CN113745507B - Sodium vanadyl chlorophosphate positive electrode material, preparation method and sodium ion battery - Google Patents

Sodium vanadyl chlorophosphate positive electrode material, preparation method and sodium ion battery Download PDF

Info

Publication number
CN113745507B
CN113745507B CN202111026182.6A CN202111026182A CN113745507B CN 113745507 B CN113745507 B CN 113745507B CN 202111026182 A CN202111026182 A CN 202111026182A CN 113745507 B CN113745507 B CN 113745507B
Authority
CN
China
Prior art keywords
sodium
positive electrode
prepared
chlorophosphate
vanadium
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.)
Active
Application number
CN202111026182.6A
Other languages
Chinese (zh)
Other versions
CN113745507A (en
Inventor
吴兴隆
谷振一
吕红艳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northeast Normal University
Original Assignee
Northeast Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Northeast Normal University filed Critical Northeast Normal University
Priority to CN202111026182.6A priority Critical patent/CN113745507B/en
Publication of CN113745507A publication Critical patent/CN113745507A/en
Application granted granted Critical
Publication of CN113745507B publication Critical patent/CN113745507B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • H01M4/58—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/455—Phosphates containing halogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/582—Halogenides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/38—Particle morphology extending in three dimensions cube-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a sodium vanadyl chlorophosphate anode material, a preparation method and a sodium ion battery, and the molecular formula of the sodium ion battery is Na 3 (VO) 2 (PO 4 ) 2 F x Cl y Space group I4/mmm belonging to tetragonal system, the Na 3 (VO) 2 (PO 4 ) 2 F x Cl y The sodium-electricity positive electrode material with high storage stability, excellent electrochemical performance and all-weather performance is successfully prepared by adopting a one-step hydrothermal mode through regulating and controlling the anion position of the material, namely, the proportion of F, cl anions is regulated and controlled, the hydrothermal temperature is regulated and controlled, the sodium-ion battery positive electrode material is prepared, the sodium vanadium oxychloride positive electrode material has more excellent electrochemical performance, the synthesis process method is simple, precise instruments are not needed, and the method is suitable for large-scale production.

