CN115084502A - NASICON type structure ternary sodium ion battery positive electrode material, preparation method and application thereof - Google Patents

NASICON type structure ternary sodium ion battery positive electrode material, preparation method and application thereof Download PDF

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CN115084502A
CN115084502A CN202210523820.3A CN202210523820A CN115084502A CN 115084502 A CN115084502 A CN 115084502A CN 202210523820 A CN202210523820 A CN 202210523820A CN 115084502 A CN115084502 A CN 115084502A
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sodium
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ion battery
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汤育欣
陈锦璇
白正帅
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Fuzhou University
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    • 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
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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

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Abstract

The invention belongs to the field of new energy material energy storage, and particularly relates to a ternary sodium-ion battery anode material with an NASICON type structure, a preparation method and application thereof. The invention adopts transition metal Mn element and Ni element to partially replace Na 3 V 2 (PO 4 ) 3 V element in (1), Na is obtained by increasing Na content while maintaining electrical neutrality 4 V x Mn y Ni z (PO 4 ) 3 A positive electrode material in which Mn element and Ni element occupy a part of V sites but still maintain an NASICON type structure and which has a large reversible capacity, Mn 2+ /Mn 3+ High oxidation-reduction voltage (more than 3.5V), good Ni compatibility substitution stability and the like. Na prepared by the invention 4 V x Mn y Ni z (PO 4 ) 3 The electrochemical performance of the cathode material can be further improved.

Description

NASICON type structure ternary sodium ion battery positive electrode material, preparation method and application thereof
Technical Field
The invention belongs to the field of new energy material energy storage, and particularly relates to a ternary sodium-ion battery anode material with an NASICON type structure, a preparation method and application thereof.
Background
With the progress of science and technology and the continuous development of human society, the demand of energy sources is more and more increased, thereby causing the exhaustion of fossil resources and the increasingly serious problem of environmental pollution. The realization of effective utilization of green renewable resources is imminent. Traditional renewable energy sources such as solar energy and wind energy are restricted by natural factors such as weather and cannot be directly used for an energy supply system. In order to sufficiently and efficiently store and use such intermittent energy sources, the development of large-scale energy storage systems is becoming a focus of attention. Lithium ion batteries have the advantages of high energy density, excellent cycling stability, environmental friendliness and the like, and have been widely used in portable electronic products and electric vehicles. But the large-scale use of lithium ion batteries also accelerates the exploitation of lithium resources. However, lithium resources have limited reserves, uneven distribution and high price, which limits the development of lithium resources in large-area energy storage. Sodium ion batteries have received global attention as the most promising alternative to lithium ion batteries because of the abundant, widespread and low cost of sodium resources in the earth's crust, in contrast to the exhaustible resources of lithium.
Among various developed positive electrode materials for sodium ion batteries, a polyanion-type positive electrode belonging to NASICON is attracting much attention because it has a stable three-dimensional framework structure, thereby promoting migration of sodium ions. Na (Na) 3 V 2 (PO 4 ) 3 (NVP) as a typical NASICON type positive electrode has high sodium ion diffusion coefficient, stable structure, small volume expansion coefficient in the process of sodium ion intercalation/deintercalation, moderate voltage platform (3.4V) and high theoretical specific capacity (400 Wh/kg), and is a promising positive electrode material of a sodium ion battery. However, the element V has higher cost, certain toxicity and is not friendly to the environment. Therefore, although NVP has a good prospect, it is more important to replace element V with an active substance which is low in cost and harmless to the environment. Benign and inexpensive three-dimensional transition metals such as Ti, Fe and Mn have the potential to be a substitute for V because of the involvement of Ti 3+ /Ti 4+ ，Fe 2+ /Fe 3+ And Mn 2+ /Mn 3+ Has been proposed and studied in the positive electrode material of NASICON. But Ti 3+ /Ti 4+ Low voltage plateau (2.1V) and Fe 2+ /Fe 3+ The low voltage plateau (2.5V) essentially determines its limited applicability to positive electrodes. And in Na 4 VMn(PO 4 ) 3 In the positive electrode material, Mn 2+ /Mn 3+ And V 3+ /V 4+ Provides larger capacity, but the material is easy to generate Jahn-Teller effect during the charge and discharge process, and leads to the irreversible damage of the electrode structure. Na (Na) 4 VNi(PO 4 ) 3 Although the cathode material has stable electrochemical performance, Ni as an inert component does not participate in redox reaction in the voltage range, so that the capacity of the cathode material is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a ternary sodium-ion battery positive electrode material with an NASICON type structure, a preparation method and application thereof.
