CN109659525A - A method of preparing manganese fluorophosphate ferrisodium composite positive pole - Google Patents

A method of preparing manganese fluorophosphate ferrisodium composite positive pole Download PDF

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CN109659525A
CN109659525A CN201811522337.3A CN201811522337A CN109659525A CN 109659525 A CN109659525 A CN 109659525A CN 201811522337 A CN201811522337 A CN 201811522337A CN 109659525 A CN109659525 A CN 109659525A
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source
manganese
sodium
ferrisodium
acid
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钟胜奎
唐式豹
伍凌
王钒
王一钒
曹普文
隋玉雷
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Suzhou University
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Suzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 methods for preparing manganese fluorophosphate ferrisodium composite positive pole, the spinning solution formed using sodium source, source of iron, manganese source, source of phosphoric acid, Fluorine source, chelating agent and high molecular polymer is outer shaft, oils spinning solution is inner shaft, coaxial electrostatic spinning, extraction is except phase of deoiling, hollow Nano fiber in use presoma is dried to obtain, is heat-treated under non-oxidizing atmosphere, cooling Na2Fe1‑xMnxPO4F/C is added in conducting high polymers object solution, is stirred, is filtered, washed dry, drying, obtains Na2Fe1‑xMnxPO4F/C- conductive polymer nanometer fiber.The present invention is by Na2Fe1‑xMnxPO4F is compound with conducting polymer, synergistic effect is generated, obtains the composite material of electrochemical performance, specific capacity high good rate capability, has extended cycle life, has a safety feature, it is a kind of novel battery composite positive pole of high-energy density, there is broad prospect of application.

Description

A method of preparing manganese fluorophosphate ferrisodium composite positive pole
Technical field
The invention belongs to sodium ion battery electrode material technical fields, and in particular to a kind of to prepare sodium-ion battery fluorine phosphorus Sour manganese ferrisodium (Na2Fe1-xMnxPO4F) the method for composite positive pole.
Background technique
With the development of world economy, the improvement of people's living standards, demand of the society to the energy can also be further increased, Other than traditional energy, the purposes of battery is also more and more extensive, other than field of household appliances, in automobile and wind power plant There has also been more applications and development in the fields such as high capacity cell.With the development of battery technology, on the basis of conventional batteries, Due to having stable safety, the small equal every advantage at low cost of size to be widely used, thus needs lithium ion battery Ask also increasing.But the resource of lithium is limited, it is difficult to meet the needs of increasingly developed.Sodium and lithium are located at same main group, Physicochemical properties are similar, and sodium is resourceful, cheap, and developing sodium-ion battery seems extremely important, therefore sodium ion Battery is likely to become one of lithium ion battery substitute.
Include PO4Polyanionic compound positive electrode etc. has stable structure, and synthetic method is simple and capacity is high Advantage makes great progress in recent years.In order to pursue the high-energy density of sodium-ion battery, sight has been invested fluorine by researcher Phosphate cathode material A2MPO4F (A=Li, Na；M=Fe, Mn, Co, Ni).This kind of material is due to introducing a fluorine ion Reach charge balance, containing there are two alkali metal ion in such material structure, it is therefore possible to realize each transition metal from Son carries out two electron exchanges, and corresponding theoretical specific capacity is about twice of corresponding phosphate theoretical specific capacity.Therefore, fluorophosphate It is a kind of promising high-energy density sodium anode material for lithium-ion batteries.Wherein Na2FePO4F is a kind of two-dimensional layered structure Material, possesses two-dimensional sodium ion transmission channel, and sodium ion diffusion coefficient is up to 10-10cm2/ s, and structure cell in charge and discharge process Volume change is only 3.7%, and stable structure during de-/embedding sodium has preferable cyclical stability, but current potential is relatively low.It is pure The Na of phase2MnPO4F has octahydrogon space structure, and fluorine ion and sodium ion are located at the gap of octahedra skeleton. Na2MnPO4F belongs to the fluorophosphoric acid salt of polyanionic compound, and the positive electrode of fluorophosphoric acid salt is because including fluorine ion and phosphorus Sulfonate groups voltage with higher and higher specific capacity, but Na2MnPO4F electro-chemical activity is very low.