Description

Sodium vanadyl chlorophosphate positive electrode material, preparation method and sodium ion battery
Technical Field
The invention relates to the technical field of sodium ion battery anode materials, in particular to a sodium vanadium oxychloride anode material, a preparation method and a sodium ion battery.
Background
Advanced electrode materials are urgently needed in order to develop high performance Sodium Ion Batteries (SIBs). Compared with the positive electrode material, the negative electrode material has higher attention and more mature research. For example: the anode materials such as hard carbon, alloy compounds, selenide and the like have proved to have excellent sodium storage characteristics and future development prospects. Thus, the electrochemical performance of SIBs is largely focused on their cathode materials. And more attention is paid to the electrochemical performance of the materials in the research process of the anode materials: high rate, long cycle, high energy density and wide temperature range performance, while ignoring the storage properties of the material. The storage property of the material is often of great significance in practical applications. It not only affects the electrochemical properties of the material, but also is closely related to the cost of manufacturing the battery.
Most positive electrode materials are subject to storage problems, and long-term exposure to air can lead to the materials absorbing water and CO in the air 2 The reaction proceeds, which impairs the surface deactivation and electrochemical performance degradation of the material.
Among the numerous positive electrode materials, layered oxides and polyanion compounds are positive electrode materials with representative and future practical development prospects, while also facing enormous storage challenges. O (O) 3 The type oxide is a relatively typical material among oxide materials, and has been widely studied and has achieved satisfactory electrochemical properties. However, the O3 type oxide is less stable and is easily reactive with water in the air. For example NaMO 2 (m=fe, mn, cr) material, na occurs upon contact with water + /H + Exchange reaction to form MOOH and NaOH, and CO in air 2 React to form insulating Na 2 CO 3 And NaHCO 3 Sodium diffuses to the surface of the material and forms inert particles within the material, causing deactivation of the entire electrode.
Polyanionic compounds are generally considered to be a relatively stable positive electrode material, and have strong covalent bonds to stabilize oxygen in the crystal lattice, so that the polyanionic compound has relatively high structural stability and safety. Besides having poor electron conductivity, the polyanion compound has another problem of having strong water absorption, and the surface thereof generates NaOH upon contact with water, which has a great influence on electrochemical properties. Will be with CO in the air 2 Reaction forms insulating Na on the surface of the material 2 CO 3 And NaHCO 3 The electrochemical performance of the material is seriously affected. For example Na 2 Fe 2 (SO 4 ) 3 、Na 3 V 2 (PO 4 ) 3 、Na 4 Fe 2 (PO 4 ) 2 P 2 O 7 The isopolyanion type material has strong water absorption, and in addition, na 3 TiV(PO 4 ) 3 Poor structural stability, and spontaneously undergoes sodium removal behavior transformation to generate Na after being placed in the air for 30 days 2 TiV(PO 4 ) 3 . Thus, such materials are not amenable to prolonged exposure to air, which can present a significant challenge for storage of the materials.
In summary, the poor storage stability of the material clearly adds cost to the storage of the material, limiting its breadth and lifetime of use. And little research is done on such materials, which is far less interesting than the research on the electrochemical properties of electrode materials. Therefore, development of a positive electrode material having both excellent electrochemical performance and good storage stability is urgently required.
At present, a coating mode is generally adopted to solve the air stability of a material, and a layer of stable oxide, high-molecular polymer and the like is coated on the surface of the material. However, these modes have higher technological requirements, which undoubtedly increases the production cost, and can also affect the performance of the electrochemical performance of the material, namely, the preparation of the sodium vanadium fluorophosphate/carbon composite and the application of the composite, and the application number is: 201711090279.7 uses a complex secondary carbon coating process. Because the carbon material can increase the quality of the material, reduce the overall mass/volume energy density of the material, the uniformity of the particle size of the material is affected, and the repeatability is low.
Therefore, we propose a simple hydrothermal mode, and the sodium-electricity anode material with high storage stability, excellent electrochemical performance and all-weather performance is successfully prepared by adopting a one-step hydrothermal mode through regulating and controlling the anion position of the material.
Disclosure of Invention
The invention aims to provide a sodium vanadyl chlorophosphate anode material, a preparation method and a sodium ion battery, which have the advantages of low cost, excellent electrochemical performance, ultra-stable storage performance, good all-weather performance and wide application range.
In order to achieve the above purpose, the present invention provides the following technical solutions: sodium vanadyl chlorophosphate anode material with molecular formula of Na 3 (VO) 2 (PO 4 ) 2 F x Cl y X+y=1 and 0.99.gtoreq.x.gtoreq.0.8, space group I4/mmm, belonging to tetragonal system, na 3 (VO) 2 (PO 4 ) 2 F x Cl y Is of uniform regular cube shape.
The preparation method of the sodium vanadyl chlorophosphate anode material is characterized by comprising the following specific steps of:
s1: adding a vanadium source, a phosphorus source and a reducing agent into water, and heating and stirring the mixture at 70-80 ℃ in a reaction container, wherein the stoichiometric ratio of vanadium in the vanadium source to water is 1:1-1:10;
s2: adding a sodium source, a fluorine source and a chlorine source into the reaction container in the step S1, and reacting for 30-60min to obtain a uniform transparent solution A; the stoichiometric ratio of fluorine in the fluorine source to chlorine in the chlorine source is 1:1-1:7;
s3: regulating the pH value of the transparent solution A prepared in the step S2 to be 5-10, transferring the regulated solution into a reaction kettle, and heating to 100-200 ℃ for 6-36 hours;
s4: centrifuging, washing and drying the product obtained after the reaction in the step S3 to obtain a solid B;
s5: and (3) carrying out high-temperature annealing at 200-600 ℃ on the solid B prepared in the step (S4) for 1-6 hours to obtain the sodium vanadium oxychloride anode material.