The technical scheme adopted by the invention is as follows: a NASICON type ternary sodium ion battery positive electrode material with a chemical formula of Na 4 V x Mn y Ni z (PO 4 ) 3 And x, y and z are all larger than 0.
The preparation method of the NASICON type structure ternary sodium-ion battery cathode material comprises the following steps:
(1) dissolving a sodium source, a phosphorus source, a vanadium source, a manganese source and a nickel source in a solvent to obtain a solution, distilling under reduced pressure to remove part of the solvent, transferring the solution to an oven to dry to obtain Na 4 V x Mn y Ni z (PO 4 ) 3 The precursor of (2);
(2) grinding the precursor obtained in the step (1) to powder, placing the powder in a tube furnace, introducing inert gas, and sintering at the high temperature of 600-800 ℃ to obtain the phosphate Na with the NASICON structure 4 V x Mn y Ni z (PO 4 ) 3 A material.
Preferably, the vanadium source is any one of sodium vanadate, sodium metavanadate, vanadium pentoxide, vanadium acetylacetonate, vanadium trioxide, chromium-containing vanadium slag, or a combination of at least two thereof, typical but non-limiting examples of which are: combinations of vanadium acetylacetonate and vanadium trioxide, and the like.
Preferably, the source of phosphorus is any one or combination of at least two of phosphoric acid, sodium phosphate, sodium metaphosphate, or sodium dihydrogen phosphate, typical but non-limiting examples of combinations are: combinations of phosphoric acid and sodium phosphate, combinations of sodium phosphate and sodium dihydrogen phosphate, and the like.
Preferably, the sodium source is any one of sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium acetate, sodium vanadate, sodium metavanadate, sodium phosphate, or a combination of at least two thereof, typical but non-limiting examples of combinations are: combinations of sodium vanadate and sodium dihydrogen phosphate, combinations of sodium metaphosphate and sodium phosphate, and the like.
Preferably, the manganese source is any one of manganese acetate, manganese acetylacetonate, manganese carbonate or manganomanganic tetraoxide or a combination of at least two of them, and a typical but non-limiting example of the combination is a combination of manganese acetylacetonate and manganese acetate, and the like.
Preferably, the nickel source is any one of nickel acetylacetonate, nickel acetate or nickel chloride or a combination of at least two of them, and typical but non-limiting examples of the combination are a combination of nickel acetylacetonate and nickel acetate, and the like.
Preferably, in the step (1), a sodium source, a phosphorus source, a vanadium source, a manganese source and a nickel source are added to a solvent, heated and stirred, and then rotary evaporation is performed.
In a preferred embodiment of the present invention, the heating and stirring reaction is carried out in a water bath.
Preferably, the heating temperature is 60 to 90 ℃, for example, 60 ℃, 70 ℃, 80 ℃, etc., but is not limited to the recited values, and other values not recited in the numerical range are also used.
Preferably, the heating and stirring time is 1 to 5 hours, for example, 2 hours, 3 hours, 4 hours, etc., but the heating and stirring time is not limited to the recited values, and other values not recited in the range of the values are also used.
In a preferred embodiment of the present invention, the reduced pressure distillation is performed in a rotary evaporator.
Preferably, the heating temperature is 40 to 60 ℃, for example, 40 ℃, 50 ℃, 60 ℃, etc., but is not limited to the recited values, and other values not recited in the numerical range are also used.
As a preferred embodiment of the present invention, the drying is performed in a forced air drying oven.
Preferably, the temperature is 60 to 100 ℃, for example, 60 ℃, 80 ℃, 100 ℃, but not limited to the recited values, and other values not recited within the range of values are also used.
