CN106450295A - Sodium-ion battery positive electrode material Na3Fe2(PO4)3 and preparation method thereof - Google Patents
Sodium-ion battery positive electrode material Na3Fe2(PO4)3 and preparation method thereof Download PDFInfo
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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
- 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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- 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 relates to a sodium-ion battery positive electrode material Na3Fe2(PO4)3 and a preparation method thereof. The preparation method is a solid-phase sintering method or a sol-gel method, wherein the solid-phase sintering method comprises the following steps of mixing an iron salt, a sodium salt and a phosphate, enabling the mole ratio of three ions of Fe<3+>, Na<+> and PO4<3+> to be 2:3:3, performing calcination in an air atmosphere to obtain a monoclinic Na3Fe2(PO4)3 positive electrode material; and the sol-gel method comprises the following steps of (1) weighing and dissolving Fe(NO<3>)<3>.9H<2>O and CH3COONa in deionized water, maintaining a stirring condition, adding citric acid, simultaneously adding NH4H2PO4 and polyvinyl alcohol, and performing stirring, heating and water bath reaction to obtain sol; and (2) drying the sol obtained in the step (1) to obtain gel, and performing calcination in the air atmosphere to obtain a pure-phase monoclinic mesopore Na3Fe2(PO4)3 positive electrode material. Compared with the prior art, the preparation method has the advantages of simple and practical synthesis process and the like, and the electrochemical performance of the positive electrode material is excellent.
Description
Technical field
The present invention relates to sodium-ion battery field, especially relate to a kind of sodium-ion battery positive material Na3Fe2(PO4)3
And preparation method thereof.
Background technology
The transition consumption of the increasingly serious and fossil energy of environmental problem, secondary cell is as a kind of energy-storage system of cleaning
Play the part of more and more important role with dynamical system in human social development.On the one hand, secondary cell is as the power of automobile
System replaces traditional internal combustion engine largely can slow down consuming excessively and greenhouse gas emission of fossil energy.Phase
Comparison is traditional to be applied to secondary cell on portable digital product, and electrokinetic cell typically requires the features such as high power, Large Copacity.Separately
On the one hand, secondary cell, as power energy storage unit, also has important application prospect in terms of new-energy grid-connected, intelligent grid.
For the secondary cell of energy storage, battery is typically required to have the features such as low cost and long circulation life.In the past few decades
In, lithium ion battery is considered most possible large-scale application in new-energy automobile and electricity because of its excellent chemical property
The secondary cell of power energy storage.However, lithium source reserves are limited on the earth, the price of lithium metal can be with the big rule of lithium ion battery
Mould is applied and is gradually increasing.The raising of cost will certainly hinder its large-scale application.
It is in the sodium of same main group with lithium, have similar chemical property to lithium.Sodium-ion battery is had with lithium ion battery
Similar principle it is important that sodium reserves on earth are far above lithium.At present, the correlational study of sodium-ion battery is again
Paid attention to by Many researchers.Research work with regard to sodium ion electrode pole material is reported in succession, such as NaxCoO2, Na0.44MnO2,
Na0.6MnO2, NaCrO2, NaxVO2, Na3V2(PO4)3, Na3V2(PO4)2F3, Na3V2O2(PO4)2F, Na2FePO4F, NaFeF3Deng,
But the performance of these positive electrodes still can not meet the requirement of the industrial applications of sodium-ion battery.Develop preferable electrode
Material is the industrialized key of sodium-ion battery.
Iron-based phosphate cathode material because raw material sources extensively, cheap, environment-protecting asepsis and widely studied.From
The LiFePO of olivine structural from reported first such as Goodenough4Since lithium ion battery electrode material, people couple
LiFePO4Expand substantial amounts of research work, current olivine-LiFePO4Positive electrode large-scale application in commercialization
Lithium ion battery.But, the iron-based phosphate sodium-ion battery material of excellent performance need to develop further, studies.