Summary of the invention
For Na2FePO4F current potential is relatively low and Na2MnPO4The problem of F electro-chemical activity difference, the quasi- searching compromise of the present invention Solution begins to focus on the solid solution Na of the two2Fe1-xMnxPO4F, 0 < X < 1.The study found that porous filamentous nanocarbon The three-dimensional hybrid conductive network formed that interweaves can realize the collaboration transport of electronics and ion, this is conducive to give full play to nano-electrode The kinetic advantage of material, so that electrode material has better performance.And nanofiber is obtained, electrostatic spinning is one Simple effective method, principle are exactly to carry out drawing-off to polymer solution using electric field force to obtain nanofiber.This hair It is bright to change by adjusting Fe and Mn content ratio, it finds suitable Fe and Mn content matches, to find Na2Fe1-xMnxPO4F's Electro-chemical activity ratio Na2MnPO4F is good, and average operation current potential ratio Na2FePO4F high.In addition, by nanofiber surface One layer of conducting polymer and construction hollow Nano fiber in use structure are coated, to further increase the conductivity and stable structure of material Property.
In view of this, the purpose of the present invention is to provide a kind of method for preparing manganese fluorophosphate ferrisodium composite positive pole, To improve Na simultaneously2FePO4F current potential is relatively low and Na2MnPO4The problem of F electro-chemical activity difference, and it is compound just to further increase this The conductivity and structural stability of pole material.
Specifically, the method for preparation manganese fluorophosphate ferrisodium composite positive pole of the invention, includes the following steps:
Suitable sodium source, source of iron, manganese source, source of phosphoric acid, Fluorine source are selected first, is dissolved in suitable solvent, and chelating agent is added And high molecular polymer, stirring certain time form it into spinning solution A.Wherein, Na: Fe: Mn: PO4: F (molar ratio)=(1.9 ~2.1): (1-X): X: (0.9~1.1): (0.9~1.1), 0 < X < 1；Manganese fluorophosphate ferrisodium: chelating agent (molar ratio)= (0.9~1.1): (1.1~1.3)；Manganese fluorophosphate ferrisodium: high molecular polymer (mass ratio)=(6.9~7.1): (0.9~ 1.1)。
Wherein, the sodium source be one of sodium fluoride, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium carbonate, sodium acetate or It is several.
The source of iron is one of iron chloride, frerrous chloride, ironic citrate, ferrous oxalate, ferrous acetate, ferric nitrate Or it is several.
The manganese source is one or more of manganese acetate, manganese carbonate, manganese nitrate, manganese monoxide, manganese dioxide.
The source of phosphoric acid is one of ammonium dihydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate or several Kind.
The Fluorine source is one or more of sodium fluoride, ammonium fluoride.
The chelating agent is one or more of oxalic acid, citric acid, ascorbic acid, tartaric acid.
Select oils as spinning solution B；Using spinning solution B as inner shaft, coaxial electrostatic spinning is carried out by outer shaft of spinning solution A, Obtain Coaxial Nanofibers；Coaxial Nanofibers are placed in extractant except phase of deoiling, hollow Nano fiber in use forerunner is obtained after drying Body.
Hollow Nano fiber in use presoma is heat-treated under non-oxidizing atmosphere, obtains Na after cooling2Fe1- xMnxPO4F/C positive electrode.
Monomer and oxidant are uniformly mixed, organic solvent is dissolved in, by Na2Fe1-xMnxPO4F/C (mass ratio, Na2Fe1- xMnxPO4F/C: conducting high polymers object=10: 1~50: 1) it is scattered in solution, is then slowly added into catalyst, stir, Polymerization reaction occurs, obtains Na2Fe1-xMnxPO4F/C- conducting high polymers object composite nano fiber.
Wherein, the monomer is one or more of aniline, pyrroles.
The oxidant is ammonium persulfate ((NH4)2S2O8), potassium bichromate (K2Cr2O7), hydrogen peroxide (H2O2), acid iodide Potassium (KIO3One or more of).
The catalyst is lewis' acid (Lewis), FeCl3、CuCl、CuCl2One or more of.
