CN107978743A - A kind of sodium-ion battery positive material and preparation method thereof, sodium-ion battery - Google Patents
A kind of sodium-ion battery positive material and preparation method thereof, sodium-ion battery Download PDFInfo
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- CN107978743A CN107978743A CN201711156026.5A CN201711156026A CN107978743A CN 107978743 A CN107978743 A CN 107978743A CN 201711156026 A CN201711156026 A CN 201711156026A CN 107978743 A CN107978743 A CN 107978743A
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- ion battery
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- 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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- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- 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
Abstract
The invention discloses a kind of sodium-ion battery positive material, the molecular formula of the sodium-ion battery positive material is Na4Fe0.5Mn0.5V(PO4)3, it is trigonal system, space group is R 3c, is irregular laminated structure.The invention also discloses the preparation method of above-mentioned sodium-ion battery positive material, and sodium source, source of iron, manganese source, vanadium source and phosphorus source are stoichiometrically dissolved in deionized water, adds the mixed solution of tetraethylene glycol and ethylene glycol, reaction is stirred at room temperature, obtains mixed liquor；Mixed liquor is transferred in reaction kettle, heating reaction, obtains thick gel, thick gel is freeze-dried, obtain presoma powder；By the high-temperature calcination under an inert atmosphere of presoma powder, sheet sodium-ion battery positive material is obtained.This method is reproducible, it is easy to operate, there is prospects for commercial application, present invention also offers a kind of sodium-ion battery using above-mentioned sodium-ion battery positive material, which has excellent chemical property.
Description
Technical field
The invention belongs to sodium-ion battery technical field, and in particular to a kind of sodium-ion battery positive material and its preparation side
Method, sodium-ion battery.
Background technology
Lithium ion battery due to height ratio capacity, high-energy-density and be widely used in portable electric appts and ion
Popularization and application of the battery in large-scale energy-storage system field.Sodium-ion battery be considered as effective substitute of lithium ion battery into
For domestic and international research hotspot.Sodium have and lithium similar in physicochemical properties, and reserves of the sodium resource in the earth's crust are considerable
(crustal abundance of lithium is 0.006%, and the crustal abundance of sodium has very big advantage for 2.64%) in cost, this
So that sodium-ion battery becomes a kind of most potential battery system available for extensive energy storage commercial applications.
To meet practical application request, high voltage, high-energy-density are the developing direction of sodium-ion battery positive material.Phase
Than in oxide system and Prussian blue similar objects system, polyanionic sodium-ion battery positive material is due to polyanion
Inductive effect, shows the voltage of higher.And polyanionic material is due to open ion diffusion admittance, and material knot
Structure stability and heat endurance are high, great application prospect.In polyanion system, and with the fast-ionic conductor type of sodium
(NASICON) material is of greatest concern.In NASICON type positive electrodes, and with vanadium phosphate sodium (Na3V2(PO4)3) attract most attention, its
Excellent big multiplying power and cyclical stability have greatly promoted the development of sodium-ion battery positive material.But Na3V2(PO4)3Conductance
Rate is relatively low, its voltage platform is 3.4V, is still had to be hoisted.
Disclosed in patent document CN201710364045 a kind of vanadium phosphate manganese sodium 3D porous graphenes composite material and its
Preparation method and the application in sodium-ion battery.Its by by sheet vanadium phosphate manganese sodium growth in situ in 3D porous graphene bones
On frame, using sheet vanadium phosphate manganese sodium specific surface area it is big, with electrolyte contacts face the advantages of big and 3D porous graphenes are stablized
The advantages that loose three-dimensional open-framework, specific surface area are big, load stability is good is combined, and effectively overcomes vanadium phosphate manganese sodium material
The problem of conductivity is low, improves the performance of material.
The content of the invention
It is low, electric it is an object of the present invention to provide a kind of cost for the deficiency and defect mentioned in background above technology
The good sodium-ion battery positive material of chemical property.
It is a further object of the invention to provide a kind of sodium-ion battery easy to operate, having prospects for commercial application
The preparation method of positive electrode.
It is a further object of the invention to provide a kind of sodium ion electricity using above-mentioned sodium-ion battery positive material
Pond, the sodium-ion battery have good specific discharge capacity, good high rate performance and cycle performance.