Content of the invention
The purpose of the present invention is exactly to overcome the defect of above-mentioned prior art presence just to provide a kind of sodium-ion battery
Pole material Na3Fe2(PO4)3And preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of sodium-ion battery positive material Na3Fe2(PO4)3, described positive electrode is monoclinic crystal material, its chemistry
Formula is Na3Fe2(PO4)3.
Sodium-ion battery positive material Na3Fe2(PO4)3Preparation method, comprise the following steps：
Iron salt, sodium salt is taken to mix with phosphate so that Fe3+、Na+And PO4 3+The mol ratio of three kinds of ions is 2:3:3, in sky
Calcine under gas atmosphere, that is, obtain monocline Na3Fe2(PO4)3Positive electrode.
Preferably, described iron salt is FePO4Or Fe2O3；
Described sodium salt is CH3COONa、Na3PO4Or NaCO3；
Described phosphate is FePO4、Na3PO4Or NH4H2PO4In at least one.
Preferably, the process step of mixing is：First dry grind in planetary ball mill 3-5h, then liquid phase ball milling 3-5h,
Finally it is dried and remove liquid phase.
Preferably, the temperature of calcining is 500～700 DEG C, and calcination time is 8-12h.
Sodium-ion battery positive material Na3Fe2(PO4)3Preparation method, can also comprise the following steps：
(1) weigh Fe (NO3)3·9H2O and CH3COONa is dissolved in deionized water, is kept stirring for condition, adds citric acid,
It is simultaneously introduced NH again4H2PO4And polyvinyl alcohol, agitating heating, water-bath, obtain colloidal sol；
(2) obtain gel after the colloidal sol that step (1) obtains being dried, under air atmosphere, calcining, that is, obtain pure phase list
Tiltedly mesoporous Na3Fe2(PO4)3Positive electrode.
Preferably, the Fe (NO adding in step (1)3)3·9H2O、NH4H2PO4And CH3COONa meets：Fe3+、Na+With
PO4 3+The mol ratio of three kinds of ions is 2:3:3.
Preferably, with every 0.03mol CH3COONa counts, and the addition of citric acid is 8～12g, and the concentration of polyvinyl alcohol is
5wt%, its addition is 4-6mL.
Preferably, in step (1), the temperature of water-bath is 50～70 DEG C, and the response time is not less than 10h.
Preferably, in step (2), the temperature of calcining is 500～700 DEG C, and the time is 1-4h.
In the preparation process of sol-gal process, material produces principle mesoporous in a large number and is：At gel heat in air atmosphere
Reason, creates substantial amounts of meso-hole structure in calcination process.Exist in calcination process, chelating agen glucose citric acid molecule is comparing
Carbonization is occurred to form carbon at a temperature of relatively low, the hard template that the carbon of formation is equivalent to.With the raising further of calcining heat,
Carbon oxidation Decomposition in air atmosphere forms carbon dioxide, and this process defines substantial amounts of meso-hole structure.
Compared with prior art, the present invention has advantages below：
(1) pass through solid sintering technology and synthesize Na with sol-gal process3Fe2(PO4)3Positive electrode, electrochemical performance,
The positive electrode made especially with sol-gel process, sintering time, compared to solid-phase sintering synthetic method, greatly shortens, and
In material, a large amount of meso-hole structures occur, specific surface area significantly increases, when as sodium-ion battery positive material, chemical property
Excellent.
(2) preparation method is simple, is easy to large-scale application,
Brief description
Fig. 1 is the Na being thermally treated resulting in using Solid phase synthesis and under condition of different temperatures3Fe2(PO4)3XRD figure
Spectrum；
Fig. 2 is the Na being thermally treated resulting in using Solid phase synthesis and under condition of different temperatures3Fe2(PO4)3Scanning electricity
Mirror photo；
The Na that Fig. 3-1 and Fig. 3-2 is using Solid phase synthesis and is thermally treated resulting under condition of different temperatures3Fe2
(PO4)3Chemical property picture；
Fig. 4 is the Na of the Solid phase synthesis using different material3Fe2(PO4)3XRD spectrum；
Fig. 5 is the Na of the Solid phase synthesis using different material3Fe2(PO4)3Stereoscan photograph；
Fig. 6-1 and Fig. 6-2 is the Na of the Solid phase synthesis using different material3Fe2(PO4)3Chemical property figure
Piece；
Fig. 7 is the mesoporous Na using sol-gel process synthesis3Fe2(PO4)3XRD spectrum；
Fig. 8 is the mesoporous Na using sol-gel process synthesis3Fe2(PO4)3Scanning electron microscope and high power transmission electricity
Mirror photo；
Fig. 9 is the mesoporous Na of monocline3Fe2(PO4)3Chemical property figure as sodium-ion battery positive material.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
1. the present invention is so the medicine being related to is all that analysis is pure；
2. the structure of material and morphology characterization in the present invention：X-ray diffraction adopts D8ADVANCE (Brute, Germany), XRD
Analysis condition is light Cu K α radiation, tube voltage 40KV, and scanning speed is 0.01 °/s, and sweep limitss are 10 °～90 °.N2Inhale de-
Attached curve adopts the BET fully-automatic analyzer (Quantachrome Instruments) that Kang Ta instrument company of the U.S. provides.Sweep
Retouch Electronic Speculum and the model of projection Electronic Speculum is respectively JSM-7800F and JEM-2100F (Hitachi, Ltd, Japan).
3. battery assembling：By graphite and carbon black according to mass ratio 4：6 ratio uniform mixing, as conductive agent.And with work
Property material according to mass ratio be 30：62 ratio mixing, using planetary ball mill by mixture with the rotating speed of 600rpm
Dry grinding 2h, ratio of grinding media to material is 10：1, add suitable alcohols as medium wet grinding 2h, take out ball milling pearl, put into baking oven at 120 DEG C
Dry 12h.The positive electrode dried using electronic balance precise 15mg, using ethanol as medium, by 92：8 mass ratio
Material and polyfluortetraethylene of binding element are ground in agate mortar.Material after grinding is coated uniformly on and is a little welded in anode cover
On, 0.24mm is thick, on the circular stainless (steel) wire wire side of a diameter of 14mm.Anode cover is put in 120 DEG C of baking ovens 4h is dried, then
With jack, positive plate is flattened, pressure is 2Mpa, the time is 3min.The positive plate of compacting is placed into baking oven do further
Dry, temperature is 120 DEG C, and the time is 8h.Electrolyte is 1mol L-1NaClO4, solvent is using volume ratio 1：1 ethylene carbonate
(EC) and dimethyl carbonate (DMC) mixed solvent.Metallic sodium piece as auxiliary electrode and participates in electrode, using glass felt fiber
As battery diaphragm, electro-chemical test adopts R2016 type button cell.Battery is assembled in and enters full of in the glove box of high-purity argon
OK.
4. constant current charge-discharge test adopts Wuhan blue electricity battery test system CT2001A.The discharge and recharge electricity of sodium-ion battery
It is 1.5～3.5V between nip, charging and discharging currents density is 20mA g-1.Charging and discharging currents size and specific discharge capacity are pressed often
1molNa3Fe2(PO4)3Two 2mol electronics of gain and loss calculate.Cyclic voltammetric adopts Shanghai occasion China CHI660C electrochemical workstation to survey
Examination, voltage range is 1.5～3.5V (vs.Na/Na+).All of electro-chemical test is carried out under the conditions of 25 DEG C of steady temperature.
Embodiment 1
Synthesize monocline Na using simple solid-phase synthesis3Fe2(PO4)3.FePO with Co deposited synthesis4As forerunner
Body, with anhydrous CH3COONa、NH4H2PO4In molar ratio 2:3:1 ball milling mixing.First solid-phase ball milling 4h, then liquid phase ball milling 4h (wine
Essence is as ball-milling medium, planetary ball mill).The mixture obtaining is dried 12h for 80 DEG C in drying baker, and ethanol volatilizees completely.