Preferably, the vanadium source is V 2 O 5 、NH 4 VO 3 VOSO 4 One or more than two of them.
Preferably, the phosphorus source (NH 4 ) 2 HPO 4 、NH 4 H 2 PO 4 、H 3 PO 4 One or more than two of them.
Preferably, the sodium source is Na 2 CO 3 、NaHCO 3 、NaNO 3 One or more than two of NaF, wherein the chlorine source is one or two of NaCl, HCl and hydroxylamine hydrochlorideThe above.
Preferably, the sodium source is NaF, the chlorine source is NaCl, and the ratio of NaF to NaCl is 1:3-1:5 respectively. .
A sodium ion battery using sodium vanadyl chlorophosphate anode material comprises metal sodium as a negative electrode, glass fiber and electrolyte for testing the sodium ion battery, wherein the electrolyte is organic electrolyte, and the organic electrolyte comprises 1M NaClO 4 Propylene carbonate and 5% by volume of fluoroethylene carbonate.
Compared with the prior art, the invention has the beneficial effects that:
(1) Na provided by the invention 3 V 2 (PO 4 ) 2 O 2 F x The Cy positive electrode material has the characteristics of high initial discharge capacity, high working voltage, excellent all-weather performance and ultra-long storage stability, and has higher working voltage platform and discharge specific capacity and higher energy density; the material has good circulation stability, is placed for a period of time without treatment under good water-oxygen conditions, and still has the original structure, the original shape and the original electrochemical stability, which certainly reduces the storage cost of the material and widens the application range of the material.
(2) The invention relates to a preparation method of a sodium vanadyl chlorophosphate anode material, which realizes modification of material crystal lattice by regulating and controlling an anion mode, namely regulating and controlling the proportion of F, cl anions and regulating and controlling the proportion of F, cl, changes the crystal growth direction of the material and ensures that the material is along [010]]And (5) directional growth. A positive electrode material of a uniform regular cube shape was obtained. Meanwhile, the electrochemical performance of the material is further optimized by adjusting the proportion of F, cl. The halogen ion is adopted to carry out double regulation and control on the anion position, not only the material lattice is modified, but also the crystal growth direction is induced, and the sodium ion migration path (Cl) is widened - Has larger ionic radius) accelerates the dynamics of sodium ions in the deintercalation process, improves the quick charge capacity of the material, stabilizes the crystal structure, improves the structural stability of the material, and ensures that the material has more excellent cycle performance.
(3) According to the invention, the crystal growth direction is changed by regulating F, cl, so that the material has excellent air stability, the [010] crystal face exposed in the air exposure is more stable, and the material is not deactivated due to the fact that the crystal face reacts with water and oxygen in the air to form byproducts Na2CO3 and NaHCO3, so that the material has high air stability, the storage of future materials is facilitated, the cost is reduced, and the service life of the future materials is prolonged. And the hydrothermal temperature is regulated and controlled to prepare the material, and the crystallinity of the crystal and the particle size of the material can be changed by regulating and controlling the hydrothermal temperature, so that the overall electrochemical performance of the material, including multiplying power, circulation and the like, is affected. The sodium ion battery anode material with good crystallinity, small material particle size and excellent electrochemical performance is obtained by regulating the hydrothermal temperature, has more excellent electrochemical performance, and the synthesis process method is simple, does not need precise instruments and is suitable for large-scale production.
(4) The invention successfully prepares the high-performance anode material with uniform and controllable morphology by adopting a one-step hydrothermal mode without carbon coating, and omits a complex secondary carbon coating process. Meanwhile, the carbon-free material can reduce the quality of the material, improve the overall mass/volume energy density of the material and reduce the production cost. The particle size of the material is uniform and controllable, the repeatability of each preparation of the material can be ensured, and the process is simpler, more convenient and mature. Compared with the material, the prepared material has more excellent cycle performance and all-weather performance, widens the application environment field of the material, and meets the market demand more.
Drawings
FIG. 1 is an XRD characterization of the material prepared in example 1;
FIG. 2 is an SEM characterization of the material prepared according to example 1;
FIG. 3 is an XRD characterization of a material after it has been left in air for various periods of time;
figure 4 SEM characterization of the material after various times of standing in air.
FIG. 5 is a graph of the rate capability of the material after being placed in air for various periods of time;
FIG. 6 is a graph of electrochemical performance for a low pressure test;
FIG. 7 is a graph of charge and discharge at different rates;
FIG. 8 is a 0.5C rate cycle chart;
fig. 9 is a graph of rate performance at different test temperatures.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Grinding the prepared positive electrode material, acetylene black, sodium carboxymethylcellulose or sodium alginate with a ratio of 7:2:1, using deionized water as a solvent to form slurry, uniformly coating the slurry on an aluminum foil, wherein the loading amount of each electrode plate active substance is 2-3mg/cm 2 . With this as the working electrode and sodium sheet as the counter electrode, the electrolytes were respectively organic electrolytes 1M NaClO 4 +propylene carbonate+5% by volume of fluoroethylene carbonate. The membrane was glass fiber (Whatman 934-AH). After the battery was assembled in an argon oxygen-free and water-free environment of the glove box, a constant current charge and discharge test was performed on the LAND.
Basic embodiment
S1: adding a vanadium source, a phosphorus source and a reducing agent into water, and heating and stirring the mixture at 70-80 ℃ in a reaction container, wherein the stoichiometric ratio of vanadium in the vanadium source to water is 1:1-1:10; the reducing agent is oxalic acid;
s2: adding a sodium source, a fluorine source and a chlorine source into the reaction container in the step S1, and reacting for 30-60min to obtain a uniform transparent solution A; the stoichiometric ratio of fluorine in the fluorine source to chlorine in the chlorine source is 1:1-1:9;
s3: regulating the pH value of the transparent solution A prepared in the step S2 to be 5-10, transferring the regulated solution into a reaction kettle, and heating to 100-200 ℃ for 6-36 hours;