As a preferred embodiment of the present invention, the high-temperature sintering is performed in a tube furnace.
Preferably, the inert gas is any one of argon and nitrogen.
Preferably, the flow rate of the inert atmosphere introduced into the tube furnace is 10-200 mL min -1 E.g., 20 mL min -1 、80 mL min -1 、160 mL min -1 And the like, but are not limited to the recited numerical values, and other numerical values not recited in the numerical range are also used.
Preferably, the high-temperature sintering temperature is 600 to 800 ℃, for example, 600 ℃, 650 ℃, 700 ℃, etc., but is not limited to the recited values, and other values not recited within the range of values are also used.
Preferably, the high-temperature sintering time is 2 to 8 hours, such as 2 hours, 3 hours, 6 hours, and the like, but is not limited to the recited values, and other values not recited in the range of the values are also used.
A sodium ion battery adopts the NASICON type structure ternary sodium ion battery cathode material.
The invention has the following beneficial effects:
(1) the invention adopts transition metal Mn element and Ni element to partially replace Na 3 V 2 (PO 4 ) 3 A V element in (1) Na in order to maintain electroneutrality while increasing the Na content 4 V x Mn y Ni z (PO 4 ) 3 A positive electrode material in which Mn element and Ni element occupyPart of V is positioned, the NASICON type structure can be still maintained, the reversible capacity is large, and Mn 2+ /Mn 3+ High oxidation-reduction voltage (more than 3.5V), good Ni compatibility substitution stability and the like.
(2) Na prepared by the invention 4 V x Mn y Ni z (PO 4 ) 3 The electrochemical performance of the cathode material is further improved, such as Na prepared in example 2 of the invention 4 V x Mn y Ni z (PO 4 ) 3 Button cell battery assembled by positive electrode material is 0.02A g -1 、0.05 A g -1 、0.1 A g -1 、0.2A g -1 、0.5 A g -1 And 1A g -1 Respectively, has a capacity of 99.4 mAh g -1 、 98.8 mAh g -1 、96.3 mAh g -1 、93.6 mAh g -1 、87.5 mAh g -1 And 74.2 mAh g -1 Has excellent rate capability and can fully utilize V 3+ /V 4+ And Mn 2+ /Mn 3+ Oxidation-reduction reaction of (1).
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 shows Na prepared in examples of the present invention and comparative examples 4 V x Mn y Ni z (PO 4 ) 3 An X-ray diffraction pattern of the material;
FIG. 2 is Na prepared in example 1 of the present invention 4 VMn 0.5 Ni 0.5 (PO 4 ) 3 SEM image of the positive electrode material;
FIG. 3 is Na prepared in example 2 of the present invention 4 VMn 0.9 Ni 0.1 (PO 4 ) 3 The positive electrode material is 0.1mV s -1 Cyclic voltammogram at a scan rate of (a);
FIG. 4 is Na prepared in example 1 of the present invention 4 VMn 0.5 Ni 0.5 (PO 4 ) 3 The positive electrode material is 0.02-1A g -1 The charge-discharge curve of (1);
FIG. 5 is Na prepared in example 2 of the present invention 4 VMn 0.9 Ni 0.1 (PO 4 ) 3 The positive electrode material is 0.02-1A g -1 The charge-discharge curve of (1);
FIG. 6 is Na prepared in example 2 of the present invention 4 VMn 0.9 Ni 0.1 (PO 4 ) 3 The positive electrode material is 0.02-0.5A g -1 The rate capability of (a);
FIG. 7 is Na prepared in example 3 of the present invention 4 V 0.6 Mn 1.5 Ni 0.1 (PO 4 ) 3 The anode material is 0.02A g -1 The first 3 cycles of charge-discharge curve;
FIG. 8 is Na prepared in comparative example 1 of the present invention 4 VMn(PO 4 ) 3 The positive electrode material is 0.02-1A g -1 The charge-discharge curve of (1);
FIG. 9 is Na prepared in comparative example 2 of the present invention 4 VNi(PO 4 ) 3 The positive electrode material is 0.02-1A g -1 The charge-discharge curve of (1);
FIG. 10 shows Na prepared in examples 1 and 2 of the present invention and comparative examples 1 and 2 4 V x Mn y Ni z (PO 4 ) 3 The material is 0.05A g -1 The cycle performance of the following.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
step one, according to Na: v: mn: ni: p = 4: 1: 0.5: 0.5: 3, respectively weighing sodium acetate, vanadium acetylacetonate, manganese acetate, nickel acetate and phosphoric acid, dissolving in a certain amount of ethanol solvent under the condition of heating and stirring, stirring for a certain time to obtain a viscous solution, transferring the viscous solution to a rotary evaporator, and reducing the temperature by 60 DEG CDistilling under pressure to volatilize excessive ethanol solvent, transferring into oven, and drying at 80 deg.C to obtain Na 4 VMn 0.5 Ni 0.5 (PO 4 ) 3 The precursor of (1).