The pressed powder obtaining 600 DEG C of calcining 10h in tube furnace, using air atmosphere (airflow rate 20mL min-1).Obtain monocline
Na3Fe2(PO4)3- 600 materials.
Embodiment 2
The present embodiment compared with Example 1, except calcining heat is 500 DEG C, other conditions and step all with embodiment 1,
Finally give a kind of sodium-ion battery positive material Na3Fe2(PO4)3-500.
Embodiment 3
Except calcining heat is 700 DEG C, other conditions and step, all with embodiment 1, finally give a kind of sodium-ion battery
Positive electrode Na3Fe2(PO4)3-700.
Sodium-ion battery positive material Na that embodiment 1-3 obtains3Fe2(PO4)3- 500, Na3Fe2(PO4)3- 600,
Na3Fe2(PO4)3- 700 XRD spectrum is as shown in Figure 1.XRD result shows, the Na of 500 DEG C of heat treatments3Fe2(PO4)3Not tangible
Become complete crystal structure, only a few diffraction maximum.When temperature rises to 600 DEG C, the material obtaining is the Na of monocline3Fe2
(PO4)3, with standard Na3Fe2(PO4)3XRD spectrum can be good at correspond to.The Na obtaining of same 700 DEG C of heat treatments3Fe2
(PO4)3Structure is corresponding be also monocline Na3Fe2(PO4)3.Can be seen that at heat from the stereoscan photograph of Fig. 2
The raising of reason temperature, the Na obtaining3Fe2(PO4)3There is serious reuniting and obvious grain growth.These three materials divide
Not as sodium-ion battery positive material, chemical property is as shown in Fig. 3-1 and Fig. 3-2.Different heat treatment temperatures shows
Different chemical properties.The Na of 500 DEG C of heat treatments3Fe2(PO4)3It is 20mA g in electric current density-1Under the conditions of first electric discharge ratio
Capacity is 88.6mAh g-1, after circulating 30 times, 82.7mAh g can be kept-1Capacity, charging and discharging curve and unformed FePO4
Charging and discharging curve be similar to, do not show obvious charge and discharge platform.The Na of 600 DEG C of heat treatments3Fe2(PO4)3Close in electric current
Spend for 20mA g-1Under the conditions of first discharge specific capacity be 82.5mAh g-1Capacity, circulation 30 times after can keep
81.7mAh g-1, occur in that obvious charging/discharging voltage platform near voltage 2.5V.When heat treatment temperature reaches 700 DEG C, first
Specific discharge capacity is 68.2mAh g-1, after circulating 30 times, 68.5mAh g can be kept-1Capacity.Compare heat treatment temperature
600 DEG C, Na3Fe2(PO4)3- 700 capacity occur significantly to decline.Result shows, obtains monocline Na by solid-phase synthesis3Fe2
(PO4)3Optimum treatment temperature be 600 DEG C.
Embodiment 4
A kind of spherical Na of sodium-ion battery positive material3Fe2(PO4)3The preparation method of-A, specifically includes following preparation step
Suddenly：
Synthesize Na using simple solid-phase synthesis3Fe2(PO4)3, with Na3PO4FePO with Co deposited synthesis4As
Raw material.Na first3PO4And FePO4In molar ratio 1:2 ball milling mixings.First dry grind four hours, (ethanol is as ball for rear liquid phase ball milling 4h
Grinding media, planetary ball mill).The mixture obtaining is dried 12h for 80 DEG C in drying baker, and ethanol volatilizees completely.Obtain consolidates
Body powder 600 DEG C of calcining 10h in tube furnace, using air atmosphere (airflow rate 20mL min-1).
Embodiment 5
A kind of sodium-ion battery positive material Na3Fe2(PO4)3The preparation method of-B, specifically includes following preparation process：
Synthesize Na using simple solid-phase synthesis3Fe2(PO4)3, with Fe2O3, NaCO3, NH4H2PO4As raw material.First
First, Fe2O3, CH3COONa、NH4H2PO4In molar ratio 1:3:3 ball milling mixings.First dry grind four hours, rear liquid phase ball milling 4h (ethanol
As ball-milling medium, planetary ball mill).The mixture obtaining is dried 12h for 80 DEG C in drying baker, and ethanol volatilizees completely.?
To pressed powder in tube furnace 600 DEG C calcining 10h, using air atmosphere (airflow rate 20mL min-1).
Sodium-ion battery positive material Na that embodiment 1,4,5 obtains3Fe2(PO4)3- 600, Na3Fe2(PO4)3- A,
Na3Fe2(PO4)3The XRD spectrum of-B is as shown in Figure 4.Na3Fe2(PO4)3- 600 before and analyzed.With Na3PO4With coprecipitated
The FePO of shallow lake method synthesis4Na as Material synthesis3Fe2(PO4)3In the XRD spectrum of-A, more diffraction maximum occurs, except monocline
Na3Fe2(PO4)3Beyond diffraction maximum, also a lot of miscellaneous peaks, to crossing relative analyses, these miscellaneous peaks may corresponding for pyrophosphate
Characteristic peak.With Fe2O3, NaCO3, NH4H2PO4Na as Material synthesis3Fe2(PO4)3The XRD spectrum result of-B shows, removes
Monocline Na3Fe2(PO4)3Beyond characteristic peak, some miscellaneous peaks, the corresponding characteristic peak for ferrum oxide, and peak equally occur
Less, result shows that the crystallinity of material is not very well to relative intensity, even if result shows to calcine 10h, solid state reaction is still
Not thorough.Stereoscan photograph from Fig. 5 can be seen that different raw materials and obtains under the conditions of identical solid-phase sintering process
The pattern of solid material is also significantly different.With Na3PO4And FePO4The material obtaining for raw material assumes the block pattern of rule, block
Body size is larger, at 3 μm about.With Fe2O3, NaCO3, NH4H2PO4Obtain material morphology and assume random block pattern, reunite
More serious., respectively as sodium-ion battery positive material, chemical property is as shown in Fig. 6-1 and Fig. 6-2 for these three materials.No
The Na of same Material synthesis3Fe2(PO4)3Show different chemical properties.Na3Fe2(PO4)3- A is 20mA in electric current density
g-1Under the conditions of first discharge specific capacity be 55.9mAh g-1, after circulating 30 times, 48.3mAh g can be kept-1Capacity, charge and discharge
Electric curve occurs in that obvious platform near 2.5V.Na3Fe2(PO4)3- B is 20mA g in electric current density-1Under the conditions of put first
Electric specific capacity is 42mAh g-1Capacity, circulation 30 times after can keep 45mAh g-1, occur in that bright near voltage 2.5V
Aobvious charging/discharging voltage platform., Na3Fe2(PO4)3- A and Na3Fe2(PO4)3The specific discharge capacity of-B is significantly lower than in embodiment 1
Na3Fe2(PO4)3- 600 specific discharge capacity, if this is because Na3Fe2(PO4)3- A and Na3Fe2(PO4)3- B positive electrode is not
It is entirely phase Na of monocline3Fe2(PO4)3, also produce some dephasigns in solid state reaction, these dephasigns generally are non-electrochemical
Active material is so that specific discharge capacity has declined.Result shows, FePO4、CH3COONa、NH4H2PO4For raw material, by solid phase
Synthesize monocline Na obtaining3Fe2(PO4)3There is optimal chemical property.
Embodiment 6
Mesoporous Na3Fe2(PO4)3Preparation：Mesoporous Na3Fe2(PO4)3Using sol-gel process.First, accurately weigh Fe respectively
(NO3)3·9H2O,NH4H2PO4,CH3COONa 8.08g, 3.45g, 2.46g are dissolved in 50mL deionized water respectively, weigh
The citric acid of 10.5g is dissolved in 50mL deionized water, in reactor in mixing Fe (NO3)3·9H2O and CH3COONa and not
Disconnected stirring, is slowly added citric acid, is then slowly added into NH4H2PO4It is simultaneously introduced 5mL 5% (wt.) polyvinyl alcohol.Instead
(500rpm) under the conditions of 60 DEG C of water-baths are stirred continuously should be maintained at.Reaction more than 10h, deionized water constantly evaporates acquisition colloidal sol,
The colloidal sol obtaining obtains gel after 12h hour being dried under the conditions of 80 DEG C.Then, the gel obtaining in tube furnace, air
Atmosphere heat treatment (airflow rate 20mL min-1), 600 DEG C of calcining 2h.Obtain mesoporous Na3Fe2(PO4)3Material.
Obtained mesoporous sodium-ion battery positive material Na3Fe2(PO4)3XRD is as shown in fig. 7, diffraction maximum and standard list
Tiltedly Na3Fe2(PO4)3Diffraction maximum can be good at corresponding (ICSD No.45-0319), no dephasign generates.Na3Fe2(PO4)3SEM, TEM photo as shown in figure 8, result shows, in Na3Fe2(PO4)3The surface of block particle defines substantial amounts of hole knot
Structure, these mesoporous diameters are about between 40nm-60nm.As sodium-ion battery positive material, chemical property such as Fig. 9-1
With shown in Fig. 9-2, in 20mA g-1Electric current density under, first capacity be 92.5mAh g-1, reach the 90% of theoretical capacity.Follow
After ring 30 times, it is maintained in 91mAh g-1, capacity almost has decay.Meso-hole structure Na3Fe2(PO4)3
Show excellent cycle performance and volumetric properties.Compare, solid phase method, sol-gel synthesis greatly reduce sintering time, and
And the material obtaining shows optimal chemical property.
Embodiment 7
Compared with Example 1, in addition to calcination time is for 8h, remaining is all the same.
Embodiment 8
Compared with Example 1, in addition to calcination time is for 12h, remaining is all the same.
Embodiment 9
Compared with Example 6, in addition to bath temperature is 50 DEG C, remaining is all the same.
Embodiment 10
Compared with Example 6, in addition to bath temperature is 70 DEG C, remaining is all the same.
Embodiment 11
Compared with Example 6, except calcining heat is 500 DEG C, calcination time is outside 4h, and remaining is all the same.
Embodiment 12
Compared with Example 6, except calcining heat is 700 DEG C, calcination time is outside 1h, and remaining is all the same.
The above-mentioned description to embodiment is to be understood that and use invention for ease of those skilled in the art.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
, according to the announcement of the present invention, the improvement made without departing from scope and modification all should be the present invention's for field technique personnel
Within protection domain.
Claims (10)
1. a kind of sodium-ion battery positive material Na3Fe2(PO4)3It is characterised in that described positive electrode is monoclinic crystal material
Material, its chemical general formula is Na3Fe2(PO4)3.
2. sodium-ion battery positive material Na as claimed in claim 13Fe2(PO4)3Preparation method it is characterised in that include
Following steps：
Iron salt, sodium salt is taken to mix with phosphate so that Fe3+、Na+And PO4 3+The mol ratio of three kinds of ions is 2:3:3, in air gas
Calcine under atmosphere, that is, obtain monocline Na3Fe2(PO4)3Positive electrode.
3. a kind of sodium-ion battery positive material Na according to claim 23Fe2(PO4)3Preparation method, its feature exists
In described iron salt is FePO4Or Fe2O3；
Described sodium salt is CH3COONa、Na3PO4Or NaCO3；
Described phosphate is FePO4、Na3PO4Or NH4H2PO4In at least one.
4. a kind of sodium-ion battery positive material Na according to claim 23Fe2(PO4)3Preparation method, its feature exists
In the temperature of calcining is 500～700 DEG C, and calcination time is 8-12h.
5. a kind of sodium-ion battery positive material Na according to claim 23Fe2(PO4)3Preparation method, its feature exists
In the process step of mixing is：First dry grind in planetary ball mill 3-5h, then liquid phase ball milling 3-5h, is finally dried and removes
Liquid phase.
6. sodium-ion battery positive material Na as claimed in claim 13Fe2(PO4)3Preparation method it is characterised in that include
Following steps：
(1) weigh Fe (NO3)3·9H2O and CH3COONa is dissolved in deionized water, is kept stirring for condition, adds citric acid, then with
When add NH4H2PO4And polyvinyl alcohol, agitating heating, water-bath, obtain colloidal sol；
(2) obtain gel after the colloidal sol that step (1) obtains being dried, under air atmosphere, calcining, that is, obtain pure phase monocline and be situated between
Hole Na3Fe2(PO4)3Positive electrode.
7. a kind of sodium-ion battery positive material Na according to claim 63Fe2(PO4)3Preparation method, its feature exists
In the Fe (NO adding in step (1)3)3·9H2O、NH4H2PO4And CH3COONa meets：Fe3+、Na+And PO4 3+Three kinds of ions
Mol ratio is 2:3:3.
8. a kind of sodium-ion battery positive material Na according to claim 63Fe2(PO4)3Preparation method, its feature exists
In with every 0.03mol CH3COONa counts, and the addition of citric acid is 8～12g, and the concentration of polyvinyl alcohol is 5wt%, its addition
Measure as 4-6mL.
9. a kind of sodium-ion battery positive material Na according to claim 63Fe2(PO4)3Preparation method, its feature exists
In in step (1), the temperature of water-bath is 50～70 DEG C, and the response time is not less than 10h.
10. a kind of sodium-ion battery positive material Na according to claim 63Fe2(PO4)3Preparation method, its feature exists
In in step (2), the temperature of calcining is 500～700 DEG C, and the time is 1-4h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108039482A (en) * | 2017-12-27 | 2018-05-15 | 东莞理工学院 | The application of ferric phosphate and phosphoric acid iron composite material as negative material in sodium-ion battery |
| CN108417815A (en) * | 2018-04-26 | 2018-08-17 | 浙江大学 | A kind of carbon-coated vanadium phosphate sodium three-dimensional meso-hole nano material and preparation method and application |
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| CN114883540A (en) * | 2022-04-03 | 2022-08-09 | 复旦大学 | Iron-based phosphate sodium-ion battery positive electrode material and preparation method thereof |
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| CN108511704A (en) * | 2018-03-06 | 2018-09-07 | 上海应用技术大学 | A kind of magnesium substitution vanadium phosphate sodium/carbon composite anode material of sodium-ion battery and preparation method thereof |
| CN108565418A (en) * | 2018-04-03 | 2018-09-21 | 武汉大学 | A kind of novel sodium-ion battery positive material and preparation method thereof |
| CN108417815A (en) * | 2018-04-26 | 2018-08-17 | 浙江大学 | A kind of carbon-coated vanadium phosphate sodium three-dimensional meso-hole nano material and preparation method and application |
| CN108649222A (en) * | 2018-05-09 | 2018-10-12 | 上海电力学院 | A kind of high-performance sodium-ion battery positive material and preparation method thereof |
| CN113526483A (en) * | 2021-07-13 | 2021-10-22 | 内蒙古大学 | Ferro-phosphorus sodalite type cathode material and preparation method and application thereof |
| CN113526483B (en) * | 2021-07-13 | 2022-12-30 | 内蒙古大学 | Ferro-phosphorus sodalite type cathode material and preparation method and application thereof |
| CN114883540A (en) * | 2022-04-03 | 2022-08-09 | 复旦大学 | Iron-based phosphate sodium-ion battery positive electrode material and preparation method thereof |
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