In order to solve the above technical problems, technical solution proposed by the present invention is：
A kind of sodium-ion battery positive material, the molecular formula of the sodium-ion battery positive material is Na4Fe0.5Mn0.5V
(PO4)3, it is trigonal system, is R-3c space groups, and be laminated structure.
As preferable scheme, the specific surface area of the sodium-ion battery positive material is 3~100m2/g。
The vanadium phosphate ferromanganese sodium positive electrode of the present invention substitutes the part vanadium in vanadium phosphate sodium by iron, manganese, wherein, iron
The electrical conductivity for improving positive electrode is added, the addition of manganese improves the voltage of positive electrode.The vanadium phosphate ferromanganese sodium of the present invention
The molecular formula of positive electrode is Na4Fe0.5Mn0.5V(PO4)3, the positive electrode that each element is formed under the special ratios is tripartite
Crystallographic system, its space group are R-3c, its shape is irregular laminated structure, purity is high and thing mutually homogeneous (each element is in other ratios
More dephasign will be formed under example, the homogeneous thing phase of high-purity can not be formed).This special crystalline structure causes vanadium phosphate manganese
Ferrisodium positive electrode has the sodium ion diffusion admittance of multidimensional, and the positive electrode compared to other structures is more advantageous to sodium ion
Fast transferring, and then be conducive to improve the chemical property of positive electrode and sodium-ion battery prepared therefrom.It is also, irregular
Laminated structure, be also beneficial to lifting material electrons/ions kinetics of diffusion, improve its chemical property.The tool of the present invention
There is the vanadium phosphate ferromanganese sodium positive electrode of special construction compared with the composite material of patent document CN201710364045, eliminate
Using expensive graphene, and using iron part substitution vanadium (price of iron is lower than vanadium), improving vanadium phosphate sodium cathode material
While expecting performance, the production cost of material is effectively reduced.
Another aspect of the present invention provides a kind of preparation method of above-mentioned sodium-ion battery positive material, including following step
Suddenly：
(1) sodium source, source of iron, manganese source, vanadium source and phosphorus source are stoichiometrically dissolved in deionized water so that in solution
The concentration of vanadium ion is 0.05~0.1mol/L, then adds the mixed solution of tetraethylene glycol and ethylene glycol, is stirred at room temperature, must mix
Liquid, the volume ratio of tetraethylene glycol and ethylene glycol is 1 in the mixed solution of the tetraethylene glycol and ethylene glycol：(0.5~2)；
(2) mixed liquor obtained by step (1) is transferred in reaction kettle, 8~12h is reacted at 160~200 DEG C, obtains sticky glue
Gained thick gel, is then freeze-dried by body, obtains presoma powder；
(3) presoma powder obtained by step (2) is calcined into 6~12h at 650~850 DEG C under an inert atmosphere, up to sodium from
Sub- cell positive material.
The present invention preparation method by sodium source, source of iron, manganese source, vanadium source and phosphorus source under special ratios, are dissolved in from
Sub- water water, then adds the mixed solution of tetraethylene glycol and ethylene glycol, forms the hydro-thermal reaction system containing tetraethylene glycol and ethylene glycol,
And by control the concentration of vanadium ion in the volume ratio of tetraethylene glycol and ethylene glycol, solution system, hydro-thermal reaction temperature and time,
The temperature and time of calcining, obtains having specific structure (trigonal system, R-3c space groups, irregular sheet)
Na4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material.The preparation method is the special construction with the present invention
Na4Fe0.5Mn0.5V(PO4)3Positive electrode is corresponding, realizes cooperateing between preparation method and product structure.
As preferable scheme, in the step (1), the volume and deionized water of the mixed solution of tetraethylene glycol and ethylene glycol
The ratio between volume be 1：(1.5~3.5).
As preferable scheme, in the step (1), the time being stirred at room temperature is 0.5~1.5h.More preferably
1h。
As preferable scheme, in the step (2), the temperature of the reaction is preferably 180 DEG C.
As preferable scheme, in the step (1), the sodium source is sodium acetate, sodium carbonate, sodium acid carbonate, di(2-ethylhexyl)phosphate
One or more in hydrogen sodium and disodium hydrogen phosphate.
As preferable scheme, in the step (1), the source of iron is ferrous oxalate, ferrous acetate, ironic citrate and lemon
One or more in lemon acid iron ammonium.