s4: centrifuging, washing and drying the product obtained after the reaction in the step S3 to obtain a solid B;
s5: and (3) carrying out high-temperature annealing at 200-600 ℃ on the solid B prepared in the step (S4) for 1-6 hours to obtain the sodium vanadium oxychloride anode material.
Example 1
S1: will V 2 O 5 Oxalic acid, NH 4 H 2 PO 4 Adding into water, V 2 O 5 : oxalic acid: NH (NH) 4 H 2 PO 4 The molar ratio of (2) is 1:3:2, V 2 O 5 The molar ratio of vanadium to water in (1-10); heating and stirring for 1 hour at 80 ℃ in a reaction container;
s2: naF and NaCl are added into the reaction vessel in the step S1 according to the proportion of 1:3, and the reaction is carried out for 45min, thus obtaining a uniform transparent solution A;
s3: adjusting the pH value of the transparent solution A prepared in the step S2, wherein the pH value=7, transferring the adjusted and controlled solution into a reaction kettle, and heating the solution in an oven at 170 ℃ for 12 hours;
s4: centrifuging and washing the product after the reaction in the step S3, and drying in a drying oven at 100 ℃ to obtain a solid B;
s5: and (3) carrying out high-temperature annealing at 400 ℃ on the solid B prepared in the step (S4) for 4 hours to obtain the sodium vanadium oxychloride anode material.
Examples two to six
The process steps are the same as in example 1, except that in step S3 the pH is 6, 8, 9, 10, respectively.
Comparative examples one to six
The method steps are the same as those in the first embodiment except that the pH in the step S3 is 2-5 and 11-12 respectively.
The discharge specific capacities of the sodium vanadyl chlorophosphate positive electrode materials prepared by implementing one to six and comparative examples one to six are shown in table 1.
TABLE 1
As can be seen from Table 1, the discharge specific capacities of the prepared sodium vanadyl chlorophosphate anode materials are all 115mAh g when the pH is adjusted to 6-10 -1 Above, wherein at ph=7, the optimum specific discharge capacity at 127mAh g is exhibited -1 The pH value in the preparation process not only affects the performance of the material, but also further affects the morphology and crystallinity of the material in the nucleation process. When the pH value at the material is less than 6, the whole solution of the solution presents stronger acidity, the material can be corroded in the nucleation process of the material, the morphology of the material is influenced, the crystallinity of the material is reduced, the particle size of the material is larger, the shape is irregular, meanwhile, the poor crystallinity can influence the stability of the crystal structure of the material, and further the overall performance of the material is poor. In a deep analysis, the influence of pH adjustment in the reaction process is regulated, so that the sodium vanadium oxychloride positive electrode material prepared at the pH of 6-10 shows excellent specific discharge capacity.
Examples seven to nine
The steps of the method are the same as those of the first embodiment, except that the ratio of NaF to NaCl in the step S2 is 1:1, 1:5, and 1:7, respectively.
Comparative example seven
The method steps are the same as those in the first embodiment, except that the ratio of NaF to NaCl in the step S2 is 1:9.
The discharge specific capacity test of the sodium vanadyl chlorophosphate anode materials prepared in examples one, seven to nine and comparative example seven is shown in table 2.
TABLE 2
As can be seen from Table 2, the ratio of NaF to NaCl is in the range of 1:1-1:7, and the prepared sodium vanadium oxychloride positive electrode material has excellent specific discharge capacity, wherein the ratio of NaF to NaCl is 1:3, and the optimal specific discharge capacity is 127mAh g -1 。
Performance test:
(1) Storage stability test
And (3) exposing the sodium vanadyl chlorophosphate anode material prepared in the first embodiment to air for 1-36 months, and then grinding the exposed material, acetylene black, sodium carboxymethylcellulose or sodium alginate in a ratio of 7:2:1 with deionized water as a solvent to form slurry, and uniformly coating the slurry on an aluminum foil, wherein the loading amount of each electrode plate active substance is 2-3mg/cm < 2 >. With this as the working electrode and sodium sheets as the counter electrode, the electrolyte was organic electrolyte 1m naclo4+propylene carbonate+5% by volume of fluoroethylene carbonate, respectively. The membrane was glass fiber (Whatman 934-AH). After the battery was assembled in an argon oxygen-free and water-free environment of the glove box, a constant current charge and discharge test was performed on the LAND. The test structures are shown in table 3.
TABLE 3 Table 3
(2) Stability testing at different storage temperatures
Exposing the sodium vanadium oxychloride anode material prepared in the first embodiment to be placed in different temperature ranges for 24 hours, grinding the exposed material, acetylene black, sodium carboxymethylcellulose or sodium alginate in a ratio of 7:2:1 with deionized water as a solvent to form slurry, and uniformly coating the slurry on an aluminum foil (the loading amount of each electrode plate active substance is 2-3 mg/cm) 2 ). With this as the working electrode and sodium sheet as the counter electrode, the electrolytes were respectively organic electrolytes 1M NaClO 4 +propylene carbonate+5% by volume of fluoroethylene carbonate. The membrane was glass fiber (Whatman 934-AH). After the battery was assembled in an argon oxygen-free and water-free environment of the glove box, a constant current charge and discharge test was performed on the LAND. The test results are shown in Table 4.
TABLE 4 Table 4
(3) Storage stability test under water environment
The sodium vanadium oxychloride anode material prepared in the first embodiment is exposed and placed in water for different time, and then the dried material, acetylene black, sodium carboxymethylcellulose or sodium alginate are ground into slurry with a solvent of deionized water in a ratio of 7:2:1, and are uniformly coated on an aluminum foil (the loading amount of each electrode plate active substance is 2-3mg/cm < 2 >). With this as the working electrode and sodium sheets as the counter electrode, the electrolyte was organic electrolyte 1m naclo4+propylene carbonate+5% by volume of fluoroethylene carbonate, respectively. The membrane was glass fiber (Whatman 934-AH). After the battery was assembled in an argon oxygen-free and water-free environment of the glove box, a constant current charge and discharge test was performed on the LAND. The test results are shown in Table 5.
TABLE 5
As can be seen from tables 3-5, the sodium vanadium oxychloride anode material prepared by the method disclosed by the invention is exposed to air for a long time in environments such as different temperatures and water environments, the specific discharge capacity of the sodium vanadium oxychloride anode material is basically stable, no obvious change occurs, and the sodium vanadium oxychloride anode material prepared by the method disclosed by the invention has good stability and is suitable for all weather.