Step two, grinding the obtained precursor into powder, then placing the powder in a tube furnace, introducing argon, keeping the temperature at 700 ℃ for 5 hours, and cooling to room temperature to obtain the phosphate Na with the NASICON structure 4 VMn 0.5 Ni 0.5 (PO 4 ) 3 A material. The X-ray diffraction analysis thereof is shown in FIG. 1.
According to Na 4 VMn 0.5 Ni 0.5 (PO 4 ) 3 KB, PVDF in a mass ratio of 80: 10: 10 preparing an electrode, taking metal sodium as a counter electrode and 1M NaPF 6 100 Vol% glycol dimethyl ether is used as electrolyte, Whatman GF/D is used as a diaphragm, and a battery is assembled in a glove box and subjected to charge and discharge tests.
The voltage range is 2.0-3.8V, and the multiplying power is 0.02-1A g -1 The test result is shown in figure 4, the material shows a relatively obvious platform at about 3.5V, and the platform corresponds to V 3+ /V 4+ And Mn 2+ /Mn 3+ Reversible electrochemical redox reactions. The material is in the range of 0.02A g -1 、0.05 A g -1 、0.1 A g -1 、0.2A g -1 、0.5 A g -1 And 1A g -1 Respectively, the capacities of the respective cells were 84.1 mAh g -1 、 84.9 mAh g -1 、83.7 mAh g -1 、81.9 mAh g -1 、78.8 mAh g -1 And 67.6 mAh g -1 . Meanwhile, the material is 0.05A g -1 The test results of the cycle are shown in FIG. 10, and the capacity of 100 cycles of the cycle is 79.2 mAh g -1 Reduced to 74.2 mAh g -1 The capacity retention rate is 93.7%; coulombic efficiency rose from 82.1% to 95.4%.
Example 2:
step one, according to Na: v: mn: ni: p = 4: 1: 0.9: 0.1: 3, respectively weighing sodium acetate, vanadium acetylacetonate, manganese acetate, nickel acetate and phosphoric acid, dissolving in a certain amount of ethanol solvent under the condition of heating and stirring, stirring for a certain time to obtain a viscous solution, and transferring to a rotary evaporatorDistilling at 60 deg.C under reduced pressure to volatilize excessive ethanol solvent, transferring into oven, and drying at 80 deg.C to obtain Na 4 VMn 0.9 Ni 0.1 (PO 4 ) 3 The precursor of (1).
Step two, grinding the obtained precursor into powder, then placing the powder in a tube furnace, introducing argon, keeping the temperature at 700 ℃ for 5 hours, and cooling to room temperature to obtain the phosphate Na with the NASICON structure 4 VMn 0.9 Ni 0.1 (PO 4 ) 3 A material. The X-ray diffraction analysis thereof is shown in FIG. 1. The morphology is shown in fig. 2, and uniform blocky particles are presented.
According to Na 4 VMn 0.9 Ni 0.1 (PO 4 ) 3 KB, PVDF in a mass ratio of 80: 10: 10 preparing an electrode, taking metal sodium as a counter electrode and 1M NaPF 6 100 Vol% glycol dimethyl ether is used as electrolyte, Whatman GF/D is used as a diaphragm, and the battery is assembled in a glove box and subjected to charge and discharge tests.
The voltage range is 2.0-3.8V, and the multiplying power is 0.02-1A g -1 The test results are shown in FIGS. 5-6, the material is 0.02A g -1 、0.05 A g -1 、0.1 A g -1 、0.2A g -1 、0.5 A g -1 And 1A g -1 Respectively, has a capacity of 99.4 mAh g -1 、 98.8 mAh g -1 、96.3 mAh g -1 、93.6 mAh g -1 、87.5 mAh g -1 And 74.2 mAh g -1 . The material is at 0.1mV s -1 The cyclic voltammogram of (A) is shown in FIG. 3, and two sharper oxidation peaks and three gentle reduction peaks exist, corresponding to V 3+ /V 4+ And Mn 2+ /Mn 3+ Oxidation-reduction reaction of (2). Meanwhile, the material is 0.05A g -1 The test results of the cycle are shown in FIG. 10, and the capacity of 100 cycles of the cycle is 95.3 mAh g -1 Reduced to 89.8 mAh g -1 The capacity retention rate is 94.2%; coulombic efficiency increased from 88.1% to 95.2%.
Example 3:
step one, according to Na: v: mn: ni: p = 4: 0.6: 1.5: 0.1: 3, respectively weighing sodium acetate, vanadium acetylacetonate, manganese acetate, nickel acetate and phosphoric acid in a heating and stirring stateDissolving in ethanol solvent, stirring to obtain viscous solution, transferring to rotary evaporator at 60 deg.C, distilling under reduced pressure to volatilize excessive ethanol solvent, transferring to oven, and drying at 80 deg.C to obtain Na 4 V 0.6 Mn 1.5 Ni 0.1 (PO 4 ) 3 The precursor of (1).
Step two, grinding the obtained precursor into powder, then placing the powder in a tube furnace, introducing argon, keeping the temperature at 700 ℃ for 5 hours, and cooling to room temperature to obtain the phosphate Na with the NASICON structure 4 V 0.6 Mn 1.5 Ni 0.1 (PO 4 ) 3 A material. The X-ray diffraction analysis thereof is shown in FIG. 1.
According to Na 4 V 0.6 Mn 1.5 Ni 0.1 (PO 4 ) 3 KB, PVDF in a mass ratio of 80: 10: 10 preparing an electrode, taking metal sodium as a counter electrode and 1M NaPF 6 100 Vol% glycol dimethyl ether is used as electrolyte, Whatman GF/D is used as a diaphragm, and a battery is assembled in a glove box and subjected to charge and discharge tests.
The voltage range is 2.0-3.8V and is 0.02A g -1 The test was carried out as shown in FIG. 7, with a capacity of only 60 mAh g -1 However, the capacity of the first three circles has no attenuation basically, and 3.4V and 3.6V platforms are obviously seen, which correspond to V respectively 3+ /V 4+ And Mn 2+ /Mn 3+ 。
Comparative example 1:
step one, according to Na: v: mn: p = 4: 1: 1: 3, respectively weighing sodium acetate, vanadium acetylacetonate, manganese acetate and phosphoric acid, dissolving in a certain amount of ethanol solvent under the condition of heating and stirring, stirring for a certain time to obtain a viscous solution, transferring to a rotary evaporator, distilling at 60 ℃ under reduced pressure to volatilize excessive ethanol solvent, transferring to an oven, and drying at 80 ℃ to obtain Na 4 VMn(PO 4 ) 3 The precursor of (1).
Step two, grinding the obtained precursor into powder, then placing the powder in a tube furnace, introducing argon, keeping the temperature at 700 ℃ for 5 hours, and cooling to room temperature to obtain the phosphate Na with the NASICON structure 4 VMn(PO 4 ) 3 A material.
According to Na 4 VMn(PO 4 ) 3 KB, PVDF in a mass ratio of 80: 10: 10 preparing an electrode, taking metal sodium as a counter electrode and 1M NaPF 6 100 Vol% glycol dimethyl ether is used as electrolyte, Whatman GF/D is used as a diaphragm, and a battery is assembled in a glove box and subjected to charge and discharge tests.