As preferable scheme, in the step (1), the manganese source for manganese acetate, manganese oxalate, one kind in manganese nitrate or
It is a variety of.
As preferable scheme, in the step (1), the vanadium source is pressed for metavanadic acid, vanadium acetylacetonate, acetylacetone,2,4-pentanedione oxygen
One or more in vanadium, sodium vanadate.
As preferable scheme, in the step (1), phosphorus source is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus
One or more in sour ammonium, disodium hydrogen phosphate and sodium dihydrogen phosphate.
As preferable scheme, in the step (3), the inert atmosphere for argon gas, nitrogen and it is hydrogen-argon-mixed in
It is one or more.
Another aspect of the present invention additionally provides a kind of sodium-ion battery, and above-mentioned sodium ion has been used in the sodium-ion battery
Cell positive material, or the sodium-ion battery positive material being prepared by above-mentioned preparation method has been used, and test
Its chemical property.For example, by the irregular sheet Na4Fe0.5Mn0.5V(PO4)3Material is mixed with conductive agent, binding agent
After conjunction, by coated in sodium-ion battery cathode on aluminium foil, is made.Used conductive agent, binding agent can use this area skill
Material known to art personnel.The method that assembling prepares sodium-ion battery positive material also refers to existing method.For example, it incite somebody to action this
Irregular sheet Na made from invention4Fe0.5Mn0.5V(PO4)3Material is with conductive black and PVDF binding agents according to 8:1:1 matter
Amount ratio is ground, and NMP is added after being sufficiently mixed and forms uniform slurry, and electrode is tested coated in being used as on aluminium foil, with
Metallic sodium is used as to electrode, its electrolyte is 1M NaClO4/ 100%PC, prepares sodium half-cell and tests its chemical property.
Compared with prior art, the advantage of the invention is that：
(1) sodium-ion battery positive material of the invention is trigonal system, is R-3c space groups, its molecular formula is
Na4Fe0.5Mn0.5V(PO4)3, purity is high and thing is mutually homogeneous, which has the sodium ion diffusion admittance of multidimensional, is conducive to
The fast transferring of sodium ion so that material has excellent chemical property.
(2) sodium-ion battery positive material of the invention uses iron partial replacement vanadium, compared to existing vanadium phosphate manganese sodium
With the composite positive pole of graphene, sodium-ion battery positive material of the invention effectively drops while material property is improved
The low production cost of material.
(3) vanadium phosphate ferromanganese sodium has irregular laminated structure in sodium-ion battery positive material of the invention, and has
There is big specific surface area, improve the electrons/ions kinetics of diffusion of material, further increase the chemical property of material.
(4) in the preparation method of sodium-ion battery positive material of the invention, in sodium source, source of iron, manganese source, vanadium source and phosphorus source
Solution in add the mixed solution (forming the hydro-thermal reaction system containing tetraethylene glycol and ethylene glycol) of tetraethylene glycol and ethylene glycol, and
Control the concentration of vanadium ion in the volume ratio of tetraethylene glycol and ethylene glycol, solution system, the temperature and time of hydro-thermal reaction, calcining
Temperature and time, obtains the Na with specific structure4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material, realizes preparation side
Method is cooperateed with product structure.
(5) preparation method of sodium-ion battery positive material of the invention it is reproducible, it is easy to operate, there is commercial Application
Prospect.
(6) sodium-ion battery being assembled into using the sodium-ion battery positive material of the present invention has high electric discharge specific volume
Amount, good high rate performance and cycle performance, its capacity under 5C multiplying powers reach more than 73mAh/g, 50 are circulated under 2C multiplying powers
Its specific discharge capacity reaches 89mAh/g after circle, its capacity retention ratio is up to 89%.
To sum up, the present invention, with reference to special preparation method, obtains having three prismatic crystals under specific element ratio
System, R-3c space groups, molecular formula Na4Fe0.5Mn0.5V(PO4)3, purity is high and thing is mutually homogeneous sodium-ion battery positive material,
Production cost is effectively reduced, improves sodium-ion battery positive material and the performance of the sodium-ion battery prepared by the material.
Brief description of the drawings
Fig. 1 is 1 gained Na of the embodiment of the present invention4Fe0.5Mn0.5V(PO4)3The scanning electron microscope (SEM) photograph of sodium-ion battery positive material
(SEM)。
Fig. 2 is 1 gained Na of the embodiment of the present invention4Fe0.5Mn0.5V(PO4)3The XRD of sodium-ion battery positive material.
Fig. 3 is 1 gained Na of the embodiment of the present invention4Fe0.5Mn0.5V(PO4)3The sodium ion of sodium-ion battery positive material assembling
The high rate performance figure of battery.
Fig. 4 is 1 gained Na of the embodiment of the present invention4Fe0.5Mn0.5V(PO4)3The sodium ion of sodium-ion battery positive material assembling
Cycle performance figure of the battery under 2C multiplying powers.
Embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, all technical terms used hereinafter and the normally understood implication of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates are dissolved in 150mL deionized waters, and add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1：1) mix
Solution, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, 10h is reacted at 180 DEG C and is obtained
Thick gel, then obtains presoma powder by thick gel is freeze-dried.Again by presoma powder under an argon atmosphere 750
8h is calcined at DEG C, obtains Na4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material.
Obtained Na4Fe0.5Mn0.5V(PO4)3The pattern (SEM) of positive electrode is shown in Fig. 1, and as seen from Figure 1, it is not advise
Laminated structure then.Fig. 2 is gained Na4Fe0.5Mn0.5V(PO4)3The XRD diagram of positive electrode, as can be seen from Figure 2, resulting materials are really
Na4Fe0.5Mn0.5V(PO4)3Target product, and dephasign is few, the mutually homogeneous purity of thing is high；Learnt through theoretical fitting, should
Na4Fe0.5Mn0.5V(PO4)3Positive electrode is trigonal system, space group R-3c.Using sodium-ion battery manufactured in the present embodiment
Positive electrode is assembled into button cell with sodium piece, and the high rate performance of gained button cell is tested, test result such as Fig. 3
It is shown.As seen from Figure 3, using Na obtained by the present embodiment4Fe0.5Mn0.5V(PO4)3Sodium-ion battery prepared by positive electrode
High rate performance it is superior, still have the capacity of 83.1mAh/g under the multiplying power of 5C.Fig. 3 exists for prepared button cell
Cycle performance figure under 2C multiplying powers.Figure 4, it is seen that its specific discharge capacity reaches after the circle of circulation 50 under 2C multiplying powers
89.8mAh/g, capacity retention ratio is up to 89%.Tested through BET, Na obtained by the present embodiment4Fe0.5Mn0.5V(PO4)3Sodium-ion battery
The specific surface area of positive electrode is 58.2m2/g。
Embodiment 2：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 100mL deionized waters：1) mix molten
Liquid, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, 10h is reacted at 180 DEG C and is glued
Thick glue body, then obtains presoma powder by thick gel is freeze-dried.Again by 750 DEG C under an argon atmosphere of presoma powder
Lower calcining 8h, obtains the Na of irregular laminated structure4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material.It is three prismatic crystals
System, space group R-3c, thing are mutually homogeneous.
Using Na manufactured in the present embodiment4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material is assembled into button with sodium piece
Battery, after tested, the button cell is under the multiplying power of 5C, specific discharge capacity 78.1mAh/g.BET tests show, are somebody's turn to do
Na4Fe0.5Mn0.5V(PO4)3The specific surface area of sodium-ion battery positive material is 57.6m2/g。
Embodiment 3：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 200mL deionized waters：1) mix molten
Liquid, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, 10h is reacted at 180 DEG C and is glued
Thick glue body, then obtains presoma powder by thick gel by freeze-drying.Again by presoma powder under an argon atmosphere 750
8h is calcined at DEG C, obtains the Na of irregular laminated structure4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material.It is three prismatic crystals
System, space group R-3c, thing are mutually homogeneous.
Using Na manufactured in the present embodiment4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material is assembled into button with sodium piece
Battery, after tested, the button cell is under the multiplying power of 5C, specific discharge capacity 81.2mAh/g.
Embodiment 4：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 150mL deionized waters：0.5) mix
Solution, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, 10h is reacted at 180 DEG C and is obtained
Thick gel, then obtains presoma powder by thick gel is freeze-dried.Again by presoma powder under an argon atmosphere 750
8h is calcined at DEG C, obtains the Na of irregular laminated structure4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material.It is three prismatic crystals
System, space group R-3c, thing are mutually homogeneous.