(4) All-weather performance test
The sodium vanadium oxy chlorophosphate anode material prepared in the first embodiment is dried, the dried sodium vanadium oxy chlorophosphate anode material, acetylene black, sodium carboxymethyl cellulose or sodium alginate are ground into slurry by using deionized water according to the ratio of 7:2:1, and the slurry is uniformly coated on an aluminum foil (the loading amount of each electrode plate active substance is 2-3mg/cm < 2 >). With this as the working electrode and sodium sheets as the counter electrode, the electrolyte was organic electrolyte 1m naclo4+propylene carbonate+5% by volume of fluoroethylene carbonate, respectively. The membrane was glass fiber (Whatman 934-AH). After a battery is assembled in an argon oxygen-free and water-free environment of a glove box, a constant-current charge-discharge test is carried out on LAND, the voltage range is modulated to 1.2-4.3V, and the wide voltage range performance is tested.
(5) All-weather performance test
The sodium vanadium oxy chlorophosphate anode material prepared in the first embodiment is dried, the dried sodium vanadium oxy chlorophosphate anode material, acetylene black, sodium carboxymethyl cellulose or sodium alginate are ground into slurry by using deionized water according to the ratio of 7:2:1, and the slurry is uniformly coated on an aluminum foil (the loading amount of each electrode plate active substance is 2-3mg/cm < 2 >). With this as the working electrode and sodium sheets as the counter electrode, the electrolyte was organic electrolyte 1m naclo4+propylene carbonate+5% by volume of fluoroethylene carbonate, respectively. The membrane was glass fiber (Whatman 934-AH). After the battery was assembled in an argon oxygen-free and water-free environment of the glove box, a constant current charge and discharge test was performed on the LAND. And testing all-weather performance of electric measurement. The test results are shown in Table 6.
TABLE 6
Fig. 1 is an XRD characterization diagram of the material prepared in example 1, where the XRD characterization data indicates that the successfully prepared sodium vanadyl chlorophosphate positive electrode material does not have any miscellaneous items and exhibits good crystallinity.
Fig. 2 is an SEM characterization diagram of the material prepared in example 1, in which the sodium vanadium oxychloride anode material has a cubic block morphology with a regular micron size, the particle size is about 1.5um, and the uniform particle size and regular morphology are beneficial to the performance of the material.
FIG. 3 is an XRD characterization of the material after various times of placement in air, and SEM characterization of the material after various times of placement in air of FIG. 4 shows that the crystal structure of the sodium vanadyl chlorophosphate positive electrode material is unchanged no matter under any conditions of placement, and good crystallinity is shown without any impurity phase; the sodium vanadyl chlorophosphate anode material has good storage stability.
FIG. 5 is a graph of the rate capability of the material after being placed in air for various periods of time; the result shows that no matter under any conditions, the initial capacity and the rate performance of the sodium vanadyl chlorophosphate anode material have larger fluctuation, and the anode material has excellent electrochemical performance; indicating that NVPFCl has good storage stability.
FIG. 6 is a graph of electrochemical performance at low voltage, showing higher specific discharge capacity (172 mAh g for rate performance at a wider voltage range -1 ) And excellent rate performance. The excellent electrochemical performance of the sodium vanadyl chlorophosphate anode material is proved.
FIG. 7 is a graph of charge and discharge at various rates, constant current charge and discharge at a relatively wide voltage range, with three discharge plateau of 4.0, 3.6 and 1.5V for the sodium vanadyl chlorophosphate positive electrode material at low rate, and with a relatively high specific discharge capacity of 172mAh g -1 。
FIG. 8 is a 0.5C rate cycle chart; the capacity retention rate of 86.8% is still maintained after 100 circles of circulation under the current density of 0.5C, which proves that the sodium vanadyl chlorophosphate anode material has excellent structural stability and good circulation life performance.
FIG. 9 is a graph of rate performance at various test temperatures, showing that the sodium vanadyl chlorophosphate positive electrode material has excellent rate performance when the temperature is increased by 50 degrees, even at 20C, 116mAh g is still present -1 Shows excellent high temperature performance. Meanwhile, the sodium vanadium oxychloride anode material still has good rate capability at the temperature of 15 ℃ and almost has the same performance as the anode material at room temperature. The method shows that the sodium vanadyl chlorophosphate anode material shows excellent temperature adaptation, can be matched with different temperature measuring intervals, and can provide greater convenience for future application.
In summary, with the analysis of tables 1-4 and FIGS. 1-9, modification of the material lattice was achieved by adjusting the ratio of F, cl, and the crystal growth direction of the material was changed to grow the material in the [010] direction. A positive electrode material of a uniform regular cube shape was obtained. Meanwhile, the electrochemical performance of the material is further optimized by adjusting the proportion of F, cl. The halogen ions are adopted to carry out double regulation and control on anion positions, so that not only is the material lattice modified, but also the crystal growth direction is induced, and the migration path of sodium ions is widened, namely Cl < - > has larger ion radius, the dynamics of sodium ions in the deintercalation process is accelerated, the quick charge capacity of the material is improved, the crystal structure is stabilized, and the structural stability of the material is improved, so that the material has more excellent cycle performance.
In addition, as can be seen from tables 5 to 6, the sodium vanadyl chlorophosphate positive electrode material prepared by the present invention still maintains a relatively excellent specific discharge capacity after a long period of exposure in air and a long period of exposure in water, since the crystal growth direction is changed by controlling F, cl, the material has excellent air stability, and the exposure is placed in air exposure from the figure [010]]The crystal face is more stable and can not react with water and oxygen in the air to form a byproduct Na 2 CO 3 And NaHCO 3 Resulting in material deactivation and thus high air stability, which also facilitates future storage of the material, reduces its cost and increases its service life.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (2)

1. A preparation method of a sodium vanadyl chlorophosphate anode material is characterized in that,
the sodium vanadyl chlorophosphate anode material is prepared by a one-step hydrothermal mode, and comprises the following specific steps:
s1: adding a vanadium source, a phosphorus source and a reducing agent into water, and heating and stirring the mixture at 70-80 ℃ in a reaction container, wherein the stoichiometric ratio of vanadium in the vanadium source to water is 1:1-1:10; the reducing agent is oxalic acid;
s2: adding NaF and NaCl into the reaction container in the step S1, and reacting for 30-60min to obtain a uniform transparent solution A;
s3: regulating the pH value of the transparent solution A prepared in the step S2 to be 6-10, transferring the regulated solution into a reaction kettle, and heating to 100-200 ℃ for 6-36 hours;
s4: centrifuging, washing and drying the product obtained after the reaction in the step S3 to obtain a solid B;
s5: carrying out high-temperature annealing at 200-600 ℃ on the solid B prepared in the step S4 for 1-6 hours to obtain a sodium vanadium oxychloride anode material;
the ratio of NaF to NaCl is 1:3-1:5 respectively;
the molecular formula of the sodium vanadium oxychloride anode material is Na 3 (VO) 2 (PO 4 ) 2 F x Cl y X+y=1 and 0.99.gtoreq.x.gtoreq.0.8, space group I4/mmm, belonging to tetragonal system, na 3 (VO) 2 (PO 4 ) 2 F x Cl y Is of a uniform regular cube shape;
the vanadium source is V 2 O 5 、NH 4 VO 3 、VOSO 4 One or more than two of them;
the phosphorus source is (NH) 4 ) 2 HPO 4 、NH 4 H 2 PO 4 、H 3 PO 4 One or more than two of them.
2. The application of the positive electrode material prepared by the preparation method according to claim 1 in sodium ion batteries, wherein the positive electrode material comprises sodium metal serving as a negative electrode, glass fiber and electrolyte for testing sodium ion batteries, the electrolyte is organic electrolyte, and the organic electrolyte comprises NaClO 4 Propylene carbonate and 5% by volume of fluoroethylene carbonate.
CN202111026182.6A 2021-09-02 2021-09-02 Sodium vanadyl chlorophosphate positive electrode material, preparation method and sodium ion battery Active CN113745507B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111026182.6A CN113745507B (en) 2021-09-02 2021-09-02 Sodium vanadyl chlorophosphate positive electrode material, preparation method and sodium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111026182.6A CN113745507B (en) 2021-09-02 2021-09-02 Sodium vanadyl chlorophosphate positive electrode material, preparation method and sodium ion battery

Publications (2)

Publication Number Publication Date
CN113745507A CN113745507A (en) 2021-12-03
CN113745507B true CN113745507B (en) 2024-01-30

Family

ID=78735028

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111026182.6A Active CN113745507B (en) 2021-09-02 2021-09-02 Sodium vanadyl chlorophosphate positive electrode material, preparation method and sodium ion battery

Country Status (1)

Country Link
CN (1) CN113745507B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116417617B (en) * 2023-05-26 2023-10-24 宁德新能源科技有限公司 Positive electrode material, positive electrode sheet, sodium ion secondary battery and electricity utilization device

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101924206A (en) * 2010-06-28 2010-12-22 宁波大学 Preparation method of chlorine-doped LiVPO4 anode material
CN102664267A (en) * 2012-04-13 2012-09-12 浙江工业大学 Co-doped cathode material lithium-vanadium-phosphate and application thereof
JP2013089391A (en) * 2011-10-14 2013-05-13 Kyushu Univ Electrode active material for sodium ion secondary battery
CN106299248A (en) * 2016-08-24 2017-01-04 东北师范大学 A kind of fluorophosphate quadrangular nano material and preparation method thereof
CN106328911A (en) * 2016-11-30 2017-01-11 合肥工业大学 Material with mixture of ions with sodium vanadium phosphate cathode material coated by carbon and preparing method thereof
CN110649261A (en) * 2018-06-27 2020-01-03 宁德时代新能源科技股份有限公司 Positive electrode active material, positive electrode plate and sodium ion secondary battery
CN110660959A (en) * 2018-06-29 2020-01-07 宁德时代新能源科技股份有限公司 Positive pole piece and sodium ion battery
CN110875473A (en) * 2018-09-03 2020-03-10 宁德时代新能源科技股份有限公司 Positive electrode active material, preparation method thereof and sodium ion battery
CN112490448A (en) * 2020-11-27 2021-03-12 中南大学 Preparation and purification method of (fluoro) vanadium sodium phosphate compound cathode material
CN112701285A (en) * 2020-12-29 2021-04-23 东北师范大学 Positive electrode material and preparation method and application thereof
CN112701283A (en) * 2020-12-29 2021-04-23 东北师范大学 Positive electrode material and preparation method and application thereof
CN113046768A (en) * 2021-03-15 2021-06-29 东北师范大学 Potassium vanadyl fluorophosphate, preparation method and application thereof, and potassium ion battery

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109980211B (en) * 2019-04-23 2021-03-19 深圳大学 Sodium ion battery positive electrode material and preparation method and application thereof

