nonaqueous electrolyte battery using same | |
| CN115207340B (en) | Sodium ion battery layered oxide positive electrode material, and preparation method and application thereof | |
| CN114256446B (en) | Polyanion type positive electrode material, and preparation method and application thereof | |
| CN108933237B (en) | Preparation method and application of lithium ion battery positive electrode material | |
| CN110911680A (en) | Preparation method of Ti and V element composite doped lithium iron phosphate | |
| CN115132981A (en) | Binary doped iron-based fluorophosphate sodium ion positive electrode material and preparation method thereof | |
| CN115101738A (en) | Carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material and preparation method and application thereof | |
| CN111606314B (en) | Preparation method of sodium ion battery anode material sodium vanadium trifluorophosphate | |
| CN117794854A (en) | Iron-based polyphosphate type sodium ion battery positive electrode material, and preparation method and application thereof | |
| CN110085862A (en) | A kind of sode cell electrode material Na1+xFexTi2-x(PO4)3And its preparation method and application | |
| CN114050244A (en) | Ferric pyrophosphate sodium ion battery positive electrode composite material and preparation method thereof | |
| CN117117197B (en) | Nickel-manganese-based layered oxide positive electrode material for sodium ion battery and preparation method thereof | |
| CN116706056A (en) | Based on ultra-small particles Na x Fe y M z (SO 4 ) 3 Non-destructive quick-charging positive electrode material, and preparation method and application thereof | |
| CN116190629A (en) | Cation doped lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN115995539A (en) | Quick ion conductor coated lithium iron phosphate positive electrode material, and preparation method and application thereof | |
| CN116101994A (en) | Heteropolyacid modified layered oxide sodium battery positive electrode material and preparation method thereof | |
| CN114566647A (en) | Calcium phosphate coated high-nickel ternary cathode material and preparation method and application thereof | |
| CN114864905A (en) | Graphene composite silicon doped vanadium sodium phosphate composite material, preparation method and application | |
| CN112467095A (en) | Sodium vanadium fluorophosphate/C dual-modified sodium manganese fluorophosphate composite material as well as preparation and application thereof | |
| CN115771887B (en) | Preparation and application methods of high-energy long-life phosphate positive electrode material | |
| CN114824212B (en) | Preparation method of modified sodium iron phosphate composite material | |
| CN116154156B (en) | Spherical lithium iron manganese phosphate positive electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |