CN106784727A - A kind of polyanionic sodium-ion battery positive material and preparation method thereof - Google Patents
A kind of polyanionic sodium-ion battery positive material and preparation method thereof Download PDFInfo
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- CN106784727A CN106784727A CN201710035232.4A CN201710035232A CN106784727A CN 106784727 A CN106784727 A CN 106784727A CN 201710035232 A CN201710035232 A CN 201710035232A CN 106784727 A CN106784727 A CN 106784727A
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/366—Composites as layered products
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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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
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- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to sodium-ion battery technical field, more particularly to a kind of polyanionic sodium-ion battery positive material, positive electrode includes core layer material and is coated on the Shell Materials on core layer material surface, and core layer material is that chemical formula is Na4‑βFe2+β/2(P2O7)2Polyanionic ferric sodium pyrophosphate, wherein, 2/3≤β≤7/8, Shell Materials are carbon.Relative to prior art, the positive electrode that the present invention is provided has the 3.0V discharge platforms of stabilization, electrochemical performance, cycle performance is excellent, and high rate performance is higher, excellent heat stability, it is a kind of sodium-ion battery positive material of new generation of great prospect,, used as redox ion, price is extremely cheap, therefore its production cost can be substantially reduced for application Fe elements simultaneously.And, the electronic conductivity of the material can be significantly improved by the coated with carbon bed in polyanionic ferric sodium pyrophosphate, effectively overcome polyanionic sodium-ion battery positive material that there is the defect of relatively low electronic conductivity.
Description
Technical field
The invention belongs to sodium-ion battery technical field, more particularly to a kind of polyanionic sodium-ion battery positive material
And preparation method thereof.
Background technology
In recent years, increasingly serious with environmental problem, the further research and development of new energy is extremely urgent.Lithium from
Sub- battery as the continuable energy for most having development potentiality now, with high security, high-energy-density, long circulation life etc.
Series of advantages, has been widely used in the energy storage field of portable electric appts, electric automobile and secondary energy sources.
But due to the consumption of global lithium source extreme skewness and its rapid, high volume, lithium ion battery sets in large-scale energy storage
Standby application will necessarily be affected because of cost factor.Therefore, sodium-ion battery is because of the extremely extensive sodium source distribution in its whole world
And receive extensive research and concern in energy storage field.For positive electrode, its heat endurance, high power capacity, cycle life,
High-energy-density is its primary evaluation index.
Polyanionic compound is a series of compounds containing tetrahedron or octahedra anion structure unit
General name, three-dimensional net structure that these construction units are linked to be by strong covalent bond and formed coordination higher by other metal ions
The space for occupying so that polyanionic compound positive electrode has the crystal phase structure different with metal oxide cathode material
And the performance of the various protrusions by structures shape.At present, polyanionic lithium ion battery anode material has obtained more
Concern and research, but, research of the people to polyanionic sodium-ion battery positive material is very few.
The principal element of restriction polyanionic sodium-ion battery positive material is its relatively low electronic conductance at present
Rate.Meanwhile, for large-scale industrial production, the preparation method of existing polyanionic positive electrode is mainly sol-gel
Method, hydro-thermal method and high temperature solid-state method etc..Wherein, sol-gel method craft is extremely complex, and organic solvent price used is more held high
It is expensive；Hydro-thermal method energy consumption is larger, and complicated whard to control into phase process, equipment amount needed for batch production is larger；High temperature solid-state method is present
Raw material mixes uneven shortcoming, causes synthesized material uniformity poor, and required high temperature is more long into the phase time, required energy
Consumption is higher.Additionally, above-mentioned several preparation methods are required to carry out post processing cladding carbon-coating, the production cycle is more long.
In view of this, it is necessory to provide a kind of polyanionic sodium-ion battery positive material and preparation method thereof, should
Positive electrode has the polyanionic sodium pyrophosphate iron of carbon-coating for Surface coating, and the positive electrode has the 3.0V electric discharges of stabilization flat
Platform, close to the specific discharge capacity of 110mAh/g, excellent heat endurance, the preparation method low cost is capable of achieving large-scale production.
The content of the invention
An object of the present invention is：In view of the shortcomings of the prior art, a kind of polyanionic sodium ion electricity is provided
Pond positive electrode and preparation method thereof, the positive electrode has the polyanionic sodium pyrophosphate iron of carbon-coating for Surface coating, and this is just
Pole material has the 3.0V discharge platforms of stabilization, close to the specific discharge capacity of 110mAh/g, excellent heat endurance, the preparation side
Method low cost, is capable of achieving large-scale production.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
A kind of polyanionic sodium-ion battery positive material, the positive electrode includes core layer material and is coated on described
The Shell Materials on core layer material surface, the core layer material is that chemical formula is Na4-βFe2+β/2(P2O7)2Polyanion formed coke phosphorus
Sour ferrisodium, wherein, 2/3≤β≤7/8, the Shell Materials are carbon.
The positive electrode has anorthic crystal structure, belongs to P1 space groups.When β=2/3, the chemical formula of the material is
Na3.32Fe2.34(P2O7)2/C；When β=7/8, the chemical formula of the material is Na3.12Fe2.44(P2O7)2/C；The shell of the material
Material is carbon, and the shell still keeps good after being circulated through 300 times.
Improved as one kind of polyanionic sodium-ion battery positive material of the present invention, the thickness of the Shell Materials is
2nm-100nm。
Improved as one kind of polyanionic sodium-ion battery positive material of the present invention, the particle diameter of the positive electrode is
200nm-1μm。
Relative to prior art, the positive electrode that the present invention is provided includes core layer material and is coated on the core layer material table
The Shell Materials in face, core layer material is that chemical formula is Na4-βFe2+β/2(P2O7)2Polyanionic ferric sodium pyrophosphate, wherein, 2/3
≤ β≤7/8, Shell Materials are carbon, and the positive electrode has the 3.0V discharge platforms of stabilization, and electrochemical performance is (close
The specific discharge capacity of 110mAh/g), cycle performance it is excellent (under 0.5C multiplying powers circulate 300 its capability retentions 92% with
On), high rate performance is (1100 capability retentions close to 90% are circulated under 5C multiplying powers) higher, and excellent heat stability is a kind of pole
The sodium-ion battery positive material of new generation of tool prospect, while using Fe elements as redox ion, price is extremely cheap,
Therefore its production cost can be substantially reduced.And, can be with bright by the coated with carbon bed in polyanionic ferric sodium pyrophosphate
The aobvious electronic conductivity for improving the material, effectively overcomes polyanionic sodium-ion battery positive material to have relatively low electricity
The defect of electron conductivity.
It is another object of the present invention to provide a kind of preparation method of polyanionic sodium-ion battery positive material,
At least comprise the following steps：
The preparation of A, precursor powder：According to chemical formula Na4-βFe2+β/2(P2O7)2Metering weighs sodium source, source of iron and phosphorus source,
And carbon source and antioxidant are weighed, wherein, the quality accounting of the antioxidant is 1%-5%, then by sodium source, source of iron, phosphorus
Source, carbon source and antioxidant are placed in the sand milling tank of sand mill, be subsequently adding grinding aid and pearl is sanded, then the sand milling tank is placed in
It is sanded in high energy bead mill, powder granule is uniformly refined, precursor powder is obtained after drying；
The calcination processing of B, precursor powder：The precursor powder of gained in step A is positioned over protective gas atmosphere
In the box reacting furnace for enclosing, first the pre-burning 3h-6h at 340 DEG C -360 DEG C, cold after then calcining 6h-24h at 580 DEG C -620 DEG C
But, positive electrode is obtained final product.Wherein, protective gas is nitrogen or argon gas.
Improved as a kind of the of preparation method of polyanionic sodium-ion battery positive material of the present invention, the sodium source is
At least one in sodium carbonate, sodium acetate, sodium acid carbonate and sodium oxalate；The source of iron is in ferric acetate, ferric oxalate and ferric carbonate
At least one；Phosphorus source is ammonium dihydrogen phosphate and/or diammonium hydrogen phosphate, and the carbon source is citric acid, stearic acid and sucrose
In at least one, the antioxidant be ascorbic acid, D-araboascorbic acid and ascorbyl palmitate at least one
Kind.
Improved as a kind of the of preparation method of polyanionic sodium-ion battery positive material of the present invention, the grinding aid
It is at least one in ethanol, acetone and ethylene glycol.
Improved as a kind of the of preparation method of polyanionic sodium-ion battery positive material of the present invention, the sand milling pearl
It is 1 with the mass ratio of raw material：(3-7), the raw material includes sodium source, source of iron, phosphorus source, carbon source and antioxidant.
Improved as a kind of the of preparation method of polyanionic sodium-ion battery positive material of the present invention, the sand milling tank
Be assembled under protective gas atmosphere and carry out, the protective gas is nitrogen or argon gas.
Improved as a kind of the of preparation method of polyanionic sodium-ion battery positive material of the present invention, the high energy sand
The rotating speed of grinding machine is 800-1200 revs/min, and run time is 6h-24h.
Improved as a kind of the of preparation method of polyanionic sodium-ion battery positive material of the present invention, when drying, will
The sand milling tank for completing to be sanded is opened in the glove box full of protective gas, and then the sand milling tank is placed in vacuum drying chamber
Be vacuum dried 10h-48h at 60 DEG C -100 DEG C, then by sub-sieve vibrator screening dried, finely dispersed precursor
End.
Relative to prior art, the preparation method at least has the advantages that：
First, polyanionic sodium-ion battery positive material Na prepared by the present invention4-βFe2+β/2(P2O7)2/C(2/3≤β
≤ 7/8), have the advantages that uniform grain diameter tiny (200nm-1 μm), particle diameter distribution, good product consistency, purity are high, and
And carbon-coating is uniform.
Second, polyanionic sodium-ion battery positive material heat endurance prepared by the present invention is good, and cycle performance is excellent,
Discharge capacity and high rate performance are higher.
3rd, the preparation method has the effect of carbon coating in situ, is not required to carry out subsequent treatment, and through 300 circulation shells
Layer material is still remained intact.
4th, the preparation method first obtains precursor powder using high energy sand-blast, then only with one-step calcination, technique stream
Journey is simple, and equipment investment is few, and serialization degree is high, and low production cost is conducive to industrialized production.
Brief description of the drawings
With reference to the accompanying drawings and detailed description, the present invention and its Advantageous Effects are described in detail.
Fig. 1 is Na prepared by embodiment 13.32Fe2.34(P2O7)2Powder obtained by the synchrotron radiation X-ray source test of/C-material
Last diffraction spectrogram and refine result (refine is carried out based on GSAS-II softwares).
Fig. 2 is Na prepared by embodiment 23.12Fe2.44(P2O7)2Powder obtained by the synchrotron radiation X-ray source test of/C-material
Last diffraction spectrogram and refine result (refine is also carried out based on GSAS-II softwares).
Fig. 3 is the refine result schematic diagram that embodiment 1 prepares resulting materials.
Fig. 4 is the refine result schematic diagram that embodiment 2 prepares resulting materials.
Fig. 5 is the scanning electron microscope (SEM) photograph that embodiment 1 prepares resulting materials.
Fig. 6 is the scanning transmission electron microscope figure that embodiment 1 prepares resulting materials.
Fig. 7 is the scanning transmission electron microscope figure that embodiment 2 prepares resulting materials.
Fig. 8 is the grain size distribution that embodiment 3 prepares resulting materials.
Fig. 9 is the thermal multigraph that embodiment 3 prepares resulting materials.
Figure 10 is the grain size distribution that embodiment 1 prepares resulting materials.
Figure 11 is 0.5C (the 1C=120mA g that embodiment 2 prepares resulting materials-1) the circulation scanning transmission electronics of 300 times
Microscope figure.
Figure 12 is that embodiment 1 prepares the circle of 0.5C circulations 300 of resulting materials and the discharge capacity figure of the circle of 5C circulations 1100.
Figure 13 is the high rate performance figure that embodiment 2 prepares resulting materials.
Figure 14 is the Mossbauer spectrogram that embodiment 1 prepares resulting materials.
Figure 15 is the cyclic voltammetry curve of first five circle that embodiment 3 prepares resulting materials.
Figure 16 is the energy dispersion X-ray spectrometer test result after embodiment 3 prepares the circle of circulation 1100 of resulting materials
And surface sweeping Electronic Speculum result.
Figure 17 is constant current Intermittent Titration test result and its corresponding the sodium ion diffusion that embodiment 1 prepares resulting materials
The result of calculation of coefficient.
Specific embodiment
Technical scheme, but protection scope of the present invention not limited to this are illustrated with specific embodiment below.
Embodiment 1
A kind of polyanionic sodium-ion battery positive material is present embodiments provided, the positive electrode includes core layer material
With the Shell Materials for being coated on core layer material surface, core layer material is that chemical formula is Na3.32Fe2.34(P2O7)2Polyanionic
Ferric sodium pyrophosphate, Shell Materials are carbon.The positive electrode has anorthic crystal structure, belongs to P1 space groups.The thickness of Shell Materials
It is 2nm-100nm to spend.The particle diameter of positive electrode is 200nm-1 μm.
Its preparation method at least comprises the following steps：
A, prepare precursor powder
According to chemical formula Na3.32Fe2.34(P2O7)2Proportioning, weigh Na2CO3(analyze pure, purity>99.5%) 176.83g
(1.66mol), FeC2O4(analyze pure, purity>98%) 343.50g (2.34mol), NH4H2PO4(analyze pure, purity>98%)
469.51g (4mol), and weigh stearic acid (pure, the purity of analysis>99%) 86.20g (0.3mol), (analysis is pure, pure for ascorbic acid
Degree>99%) 53.80g (5wt%), ethanol (analyzes pure, purity>99.5%) then 35mL adds above-mentioned material as grinding aid
Enter to containing zirconium oxide sand milling pearl, (5.59kg is 5 with material ratio:1) in sand milling tank, after the sand milling tank is placed in glove box
With argon gas is as inert atmosphere protection and completes assembling, then the sand milling tank is placed in high energy bead mill it is sanded, setting is high
The rotating speed of energy sand mill is 800 revs/min, total run time 24h, then the sand milling tank for completing will be sanded in the gloves full of argon gas
Opened in case, after be placed in vacuum drying chamber 24h be vacuum dried at 80 DEG C, then shaken with the supporting sub-sieve of pearl is sanded with zirconium oxide
Dynamic device obtains dry, finely dispersed precursor powder.
B, pre-burning and calcining
Above-mentioned dried precursor powder is placed in box reacting furnace, and is protected with nitrogen, furnace pressure is normal
Pressure.Calcined temperature is set in 340 DEG C, and heating rate is 2 DEG C/min, soaking time 6h.Then proceed to be warming up to 580 DEG C, heat up
5 DEG C/min of speed, soaking time 24h.Normal temperature is naturally cooled to afterwards.Above-mentioned all processes are entered under nitrogen atmosphere protection
OK, the grey powder as Na for finally giving3.32Fe2.34(P2O7)2/ C positive electrode material.
Obtained by the present embodiment synchronous material radiation X ray source test obtained by powder diffractogram and refine result see figure
1, specific occupy-place information is shown in Table 1, and refine result schematic diagram is shown in Fig. 3, it follows that the material has anorthic crystal structure, belongs to
P1 space groups.Its pattern and carbon coating situation are shown in Fig. 5 and Fig. 6.As shown in Figure 5, the material is in granular form, as can be seen from Figure 6, its table
Face is formed with a thin layer of clad.
Table 1：The specific occupy-place of refine of the resulting materials of embodiment 1 and percentage result
The grain size distribution of the present embodiment resulting materials is shown in Figure 10, as seen from Figure 10 material manufactured in the present embodiment
Particle diameter distribution is narrow.Its Mossbauer spectrogram is shown in Figure 14, and Mossbauer effect is related to solid center excitation state and ground state level
Between resonant transition, therefore the level structure of core decides spectral shape and all parameters, and the level structure of resonant nucleus is decided by
Chemical environment residing for core, so Mo＆4＆ssbauer spectrum extremely can delicately reflect the change of resonating atoms core surrounding chemical environment；
And the change of resonating atoms core surrounding chemical environment can be obtained, oxidation state, spin state, the change of resonating atoms can be obtained by it
The information about solid microstructure such as property of key is learned, but, there was only a small number of Mossbauer core such as 57Fe and 119Sn at present
Abundant application is obtained, therefore the material of the iron content that the present embodiment is prepared can have been analyzed with Mossbauer spectrogram.
Material to the present embodiment carries out charge-discharge performance test：In mass ratio 80:13:7 weigh it is manufactured in the present embodiment
Na3.32Fe2.34(P2O7)2/ C positive electrode material, acetylene black and Kynoar (PVDF), are added in appropriate 1-METHYLPYRROLIDONE
It is tuned into after slurry and is coated on aluminium foil that (surface density is in 2~3mg cm-2), it is vacuum dried (vacuum 0.094MPa) at 120 DEG C
12h, then cuts into positive plate and in carrying out compressing tablet under 20MPa.With metallic sodium piece as negative pole, the life of SIGMA-ALDRICH companies
The glass fibre of product is barrier film, and the button cell of model CR2032 is assembled into the glove box full of argon gas.1.5~
Electrochemical property test is carried out in the voltage range of 4.0V, as a result shows that positive electrode manufactured in the present embodiment has more excellent
Chemical property, in 0.1C (1C=120mA g-1) current density under can obtain 107.4mAh g-1Electric discharge specific volume
Amount.Meanwhile, under the discharge-rate of 0.5C, its capability retention is up to 92.3% after the circle of circulation 300；In the discharge-rate of 5C
Under, capability retention still can reach 89.6% after circulating 1100 times.Its cycle performance is shown in Figure 12, as seen from Figure 12, its tool
There is very excellent cycle performance.Embodiment 1 prepares the constant current Intermittent Titration test result and its corresponding sodium of resulting materials
As shown in figure 17, the sodium ion diffusion coefficient of the material is larger as seen from Figure 17 for the result of calculation of ionic diffusion coefficient.
Embodiment 2
A kind of polyanionic sodium-ion battery positive material is present embodiments provided, the positive electrode includes core layer material
With the Shell Materials for being coated on core layer material surface, core layer material is that chemical formula is Na3.12Fe2.44(P2O7)2Polyanionic
Ferric sodium pyrophosphate, Shell Materials are carbon.The positive electrode has anorthic crystal structure, belongs to P1 space groups.The thickness of Shell Materials
It is 2nm-100nm to spend.The particle diameter of positive electrode is 200nm-1 μm.
Its preparation method at least comprises the following steps：
A, prepare precursor powder
According to chemical formula Na3.12Fe2.44(P2O7)2Proportioning, weigh Na2C2O4(analyze pure, purity>99.5%) 210.09g
(1.56mol), FeCO3(analyze pure, purity>98%) 288.45g (2.44mol), (NH4)2HPO4(analyze pure, purity>98%)
539.02g (4mol), and weigh citric acid (pure, the purity of analysis>99%) 58.23g (0.3mol), (analysis is pure, pure for ascorbic acid
Degree>99%) 32.88g (3wt%), acetone (analyzes pure, purity>99.5%) then 35mL adds above-mentioned material as grinding aid
Enter to containing zirconium oxide sand milling pearl, (5.69kg is 5 with material ratio:1) in sand milling tank, after the sand milling tank is placed in glove box
With argon gas is as inert atmosphere protection and completes assembling, then the sand milling tank is placed in high energy bead mill it is sanded, setting is high
1200 revs/min of the rotating speed of energy sand mill, total run time 6h, then the sand milling tank for completing will be sanded in the glove box full of argon gas
Middle opening, after be placed in vacuum drying chamber 6h be vacuum dried at 120 DEG C, then vibrated with the supporting sub-sieve of pearl is sanded with zirconium oxide
Device obtains dry, finely dispersed precursor powder.
B, pre-burning and calcining：Above-mentioned dried precursor powder is placed in box reacting furnace, and is protected with nitrogen,
Furnace pressure is normal pressure.Calcined temperature is set in 350 DEG C, 1.5 DEG C/min of heating rate, soaking time 3h.Then proceed to heat up
To 600 DEG C, 3 DEG C/min of heating rate, soaking time 6h.Normal temperature is naturally cooled to afterwards.Above-mentioned all processes are in nitrogen gas
Carried out under atmosphere protection.The grey powder as Na for finally giving3.12Fe2.44(P2O7)2/ C positive electrode material.
Obtained by the present embodiment synchronous material radiation X ray source test obtained by powder diffractogram and refine result see figure
2, refine result schematic diagram is shown in Fig. 4, it follows that the material has anorthic crystal structure, belongs to P1 space groups.Its carbon coating feelings
Condition is shown in and Fig. 7 that as can be seen from Figure 7, its surface is formed with a thin layer of clad.
The scanning transmission electron microscope figure of 300 times is circulated under material 0.5C discharge current densities obtained by the present embodiment such as
Shown in Figure 11, as seen from Figure 11, after experiencing 300 circulations, the carbon-coating of the material is remained in that completely, the multiplying power of the material
Performance map is shown in Figure 13, and as seen from Figure 13, material manufactured in the present embodiment has excellent high rate performance.
Embodiment 3
A kind of polyanionic sodium-ion battery positive material is present embodiments provided, the positive electrode includes core layer material
With the Shell Materials for being coated on core layer material surface, core layer material is that chemical formula is Na3.22Fe2.39(P2O7)2Polyanionic
Ferric sodium pyrophosphate, Shell Materials are carbon.The positive electrode has anorthic crystal structure, belongs to P1 space groups.The thickness of Shell Materials
It is 2nm-100nm to spend.The particle diameter of positive electrode is 200nm-1 μm.
Its preparation method at least comprises the following steps：
A, prepare precursor powder
According to chemical formula Na3.22Fe2.39(P2O7)2The proportioning of/C, weighs CH3COONa (analyzes pure, purity>99%)
266.71g (3.22mol), Fe (CH3COO)2(analyze pure, purity>98%) 424.18g (2.39mol), (NH4)2HPO4(analysis
It is pure, purity>98%) 539.02g (4mol), and weigh sucrose (pure, the purity of analysis>99%) 102.69g (0.3mol), Vitamin C
Acid (analyzes pure, purity>99%) 13.326g (1wt%), ethylene glycol (analyzes pure, purity>99.5%) 35mL is used as grinding aid.
It is subsequently adding to containing zirconium oxide sand milling pearl, (6.88kg is 5 with material ratio:1) in sand milling tank, after the sand milling tank is placed in hand
With argon gas is as inert atmosphere protection and completes assembling in casing.The sand milling tank is placed in high energy bead mill is again sanded,
1000 revs/min of the rotating speed of high energy bead mill, total run time 15h are set, then the sand milling tank for completing will be sanded full of argon gas
Glove box in open, after be placed in vacuum drying chamber 15h be vacuum dried at 100 DEG C, it is then supporting with zirconium oxide pearl being sanded
Sub-sieve vibrator obtain dry, finely dispersed precursor powder.
B, pre-burning and calcining：Above-mentioned dried precursor powder is placed in box reacting furnace, and is protected with nitrogen,
Furnace pressure is normal pressure.Calcined temperature is set in 360 DEG C, 1 DEG C/min of heating rate, soaking time 4.5h.Then proceed to heat up
To 620 DEG C, 2 DEG C/min of heating rate, soaking time 15h.Normal temperature is naturally cooled to afterwards.Above-mentioned all processes are in nitrogen
Carried out under atmosphere protection.The grey powder as Na for finally giving3.22Fe2.39(P2O7)2/ C positive electrode material.
The grain size distribution of the positive electrode obtained by the present embodiment as shown in figure 8, its thermal multigraph is shown in Fig. 9, its first five circle
Cyclic voltammetry curve is shown in Figure 15, energy dispersion X-ray spectrometer test result and surface sweeping Electronic Speculum result after its circle of circulation 1100
Figure 16 is seen, it follows that after circulation 1100, the carbon-coating of material surface is still consolidated.
Result above shows in Na4-βFe2+β/2(P2O7)2Material in the range of the β value of/C (2/3≤β≤7/8) has more
Excellent chemical property.
Certainly, antioxidant can also use D-araboascorbic acid and ascorbic acid palm in addition to using ascorbic acid
Acid esters replaces, as long as pearl is sanded with the mass ratio of raw material 1：In the range of (3-7).
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in specific embodiment disclosed and described above, to of the invention
Some modifications and changes should also be as falling into scope of the claims of the invention.Although additionally, being used in this specification
Some specific terms, but these terms are merely for convenience of description, do not constitute any limitation to the present invention.
Claims (10)
1. a kind of polyanionic sodium-ion battery positive material, it is characterised in that：The positive electrode include core layer material and
The Shell Materials on the core layer material surface are coated on, the core layer material is that chemical formula is Na4-βFe2+β/2(P2O7)2Poly- the moon
Ionic ferric sodium pyrophosphate, wherein, 2/3≤β≤7/8, the Shell Materials are carbon.
2. polyanionic sodium-ion battery positive material according to claim 1, it is characterised in that：The Shell Materials
Thickness be 2nm-100nm.
3. polyanionic sodium-ion battery positive material according to claim 1, it is characterised in that：The positive electrode
Particle diameter be 200nm-1 μm.
4. a kind of preparation method of polyanionic sodium-ion battery positive material, it is characterised in that at least comprise the following steps：
The preparation of A, precursor powder：According to chemical formula Na4-βFe2+β/2(P2O7)2Metering weighs sodium source, source of iron and phosphorus source, and claims
Carbon source and antioxidant are taken, wherein, the quality accounting of the antioxidant is 1%-5%, then by sodium source, source of iron, phosphorus source, carbon
Source and antioxidant are placed in the sand milling tank of sand mill, be subsequently adding grinding aid and pearl is sanded, then the sand milling tank is placed in into high energy
It is sanded in sand mill, precursor powder is obtained after drying；
The calcination processing of B, precursor powder：The precursor powder of gained in step A is positioned over protective gas atmosphere
In box reacting furnace, first the pre-burning 3h-6h at 340 DEG C -360 DEG C, cools down after then calcining 6h-24h at 580 DEG C -620 DEG C,
Obtain final product positive electrode.
5. the preparation method of polyanionic sodium-ion battery positive material according to claim 4, it is characterised in that：Institute
It is at least one in sodium carbonate, sodium acetate, sodium acid carbonate and sodium oxalate to state sodium source；The source of iron be ferric acetate, ferric oxalate and
At least one in ferric carbonate；Phosphorus source is ammonium dihydrogen phosphate and/or diammonium hydrogen phosphate, and the carbon source is citric acid, tristearin
At least one in acid and sucrose, the antioxidant is in ascorbic acid, D-araboascorbic acid and ascorbyl palmitate
At least one.
6. the preparation method of polyanionic sodium-ion battery positive material according to claim 4, it is characterised in that：Institute
It is at least one in ethanol, acetone and ethylene glycol to state grinding aid.
7. the preparation method of polyanionic sodium-ion battery positive material according to claim 4, it is characterised in that：Institute
It is 1 to state and pearl is sanded with the mass ratio of raw material：(3-7), the raw material includes sodium source, source of iron, phosphorus source, carbon source and antioxidant.
8. the preparation method of polyanionic sodium-ion battery positive material according to claim 4, it is characterised in that：Institute
State and being assembled under protective gas atmosphere for tank is sanded carries out, the protective gas is nitrogen or argon gas.
9. the preparation method of polyanionic sodium-ion battery positive material according to claim 4, it is characterised in that：Institute
The rotating speed of high energy bead mill is stated for 800-1200 revs/min, run time is 6h-24h.
10. the preparation method of polyanionic sodium-ion battery positive material according to claim 4, it is characterised in that：
When drying, the sand milling tank for completing to be sanded is opened in the glove box full of protective gas, the sand milling tank is then placed in vacuum
It is vacuum dried 10h-48h in drying box at 60 DEG C -100 DEG C, then is dried, be uniformly dispersed by the screening of sub-sieve vibrator
Precursor powder.
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