Compared with prior art, method provided by the invention has the beneficial effect that
1, with the electric conductivity of conducting polymer and high capacity come to Na2Fe1-xMnxPO4F material is modified, and is improved Na2Fe1-xMnxPO4F electric conductivity, specific capacity and high rate performance.Advantage i.e. high using conducting polymer electric conductivity, Lai Tigao Na2Fe1-xMnxPO4The ionic conductivity of F；Using conducting polymer to Na2Fe1-xMnxPO4F is coated, and material powder can be prevented Change, improves the cyclical stability of battery.
2、Na2Fe1-xMnxPO4F is compound with conducting polymer, can make up other side's disadvantage mutually, generates synergistic effect, obtains Obtain the composite material Na of electrochemical performance2Fe1-xMnxPO4F/ conducting polymer, specific capacity height, good rate capability, circulation Service life is long, has a safety feature, and is a kind of novel battery composite positive pole of high-energy density, has broad prospect of application.
3, the hollow porous nano-fibre structure that electrostatic spinning is prepared, material granule are the hollow tubular structure of rule, Be conducive to electrolyte to come into full contact with positive electrode, so that interlaced efficent electronic/Ar ion mixing conductive network is formed, this So that electronics and Na+It can be quickly transferred to each active particle surface, to significantly improve its electronic conductivity and ionic conductance Rate.Obtain the composite material Na of electrochemical performance2Fe1-xMnxPO4F/ conducting polymer, specific capacity height, high rate performance Well, it has extended cycle life.
Detailed description of the invention
Fig. 1 is the hollow cladding schematic diagram of particle of sample A1 in embodiment 1；
It is hollow structure, and 1 is Na2Fe1-xMnxPO4F/C, 2 be conducting high polymers object.
Specific embodiment
Below in conjunction with the embodiment of the present invention and attached drawing, technical solution in the embodiment of the present invention carries out detailed retouch It states.
Embodiment 1
In molar ratio Na: Fe: Mn: PO4: weigh sodium carbonate, ironic citrate, manganese acetate, phosphoric acid at F=2: 0.6: 0.4: 1: 1 Ammonium dihydrogen and ammonium fluoride are stirred at room temperature to being completely dissolved using deionized water as solvent, oxalic acid (molar ratio, fluorophosphoric acid are added Manganese ferrisodium: polyvinyl alcohol (mass ratio, manganese fluorophosphate ferrisodium: poly- second that average molecular weight be 6000 oxalic acid=1: 1.2) are added, Enol=7: 1), continue stirring to form uniform spinning solution A.
Select mineral oil as spinning solution B.
Spinning solution A and spinning solution B are drawn into syringe respectively, install coaxial spinning syringe needle, the internal-and external diameter of syringe needle Respectively 0.3mm and 0.5mm, filament mouth are 15cm, voltage 12kV, spinning speed 0.15mm/ at a distance from receiver Min is prepared into Coaxial Nanofibers presoma.
Coaxial Nanofibers presoma is placed in extractant n-hexane except phase of deoiling, hollow Nano fiber in use forerunner is dried to obtain Body.
Obtained Coaxial Nanofibers presoma will be collected to be placed in tube furnace, under an argon atmosphere, with 5 DEG C/min heating To 650 DEG C, then constant temperature 10h cools to room temperature with the furnace, obtains the positive electrode of hollow porous nano-fibre Na2Fe0.6Mn0.4PO4F/C。
In glass container in molar ratio 1: 1 after mixing by aniline and phosphoric acid, according to mass ratio (Na2Fe0.6Mn0.4PO4F: the positive electrode of hollow porous nano-fibre made from above-mentioned steps polyaniline=10: 1) is added Na2Fe0.6Mn0.4PO4System temperature is reduced to 0 DEG C with ice-water bath by F/C, and hydrogen peroxide is added dropwise under stiring, is stirred 90 minutes Polymerization reaction occurs, then filters, washs, drying.Obtain Na2Fe0.6Mn0.4PO4The hollow porous composite Nano of F/C- polyaniline is fine Dimension, sample are denoted as A1.
Embodiment 2
In molar ratio Na: Fe: Mn: PO4: weigh sodium acetate, ironic citrate, manganese acetate, phosphorus at F=2: 0.4: 0.6: 1: 1.05 Acid dihydride ammonium and sodium fluoride are stirred at room temperature to being completely dissolved using deionized water as solvent, oxalic acid (molar ratio, fluorine phosphorus are added Sour manganese ferrisodium: oxalic acid=0.9: 1.2), and add average molecular weight be 6000 polyvinyl alcohol (mass ratio, manganese fluorophosphate ferrisodium: Polyvinyl alcohol=6.9: 1), continue stirring to form uniform spinning solution A.
Select mineral oil as spinning solution B.
Spinning solution A and spinning solution B are drawn into syringe respectively, install coaxial spinning syringe needle, the internal-and external diameter of syringe needle Respectively 0.3mm and 0.5mm, filament mouth are 15cm, voltage 12kV, spinning speed 0.15mm/ at a distance from receiver Min is prepared into Coaxial Nanofibers presoma.
Coaxial Nanofibers are placed in extractant n-hexane except phase of deoiling, hollow Nano fiber in use presoma is dried to obtain.
Obtained Coaxial Nanofibers presoma will be collected to be placed in tube furnace, under an argon atmosphere, with 5 DEG C/min heating To 650 DEG C, constant temperature 10h is cooled to room temperature after heat treatment, obtains the positive electrode of hollow porous nano-fibre Na2Fe0.4Mn0.6PO4F/C。
Be added aniline and dodecyl benzene sulfonic acid at 0.8: 1 in molar ratio in the reactor, be uniformly mixed, sequentially add water, Dimethylbenzene is sufficiently stirred, and obtains transparency emulsion, and the positive electrode of hollow porous nano-fibre made from above-mentioned steps is added Na2Fe0.4Mn0.6PO4F/C (mass ratio, Na2Fe0.4Mn0.6PO4F: it polyaniline=25: 1), is uniformly dispersed, is then dripped into system Add ammonium persulfate aqueous solution, be added dropwise in 2 minutes, the color of system deepens quickly, and system temperature is maintained at 20 DEG C, stirring Product, is then successively used water and ethanol washing, filtering, drying, obtained by 120 minutes generation polymerization reactions Na2Fe0.4Mn0.6PO4The hollow porous composite nano fiber of F/C- polyaniline, sample are denoted as A2.
Embodiment 3
In molar ratio Na: Fe: Mn: PO4: F=2: 0.95: 0.05: 1: 1 weigh sodium hydroxide, ironic citrate, manganese acetate, Ammonium dihydrogen phosphate and sodium fluoride are stirred at room temperature uniformly using deionized water as solvent, citric acid (molar ratio, fluorophosphoric acid are added Manganese ferrisodium: citric acid=0.9: 1.3), and add average molecular weight be 6000 polyvinyl alcohol (mass ratio, manganese fluorophosphate ferrisodium: Polyvinyl alcohol=6.9: 1.1), continue stirring to form uniform spinning solution A.
Select mineral oil as spinning solution B.
Spinning solution A and spinning solution B are drawn into syringe respectively, install coaxial spinning syringe needle, the internal-and external diameter of syringe needle Respectively 0.3mm and 0.5mm, filament mouth are 15cm, voltage 12kV, spinning speed 0.15mm/ at a distance from receiver Min is prepared into Coaxial Nanofibers presoma.
Coaxial Nanofibers are placed in extractant n-hexane except phase of deoiling, hollow Nano fiber in use presoma is dried to obtain.
Obtained Coaxial Nanofibers presoma will be collected to be placed in tube furnace, under an argon atmosphere, with 5 DEG C/min heating To 650 DEG C, constant temperature 10h is cooled to room temperature after heat treatment, obtains the positive electrode of hollow porous nano-fibre Na2Fe0.95Mn0.05PO4F/C。
Pyrrole monomer and lewis' acid are dissolved in ethyl alcohol at 1: 1 in molar ratio, are added hollow porous made from above-mentioned steps The positive electrode Na of nanofiber2Fe0.95Mn0.05PO4F/C (mass ratio, Na2Fe0.95Mn0.05PO4F: it polypyrrole=50: 1), stirs Reaction 2h is mixed, the polymer that polymerization reaction formation pyrroles occurs obtains then by product ethyl alcohol and water washing, filtering, drying Na2Fe0.95Mn0.05PO4The hollow porous composite nano fiber of F/C- polypyrrole, is denoted as A3 for sample.
Embodiment 4
In molar ratio Na: Fe: Mn: PO4: weigh sodium carbonate, ferrous oxalate, acetic acid at F=2: 0.05: 0.95: 1.05: 1.05 Manganese, sodium dihydrogen phosphate and sodium fluoride are stirred at room temperature uniformly using deionized water as solvent, citric acid (molar ratio, fluorine are added Manganese phosphate ferrisodium: polyvinyl alcohol (mass ratio, manganese fluorophosphate iron that average molecular weight be 6000 citric acid=1: 1.1) are added, Sodium: polyvinyl alcohol=7.1: 0.9), continue stirring to form uniform spinning solution A.
Select mineral oil as spinning solution B.
Spinning solution A and spinning solution B are drawn into syringe respectively, install coaxial spinning syringe needle, the internal-and external diameter of syringe needle Respectively 0.3mm and 0.5mm, filament mouth are 15cm, voltage 12kV, spinning speed 0.15mm/ at a distance from receiver Min is prepared into Coaxial Nanofibers presoma.
Coaxial Nanofibers are placed in extractant n-hexane except phase of deoiling, hollow Nano fiber in use presoma is dried to obtain.
Obtained Coaxial Nanofibers presoma will be collected to be placed in tube furnace, under an argon atmosphere, with 5 DEG C/min heating To 650 DEG C, constant temperature 10h is cooled to room temperature after heat treatment, obtains the positive electrode of hollow porous nano-fibre Na2Fe0.05Mn0.95PO4F/C。
Select chloroform and water as two-phase solvent, by pyrrole monomer and ammonium persulfate in molar ratio 1: 1 be dissolved in it is organic In solvent, the positive electrode Na of hollow porous nano-fibre made from above-mentioned steps is then added2Fe0.05Mn0.95PO4F/C (matter Measure ratio, Na2Fe0.05Mn0.95PO4F: polypyrrole=20: 1), being stirred to react 2h, and the polymer that polymerization reaction forms pyrroles occurs, Then it is filtered, washed drying, dries, obtains Na2Fe0.05Mn0.95PO4The hollow porous composite nano fiber of F/C- polypyrrole, by sample Product are denoted as A4.
Comparative example 1
Method of electrostatic spinning prepares Na2Fe0.6Mn0.4PO4The hollow porous nano-fibre of F/C (conducting polymer is not added):
The Na that will be prepared in embodiment 12Fe0.6Mn0.4PO4F/C hollow porous nano-fibre (not compound polyphenylamine) sample note For D1.
Comparative example 2
Method of electrostatic spinning prepares Na2Fe0.6Mn0.4PO4F/C- polyaniline solid nanofiber (adds conducting polymer, does not do Vacancy reason):
In molar ratio Na: Fe: Mn: PO4: weigh sodium carbonate, ironic citrate, manganese acetate, phosphoric acid at F=2: 0.6: 0.4: 1: 1 Ammonium dihydrogen and ammonium fluoride are stirred at room temperature to being completely dissolved using deionized water as solvent, oxalic acid (molar ratio, fluorophosphoric acid are added Manganese ferrisodium: polyvinyl alcohol (mass ratio, manganese fluorophosphate ferrisodium: poly- second that average molecular weight be 6000 oxalic acid=1: 1.2) are added, Enol=7: 1), continue stirring to form uniform spinning solution.
Spinning solution is drawn into syringe, syringe needle internal diameter is 0.5mm, and filament mouth is 15cm, electricity at a distance from receiver Pressure is 12kV, spinning speed 0.15mm/min, is prepared into nanofiber presoma, is dried.
Obtained nanofiber presoma will be collected to be placed in tube furnace, under an argon atmosphere, be warming up to 5 DEG C/min 650 DEG C, then constant temperature 10h cools to room temperature with the furnace, obtains solid nanofiber positive electrode Na2Fe0.6Mn0.4PO4F/C。
In glass container in molar ratio 1: 1 after mixing by aniline and phosphoric acid, according to mass ratio (Na2Fe0.6Mn0.4PO4F: solid nanofiber positive electrode made from above-mentioned steps polyaniline=10: 1) is added Na2Fe0.6Mn0.4PO4System temperature is reduced to 0 DEG C with ice-water bath by F/C, and hydrogen peroxide is added dropwise under stiring, is stirred 90 minutes Polymerization reaction occurs, then filters, washs, drying.Obtain Na2Fe0.6Mn0.4PO4F/C- polyaniline solid composite nanofiber, Sample is denoted as D2.
Comparative example 3
Solid phase method prepares Na2Fe0.6Mn0.4PO4F/C:
By Na2Fe0.6Mn0.4PO4The stoichiometric ratio of F weighs sodium carbonate, ironic citrate, manganese acetate, ammonium dihydrogen phosphate and fluorine Change ammonium, glucose (Na in mass ratio is added2Fe0.6Mn0.4PO4F: glucose=5: 1), mechanical activation 6h obtains presoma after mixing, Precursor powder is placed in tube furnace, under an argon atmosphere, is warming up to 650 DEG C with 5 DEG C/min, constant temperature 10h is then cold with furnace But to room temperature, Na is obtained2Fe0.6Mn0.4PO4F/C powder positive electrode, sample are denoted as D3.
The performance comparison of sample is prepared in each implementation column of table 1

Claims (10)

1. a kind of method for preparing manganese fluorophosphate ferrisodium composite positive pole, which is characterized in that include the following steps:
S1, sodium source, source of iron, manganese source, source of phosphoric acid, Fluorine source are dissolved in suitable solvent, chelating agent and high molecular polymer are added, Stirring forms spinning solution A, wherein with molar ratio computing, Na: Fe: Mn: PO4: F=(1.9~2.1): (1-X): X: (0.9~1.1) : (0.9~1.1), 0 < X < 1, manganese fluorophosphate ferrisodium: chelating agent=(0.9~1.1): (1.1~1.3)；By quality ratio, fluorine Manganese phosphate ferrisodium: high molecular polymer=(6.9~7.1): (0.9~1.1)；
S2, using oils spinning solution B as inner shaft, spinning solution A be outer shaft carry out coaxial electrostatic spinning, obtain Coaxial Nanofibers, will It is placed in extractant except phase of deoiling, and dries to obtain hollow Nano fiber in use presoma；
S3, hollow Nano fiber in use presoma is heat-treated under non-oxidizing atmosphere, obtains Na after cooling2Fe1- xMnxPO4F/C；
S4, monomer and oxidant are uniformly mixed, are dissolved in organic solvent, by Na2Fe1-xMnxPO4F/C is scattered in solution, then It is slowly added to catalyst, is stirred, polymerization reaction occurs, obtains Na2Fe1-xMnxPO4F/C- conducting high polymers object composite Nano Fiber, wherein Na2Fe1-xMnxPO4F/C and the conducting high polymers amount of substance ratio of generation are 10: 1~50: 1.
2. the method according to claim 1, wherein the sodium source is sodium fluoride, sodium dihydrogen phosphate, phosphoric acid hydrogen One or more of disodium, sodium carbonate, sodium acetate.
3. the method according to claim 1, wherein the source of iron is iron chloride, frerrous chloride, citric acid One or more of iron, ferrous oxalate, ferrous acetate, ferric nitrate.
4. the method according to claim 1, wherein the manganese source is manganese acetate, manganese carbonate, manganese nitrate, one One or more of manganese oxide, manganese dioxide.
5. the method according to claim 1, wherein the source of phosphoric acid be ammonium dihydrogen phosphate, sodium dihydrogen phosphate, One or more of diammonium hydrogen phosphate, disodium hydrogen phosphate.
6. the method according to claim 1, wherein the Fluorine source be one of sodium fluoride, ammonium fluoride or It is several.
7. the method according to claim 1, wherein the chelating agent be oxalic acid, citric acid, ascorbic acid, One or more of tartaric acid.
8. the method according to claim 1, wherein the monomer is one or more of aniline, pyrroles.
9. the method according to claim 1, wherein the oxidant is ammonium persulfate, potassium bichromate, peroxide Change one or more of hydrogen, Potassiumiodate.
10. the method according to claim 1, wherein the catalyst is lewis' acid, FeCl3、CuCl、 CuCl2One or more of.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110289411A (en) * 2019-07-02 2019-09-27 中南大学 A kind of fluorinated phosphate zirconium manganese sodium/carbon composite, positive electrode, anode and sodium-ion battery and preparation method thereof
WO2021036791A1 (en) * 2019-08-28 2021-03-04 宁德时代新能源科技股份有限公司 Positive electrode material for sodium ion battery, preparation method therefor and related sodium ion battery, battery module, battery pack and device thereof
CN112968154A (en) * 2021-02-01 2021-06-15 武汉大学 Conductive composite material, preparation method thereof and application thereof in lithium ion battery electrode
CN113991109A (en) * 2021-09-04 2022-01-28 桂林理工大学 Sodium manganese fluorophosphate/titanium carbide sheet-carbon quantum dot composite material and preparation method and application thereof
CN114142026A (en) * 2021-12-02 2022-03-04 河南师范大学 Manganese-based polyanion positive electrode material, preparation method thereof and sodium-ion battery
CN114906832A (en) * 2022-03-11 2022-08-16 新疆师范大学 Preparation method of sodium iron fluorophosphate cathode material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101237036A (en) * 2008-01-21 2008-08-06 湘潭大学 Making method for positive material LiFePO4 of poly-aniline coated lithium ion battery
CN102574687A (en) * 2009-10-08 2012-07-11 住友化学株式会社 Transition metal phosphate, and sodium secondary battery
CN106328942A (en) * 2016-11-11 2017-01-11 宁德新能源科技有限公司 Lithium ferric manganese phosphate anode material, preparation method and application thereof
CN107039641A (en) * 2017-03-22 2017-08-11 苏州大学 A kind of method for preparing hollow porous Na2MnPO4F/C nanofibers positive electrode

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101237036A (en) * 2008-01-21 2008-08-06 湘潭大学 Making method for positive material LiFePO4 of poly-aniline coated lithium ion battery
CN102574687A (en) * 2009-10-08 2012-07-11 住友化学株式会社 Transition metal phosphate, and sodium secondary battery
CN106328942A (en) * 2016-11-11 2017-01-11 宁德新能源科技有限公司 Lithium ferric manganese phosphate anode material, preparation method and application thereof
CN107039641A (en) * 2017-03-22 2017-08-11 苏州大学 A kind of method for preparing hollow porous Na2MnPO4F/C nanofibers positive electrode

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YONG HU 等: "Electrospinning synthesis of Na2MnPO4F/C nanofibers as a high voltage cathode material for Na-ion batteries", 《CERAMICS INTERNATIONAL》 *
耿海龙 等: "橄榄石结构正极材料Li1+xFe1-xMnxPO4Fx电化学性能", 《电源技术》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110289411A (en) * 2019-07-02 2019-09-27 中南大学 A kind of fluorinated phosphate zirconium manganese sodium/carbon composite, positive electrode, anode and sodium-ion battery and preparation method thereof
CN110289411B (en) * 2019-07-02 2020-08-14 中南大学 Zirconium fluoride manganese sodium phosphate/carbon composite material, positive electrode, sodium ion battery and preparation method thereof
WO2021036791A1 (en) * 2019-08-28 2021-03-04 宁德时代新能源科技股份有限公司 Positive electrode material for sodium ion battery, preparation method therefor and related sodium ion battery, battery module, battery pack and device thereof
EP3968410A4 (en) * 2019-08-28 2022-08-17 Contemporary Amperex Technology Co., Limited Positive electrode material for sodium ion battery, preparation method therefor and related sodium ion battery, battery module, battery pack and device thereof
CN112968154A (en) * 2021-02-01 2021-06-15 武汉大学 Conductive composite material, preparation method thereof and application thereof in lithium ion battery electrode
CN113991109A (en) * 2021-09-04 2022-01-28 桂林理工大学 Sodium manganese fluorophosphate/titanium carbide sheet-carbon quantum dot composite material and preparation method and application thereof
CN113991109B (en) * 2021-09-04 2023-12-26 桂林理工大学 Sodium manganese fluorophosphate/titanium carbide lamellar-carbon quantum dot composite material and preparation method and application thereof
CN114142026A (en) * 2021-12-02 2022-03-04 河南师范大学 Manganese-based polyanion positive electrode material, preparation method thereof and sodium-ion battery
CN114142026B (en) * 2021-12-02 2023-10-20 河南师范大学 Manganese-based polyanion positive electrode material, preparation method thereof and sodium ion battery
CN114906832A (en) * 2022-03-11 2022-08-16 新疆师范大学 Preparation method of sodium iron fluorophosphate cathode material

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