Using Na manufactured in the present embodiment4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material is assembled into button with sodium piece
Battery, after tested, the button cell is under the multiplying power of 5C, specific discharge capacity 76.4mAh/g.
Embodiment 5：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol metavanadic acids by with
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 150mL deionized waters：2) mix molten
Liquid, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, 10h is reacted at 180 DEG C and is glued
Thick glue body, then obtains presoma powder by thick gel is freeze-dried.Again by 750 DEG C under an argon atmosphere of presoma powder
Lower calcining 8h, obtains the Na of irregular laminated structure4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material.It is three prismatic crystals
System, space group R-3c, thing are mutually homogeneous.
Using Na manufactured in the present embodiment4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material is assembled into button with sodium piece
Battery, after tested, the button cell is under the multiplying power of 5C, specific discharge capacity 73.7mAh/g.
Embodiment 6：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 150mL deionized waters：1) mix molten
Liquid, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, reaction 8h is obtained sticky at 180 DEG C
Colloid, then obtains presoma powder by thick gel is freeze-dried.Again by presoma powder under an argon atmosphere 850 DEG C
8h is calcined, obtains the Na of irregular laminated structure4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material.It is trigonal system,
Space group is R-3c, and thing is mutually homogeneous.
Using Na manufactured in the present embodiment4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material is assembled into button with sodium piece
Battery, after tested, the button cell is under the multiplying power of 5C, specific discharge capacity 80.4mAh/g.
Embodiment 7：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 150mL deionized waters：1) mix molten
Liquid, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, 12h is reacted at 180 DEG C and is glued
Thick glue body, then obtains presoma powder by thick gel is freeze-dried.Again by 650 DEG C under an argon atmosphere of presoma powder
Lower calcining 6h, obtains the Na of irregular laminated structure4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material.It is three prismatic crystals
System, space group R-3c, thing are mutually homogeneous.
Using Na manufactured in the present embodiment4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material is assembled into button with sodium piece
Battery, after tested, the button cell is under the multiplying power of 5C, specific discharge capacity 76.3mAh/g.
Comparative example 1：
Take 0.04mol sodium acetates, 0.003mol ferrous oxalates, 0.007mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates are dissolved in 150mL deionized waters, and add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1：1) mix
Solution, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, 10h is reacted at 180 DEG C and is obtained
Thick gel, then obtains presoma powder by thick gel is freeze-dried.Again by presoma powder under an argon atmosphere 750
8h is calcined at DEG C, for the button cell of resulting materials assembling under the multiplying power of 5C, specific discharge capacity is only 18.6mAh/g.XRD results
It has been shown that, the material contain substantial amounts of dephasign, and the purity and chemical property that have impact on material play.
Comparative example 2：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates are dissolved in 150mL deionized waters, and 1h is stirred at room temperature, and obtain mixed liquor.Then gained mixed liquor is shifted
Into reaction kettle, at 180 DEG C react 10h obtain with precipitation solution, then by resulting solution is freeze-dried obtain before
Drive body powder.8h will be calcined at presoma powder under an argon atmosphere 750 DEG C again, obtained material does not have corresponding crystal form knot
Structure, and pattern is bulk.Illustrate the addition of the mixed solution of tetraethylene glycol and ethylene glycol to forming laminated structure
Na4Fe0.5Mn0.5V(PO4)3It is most important.
Comparative example 3：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol metavanadic acids by with
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 150mL deionized waters：4) mix molten
Liquid, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, reaction 8h is obtained sticky at 180 DEG C
Colloid, then obtains presoma powder by thick gel is freeze-dried.Again by presoma powder under an argon atmosphere 750 DEG C
Calcine 8h, obtained Na4Fe0.5Mn0.5V(PO4)3Material does not have irregular laminated structure.
The Na prepared using this comparative example4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material is assembled into button with sodium piece
Battery, after tested, under the multiplying power of 5C, specific discharge capacity 41.2mAh/g, its specific discharge capacity is significantly less than the button cell
Na with irregular laminated structure4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material.Illustrate tetraethylene glycol and ethylene glycol
The volume ratio of tetraethylene glycol and ethylene glycol is not 1 in mixed solution：(this comparative example is 1 when in the range of (0.5~2)：4), can not obtain
To the Na with laminated structure4Fe0.5Mn0.5V(PO4)3Material, its chemical property are less than with laminated structure
Na4Fe0.5Mn0.5V(PO4)3Material.
Comparative example 4：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol metavanadic acids by with
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 150mL deionized waters：0.3) mix
Solution, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, 8h is reacted at 180 DEG C and is glued
Thick glue body, then obtains presoma powder by thick gel is freeze-dried.Again by 750 DEG C under an argon atmosphere of presoma powder
Lower calcining 8h, obtained Na4Fe0.5Mn0.5V(PO4)3Material does not have irregular laminated structure.Illustrate the mixed of tetraethylene glycol and ethylene glycol
The volume ratio of tetraethylene glycol and ethylene glycol is not 1 in conjunction solution：(this comparative example is 1 when in the range of (0.5~2)：0.3), can not obtain
To the Na with laminated structure4Fe0.5Mn0.5V(PO4)3Material.
Comparative example 5：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 300mL deionized waters：1) mix molten
Liquid, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, reaction 8h is obtained sticky at 180 DEG C
Colloid, then obtains presoma powder by thick gel is freeze-dried.Again by presoma powder under an argon atmosphere 750 DEG C
Calcine 8h, obtained Na4Fe0.5Mn0.5V(PO4)3Material does not have irregular laminated structure.
The Na prepared using this comparative example4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material is assembled into button with sodium piece
Battery, after tested, under the multiplying power of 5C, specific discharge capacity 37.7mAh/g, its specific discharge capacity is significantly less than the button cell
Na with irregular laminated structure4Fe0.5Mn0.5V(PO4)3Sodium-ion battery positive material.Illustrate when sodium source, source of iron, manganese source,
When the concentration that vanadium source and phosphorus source are stoichiometrically dissolved in vanadium ion in the solution formed after deionized water is less than 0.05mol/L
(this comparative example is 0.033mol/L), can not obtain the Na with laminated structure4Fe0.5Mn0.5V(PO4)3Material, its electrochemistry
The Na with laminated structure can be less than4Fe0.5Mn0.5V(PO4)3Material.
Comparative example 6：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 70mL deionized waters：1) mix molten
Liquid, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, reaction 8h is obtained sticky at 180 DEG C
Colloid, then obtains presoma powder by thick gel is freeze-dried.Again by presoma powder under an argon atmosphere 750 DEG C
Calcine 8h, obtained Na4Fe0.5Mn0.5V(PO4)3Material does not have irregular laminated structure.Illustrate when sodium source, source of iron, manganese source, vanadium
(this when concentration that source and phosphorus source are stoichiometrically dissolved in vanadium ion in the solution formed after deionized water is more than 0.1mol/L
Comparative example is 0.14mol/L), the Na with laminated structure can not be obtained4Fe0.5Mn0.5V(PO4)3Material.
Comparative example 7：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 150mL deionized waters：1) mix molten
Liquid, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, 16h is reacted at 180 DEG C and is glued
Thick glue body, then obtains presoma powder by thick gel is freeze-dried.Again by 750 DEG C under an argon atmosphere of presoma powder
Lower calcining 8h, obtained Na4Fe0.5Mn0.5V(PO4)3Material does not have irregular laminated structure.Illustrate that mixed liquor is anti-in a kettle
Between seasonable not in the range of 8h~12h (this comparative example is 16h), it can not obtain that there is irregular laminated structure
Na4Fe0.5Mn0.5V(PO4)3Material.
Comparative example 8：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 150mL deionized waters：1) mix molten
Liquid, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, reaction 6h is obtained sticky at 180 DEG C
Colloid, then obtains presoma powder by thick gel is freeze-dried.Again by presoma powder under an argon atmosphere 750 DEG C
Calcine 8h, obtained Na4Fe0.5Mn0.5V(PO4)3Material does not have irregular laminated structure.Illustrate that mixed liquor reacts in a kettle
Time (this comparative example is 6h) not in the range of 8h~12h, the Na with irregular laminated structure can not be obtained4Fe0.5Mn0.5V
(PO4)3Material.
Comparative example 9：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol ammonium metavanadates and
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 150mL deionized waters：1) mix molten
Liquid, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, 10h is reacted at 180 DEG C and is glued
Thick glue body, then obtains presoma powder by thick gel is freeze-dried.Again by 550 DEG C under an argon atmosphere of presoma powder
Lower calcining 8h, product X RD do not have the correspondence peak shape of target product.When illustrating calcining heat not in the range of 650 DEG C~850 DEG C
(this comparative example is 550 DEG C), can not obtain Na4Fe0.5Mn0.5V(PO4)3The target product of molecular formula.