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101924206A (en) * 2010-06-28 2010-12-22 宁波大学 Preparation method of chlorine-doped LiVPO4 anode material
JP2013089391A (en) * 2011-10-14 2013-05-13 Kyushu Univ Electrode active material for sodium ion secondary battery
CN102664267A (en) * 2012-04-13 2012-09-12 浙江工业大学 Co-doped cathode material lithium-vanadium-phosphate and application thereof
CN106299248A (en) * 2016-08-24 2017-01-04 东北师范大学 A kind of fluorophosphate quadrangular nano material and preparation method thereof
CN106328911A (en) * 2016-11-30 2017-01-11 合肥工业大学 Material with mixture of ions with sodium vanadium phosphate cathode material coated by carbon and preparing method thereof
CN110649261A (en) * 2018-06-27 2020-01-03 宁德时代新能源科技股份有限公司 Positive electrode active material, positive electrode plate and sodium ion secondary battery
CN110660959A (en) * 2018-06-29 2020-01-07 宁德时代新能源科技股份有限公司 Positive pole piece and sodium ion battery
CN110875473A (en) * 2018-09-03 2020-03-10 宁德时代新能源科技股份有限公司 Positive electrode active material, preparation method thereof and sodium ion battery
CN112490448A (en) * 2020-11-27 2021-03-12 中南大学 Preparation and purification method of (fluoro) vanadium sodium phosphate compound cathode material
CN112701285A (en) * 2020-12-29 2021-04-23 东北师范大学 Positive electrode material and preparation method and application thereof
CN112701283A (en) * 2020-12-29 2021-04-23 东北师范大学 Positive electrode material and preparation method and application thereof
CN113046768A (en) * 2021-03-15 2021-06-29 东北师范大学 Potassium vanadyl fluorophosphate, preparation method and application thereof, and potassium ion battery

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Na3V2(PO4)2O2F的合成及其在钠离子电池中的应用;吴凯;《电化学》;第27卷(第1期);第56-62页 *
钠离子电池正极材料Na3V2(PO4)2O2F的控制合成与电化学性能优化;谷振一等;《无机化学学报》(第09期);第1641-1648页 *
高性能聚阴离子型钒基钠电正极材料的设计制备与性能研究;郭晋芝;《中国博士学位论文全文数据库》(第09期);第B015-22页 *

Also Published As

Publication number Publication date
CN113745507A (en) 2021-12-03

Similar Documents

Publication Publication Date Title
US8865349B2 (en) Method of producing positive electrode active material and nonaqueous electrolyte battery using the same
CN105895879B (en) Fluorine-doped carbon-coated positive electrode composite material and preparation method and application thereof
CN103956485B (en) Lithium iron phosphate electrode material of a kind of three-dimensional hierarchical structure and preparation method thereof
KR20100083730A (en) Method of producing crystalline titanium oxide power, method of producing negative active material, negative active material and rechargeable lithium battery
CN111029560A (en) Spinel structure positive active material doped with sodium ions in gradient manner and preparation method thereof
CN111009659A (en) Preparation method and application of biomass carbon/poly-sodium manganese fluorophosphate composite material
CN113745507B (en) Sodium vanadyl chlorophosphate positive electrode material, preparation method and sodium ion battery
CN111162252B (en) Preparation method, product and application of RGO modified fluoro-substituted sodium vanadyl phosphate composite material
CN116826008A (en) 4d transition metal doped modified vanadium manganese sodium phosphate positive electrode material and preparation method thereof
CN113896193B (en) Surface modified exfoliated graphite as well as preparation method and application thereof
CN107069034B (en) Lithium ion battery positive electrode material and preparation method and application thereof
CN115504447A (en) Preparation method of lithium titanate coated ferric sodium pyrophosphate composite material
CN114084882A (en) Doping of different valence states with Na3V2(PO4)2F3Carbon-coated cubic crystal material and preparation method and application thereof
CN114094073A (en) Tin dioxide @ carbon foam self-supporting composite material and preparation method and application thereof
CN113871592A (en) Coated composite material and preparation method and application thereof
CN113991103A (en) Aqueous lithium ion battery NaTi2(PO4)3Preparation method of/C negative electrode material
CN109216673B (en) Lithium iron phosphate/multilayer graphene composite material, preparation method thereof and lithium ion battery using same
CN112242525A (en) Nitrogen-doped carbon-coated vanadium manganese sodium phosphate composite material and preparation method and application thereof
CN106935849A (en) A kind of anode material for lithium-ion batteries and preparation method thereof
Wen et al. improved electrochemical performance of LaF3-coated layered oxide Li1. 2Mn0. 54Ni0. 13Co0. 13O2 cathode material for lithium-ion batteries prepared by sol-gel method
CN114944488B (en) Preparation method of coated positive electrode material, product and application thereof
CN116154155B (en) Carbon-coated medium-entropy phosphate composite material and preparation method and application thereof
CN113880130B (en) Stannous sulfide carbon composite material and preparation method and application thereof
CN110880590B (en) Carbon nitride and carbon-coated NASICON type electrode material and preparation method thereof
CN109599544B (en) Lithium vanadium phosphate/carbon composite cathode 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
GR01 Patent grant
GR01 Patent grant