The voltage range is 2.0-3.8V, and the multiplying power is 0.02-1A g -1 The test result is shown in FIG. 8, and the material is 0.02A g -1 、0.05 A g -1 、0.1 A g -1 、0.2 A g -1 、0.5 A g -1 And 1A g -1 The capacity of each of the cells was 96.3 mAh g -1 、 94.7 mAh g -1 、90.9 mAh g -1 、85.6 mAh g -1 、73.1 mAh g -1 And 55.5 mAh g -1 . Meanwhile, the material is 0.05A g -1 The test results of the cycle are shown in FIG. 10, and the capacity of 100 cycles of the cycle is 91.1 mAh g -1 Reduced to 83.8 mAh g -1 The capacity retention rate is 91.9%; the coulombic efficiency is reduced from 91.8% to 85.5%.
Comparative example 2:
step one, according to Na: v: ni: p = 4: 1: 1: 3, respectively weighing sodium acetate, vanadium acetylacetonate, manganese acetate and phosphoric acid, dissolving in a certain amount of ethanol solvent under the condition of heating and stirring, stirring for a certain time to obtain a viscous solution, transferring to a rotary evaporator, distilling at 60 ℃ under reduced pressure to volatilize excessive ethanol solvent, transferring to an oven, and drying at 80 ℃ to obtain Na 4 VNi(PO 4 ) 3 The precursor of (1).
Step two, grinding the obtained precursor into powder, then placing the powder in a tube furnace, introducing argon, keeping the temperature at 700 ℃ for 5 hours, and cooling to room temperature to obtain the phosphate Na with the NASICON structure 4 VNi(PO 4 ) 3 A material.
According to Na 4 VNi(PO 4 ) 3 KB, PVDF in a mass ratio of 80: 10: 10 preparing an electrode, taking metal sodium as a counter electrode and 1M NaPF 6 100 Vol% glycol dimethyl ether is taken as electrolyte, Whatman GF/D is taken as diaphragm, and the electrolyte is assembled in a glove boxAnd carrying out charge and discharge tests on the battery.
The voltage range is 2.0-3.8V, and the multiplying power is 0.02-1A g -1 The test result is shown in FIG. 9, and the material is 0.02A g -1 、0.05 A g -1 、0.1 A g -1 、0.2A g -1 、0.5 A g -1 And 1A g -1 Respectively, has a capacity of 46.9 mAh g -1 、 52.1 mAh g -1 、52.2 mAh g -1 、52.0 mAh g -1 、51.5 mAh g -1 And 46.5 mAh g -1 . Meanwhile, the material is 0.05A g -1 The test results of the cycle are shown in FIG. 10, and the capacity of the cycle of 100 circles is 47.4 mAh g -1 Reduced to 46.9 mAh g -1 The capacity retention rate is 98.9%; coulombic efficiency increased from 68.9% to 96.3%.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.

Claims (10)

1. The NASICON type structure ternary sodium ion battery cathode material is characterized in that: has a chemical formula of Na 4 V x Mn y Ni z (PO 4 ) 3 And x, y and z are all larger than 0.
2. The method for preparing the NASICON-type structure ternary sodium-ion battery positive electrode material according to claim 1, characterized by comprising the following steps:
(1) dissolving a sodium source, a phosphorus source, a vanadium source, a manganese source and a nickel source in a solvent to obtain a solution, distilling under reduced pressure to remove part of the solvent, transferring the solution to an oven to dry to obtain Na 4 V x Mn y Ni z (PO 4 ) 3 A precursor of (a);
(2) grinding the precursor obtained in the step (1) to powder, placing the powder in a tube furnace, introducing inert gas, and sintering at the high temperature of 600-800 ℃ to obtain the phosphate Na with the NASICON structure 4 V x Mn y Ni z (PO 4 ) 3 A material.
3. The preparation method of the NASICON-type structure ternary sodium-ion battery positive electrode material according to claim 2, characterized in that: the vanadium source is any one of or a combination of at least two of chromium-containing vanadium slag containing sodium vanadate, sodium metavanadate, vanadium pentoxide, vanadium acetylacetonate and vanadium trioxide.
4. The preparation method of the NASICON-type structure ternary sodium-ion battery positive electrode material according to claim 2, characterized in that: the phosphorus source is any one or the combination of at least two of phosphoric acid, sodium phosphate, sodium metaphosphate and sodium dihydrogen phosphate.
5. The preparation method of the NASICON-type structure ternary sodium-ion battery positive electrode material according to claim 2, characterized in that: the sodium source is any one or the combination of at least two of sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium acetate, sodium vanadate, sodium metavanadate and sodium phosphate.
6. The preparation method of the NASICON-type structure ternary sodium-ion battery positive electrode material according to claim 2, characterized in that: the manganese source is any one of manganese acetate, manganese acetylacetonate, manganese carbonate or manganous manganic oxide or the combination of at least two of the manganese acetate, the manganese acetylacetonate and the manganese carbonate.
7. The preparation method of the NASICON-type structure ternary sodium-ion battery positive electrode material according to claim 2, characterized in that: the nickel source is any one or the combination of at least two of nickel acetylacetonate, nickel acetate and nickel chloride.
8. The preparation method of the NASICON-type structure ternary sodium-ion battery cathode material according to claim 2, characterized in that: in the step (1), a sodium source, a phosphorus source, a vanadium source, a manganese source and a nickel source are added into a solvent, heated and stirred for 1-5 hours at the temperature of 60-90 ℃, and then rotary evaporation is carried out at the temperature of 40-60 ℃, wherein the rotary evaporation time is 10-30 min.
9. The preparation method of the NASICON-type structure ternary sodium-ion battery positive electrode material according to claim 2, characterized in that: in the step (2), the inert atmosphere is any one of argon and nitrogen; the flow of the inert atmosphere introduced into the tube furnace is 10-200 mL min -1 And the sintering time is 2-8 h.
10. A sodium ion battery using the NASICON-type structure ternary sodium ion battery positive electrode material as claimed in claim 1.
CN202210523820.3A 2022-05-13 2022-05-13 NASICON type structure ternary sodium ion battery positive electrode material, preparation method and application thereof Pending CN115084502A (en)

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CN102569797A (en) * 2012-01-20 2012-07-11 中国科学院宁波材料技术与工程研究所 Novel phosphate based composite cathode material, its preparation method and application thereof
CN107123796A (en) * 2017-05-11 2017-09-01 中南大学 A kind of violent sodium composite of carbon coating vanadium phosphate and preparation method thereof and the application in sodium-ion battery
CN107978743A (en) * 2017-11-20 2018-05-01 中南大学 A kind of sodium-ion battery positive material and preparation method thereof, sodium-ion battery
CN112421040A (en) * 2020-11-16 2021-02-26 中国科学院过程工程研究所 Phosphate anode material and preparation method and application thereof
CN112447947A (en) * 2019-08-28 2021-03-05 宁德时代新能源科技股份有限公司 Positive electrode material for sodium ion battery and preparation method thereof
CN113929069A (en) * 2021-10-08 2022-01-14 中国科学院过程工程研究所 Manganese-rich phosphate cathode material and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569797A (en) * 2012-01-20 2012-07-11 中国科学院宁波材料技术与工程研究所 Novel phosphate based composite cathode material, its preparation method and application thereof
CN107123796A (en) * 2017-05-11 2017-09-01 中南大学 A kind of violent sodium composite of carbon coating vanadium phosphate and preparation method thereof and the application in sodium-ion battery
CN107978743A (en) * 2017-11-20 2018-05-01 中南大学 A kind of sodium-ion battery positive material and preparation method thereof, sodium-ion battery
CN112447947A (en) * 2019-08-28 2021-03-05 宁德时代新能源科技股份有限公司 Positive electrode material for sodium ion battery and preparation method thereof
CN112421040A (en) * 2020-11-16 2021-02-26 中国科学院过程工程研究所 Phosphate anode material and preparation method and application thereof
CN113929069A (en) * 2021-10-08 2022-01-14 中国科学院过程工程研究所 Manganese-rich phosphate cathode material and preparation method and application thereof

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