Comparative example 10：
Take 0.04mol sodium acetates, 0.005mol ferrous oxalates, 0.005mol manganese acetates, 0.01mol metavanadic acids by with
0.03mol ammonium dihydrogen phosphates add 60mL tetraethylene glycols and ethylene glycol (volume ratio 1 in 150mL deionized waters：1) mix molten
Liquid, is stirred at room temperature 1h, obtains mixed liquor.Then gained mixed liquor is transferred in reaction kettle, 10h is reacted at 180 DEG C and is glued
Thick glue body, then obtains presoma powder by thick gel is freeze-dried.Again by 900 DEG C under an argon atmosphere of presoma powder
Lower calcining 16h, product X RD do not have the correspondence peak shape of target product.Illustrate that calcining heat in the range of 650 DEG C~850 DEG C, is not forged
When burning the time not in the range of 6h~12h (this comparative example is 900 DEG C, 16h), Na can not be obtained4Fe0.5Mn0.5V(PO4)3Molecule
The target product of formula.
Claims (9)
1. a kind of sodium-ion battery positive material, it is characterised in that the molecular formula of the sodium-ion battery positive material is
Na4Fe0.5Mn0.5V(PO4)3, it is trigonal system, R-3c space groups, laminated structure.
2. sodium-ion battery positive material according to claim 1, it is characterised in that the sodium-ion battery positive material
Specific surface area be 3~100m2/g。
A kind of 3. preparation method of sodium-ion battery positive material as claimed in claim 1 or 2, it is characterised in that including with
Lower step：
(1) sodium source, source of iron, manganese source, vanadium source and phosphorus source are stoichiometrically dissolved in deionized water, and cause vanadium in solution
The concentration of ion is 0.05~0.1mol/L, then adds the mixed solution of tetraethylene glycol and ethylene glycol, is stirred at room temperature, must mix
Liquid, the volume ratio of tetraethylene glycol and ethylene glycol is 1 in the mixed solution of the tetraethylene glycol and ethylene glycol：(0.5~2)；
(2) mixed liquor obtained by step (1) is transferred in reaction kettle, 8~12h is reacted at 160~200 DEG C, obtains thick gel, so
Gained thick gel is freeze-dried afterwards, obtains presoma powder；
(3) 6~12h will be calcined at presoma powder obtained by step (2) under an inert atmosphere 650~850 DEG C, up to sodium ion electricity
Pond positive electrode.
4. the preparation method of sodium-ion battery positive material according to claim 3, it is characterised in that the step (1)
In, the ratio between the volume of the mixed solution of tetraethylene glycol and ethylene glycol and the volume of deionized water are 1：(1.5~3.5).
5. the preparation method of sodium-ion battery positive material according to claim 3, it is characterised in that the step (1)
In, the time being stirred at room temperature is 0.5~1.5h.
6. the preparation method of sodium-ion battery positive material according to claim 3, it is characterised in that the step (1)
In, the sodium source is the one or more in sodium acetate, sodium carbonate, sodium acid carbonate, sodium dihydrogen phosphate and disodium hydrogen phosphate；It is described
Source of iron is the one or more in ferrous oxalate, ferrous acetate, ironic citrate and ferric citrate.
7. the preparation method of sodium-ion battery positive material according to claim 3, it is characterised in that the step (1)
In, the manganese source is manganese acetate, the one or more in manganese oxalate, manganese nitrate；The vanadium source is pressed for metavanadic acid, acetylacetone,2,4-pentanedione
One or more in vanadium, vanadyl acetylacetonate, sodium vanadate；Phosphorus source for phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate,
One or more in ammonium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate.
8. the preparation method of sodium-ion battery positive material according to claim 3, it is characterised in that the step (3)
In, the inert atmosphere for argon gas, nitrogen and it is hydrogen-argon-mixed in one or more.
A kind of 9. sodium-ion battery, it is characterised in that in the sodium-ion battery using sodium as claimed in claim 1 or 2 from
Sub- cell positive material, or the sodium ion electricity being prepared using the preparation method as any one of claim 3~8
Pond positive electrode.
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