CN105810910B - A kind of Na2‑2xFe1+xP2O7/ carbon composite and its preparation method and application - Google Patents

A kind of Na2‑2xFe1+xP2O7/ carbon composite and its preparation method and application Download PDF

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CN105810910B
CN105810910B CN201610246447.6A CN201610246447A CN105810910B CN 105810910 B CN105810910 B CN 105810910B CN 201610246447 A CN201610246447 A CN 201610246447A CN 105810910 B CN105810910 B CN 105810910B
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sodium
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carbon
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iron
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CN105810910A (en
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张治安
陈晓彬
赖延清
李劼
史晓东
张凯
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Central South 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

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Abstract

The invention discloses a kind of Na2‑2xFe1+xP2O7/ carbon composite and its preparation method and application, the material are by Na2‑2xFe1+ xP2O7The composite that particle surface carbon coated stratum reticulare is formed.The synthetic method of the present invention is simple, mild condition, and yield is high, and the composite being prepared has height ratio capacity, high working voltage, good stable circulation performance and excellent high rate performance when applying as sodium ion positive electrode.

Description

A kind of Na2-2xFe1+xP2O7/ carbon composite and its preparation method and application
Technical field
The present invention relates to a kind of Na2-2xFe1+xP2O7/ carbon composite and its preparation method and application, belong to sodium ion electricity Pond field.
Background technology
With the fast development in net epoch, realize and commercially produce from the lithium ion battery nineties in last century, lithium-ion electric Pond achieves fast development in 3C Product and electric automobiles, and shows good development prospect.However, due to the whole world The scarcity of metal lithium resource, the manufacturing cost of lithium ion battery are in the trend constantly risen.Meanwhile lithium ion battery is due to safety Property is bad, and its development in electric automobile and large-scale energy storage field is greatly limited.However, sodium element, is in lithium Same main group is in the periodic table of elements, so there is its similar property with lithium electrode.And compared with the elemental lithium of scarcity, sodium Element rich reserves and source is more extensive, the manufacturing cost of relative moderate make sodium-ion battery turn into it is a kind of it is most potential can Realize the usable battery system of storage on a large scale of industry.However, due to sodium ion ionic radius than lithium ion ion half Footpath is big so that in kinetically sodium ion, insertion is more difficult than lithium ion with deviating from electrode material, and sodium ion is relative The oxidation-reduction potential of calibration and larger atomic mass so that the low voltage of sodium-ion battery positive material, energy density It is not high.Therefore, sodium-ion battery positive material voltage and the emphasis for turning into research of energy density are improved.
Researchers have studied the sodium-ion battery positive material of different systems, wherein it is more representational be P2 types and O3 type layered oxide systems, such as P2-Na2/3[Fe1/2Mn1/2]O2, O3-NaFe0.5Co0.5O2, but the cycle life of these materials Short, voltage platform is relatively low.
The content of the invention
It is an object of the invention to provide a kind of Nano grade Na of coated with carbon stratum reticulare2-2xFe1+xP2O7/ carbon composite wood Material, the material morphology is controllable, conducts electricity very well, and has height ratio capacity, high working voltage, good stable circulation performance and excellent Different high rate performance.
Another object of the present invention is to provide, a kind of reaction condition is gentle, synthetic method is simple, cost is cheap Na2-2xFe1+xP2O7The preparation method of/carbon composite.
Another object of the present invention is to provide a kind of Na2-2xFe1+xP2O7The application of/carbon composite, by Na2-2xFe1+ xP2O7// carbon composite is applied and is used as sodium ion positive electrode.
Technical program of the present invention lies in provide a kind of Na2-2xFe1+xP2O7/ carbon composite, the composite are surface The Na of carbon coated stratum reticulare2-2xFe1+xP2O7The scope of material, wherein x is 0~1.
The present invention further comprises following preferred scheme：
In preferable scheme, the Na2-2xFe1+xP2O7/ carbon composite crystal formation is reddingite type.
In preferable scheme, the particle diameter of composite is 10~500nm.
In preferable scheme, the thickness of the carbon stratum reticulare is 5~20nm.
The present invention further comprises Na2-2xFe1+xP2O7The preparation method of/carbon composite, comprises the following steps：
(1) carbon source is dissolved in deionized water or alcoholic solution；Source of iron, phosphorus source, sodium source are dissolved separately in deionized water In, stir, be added dropwise to successively according to source of iron, phosphorus source, the order of sodium source in the solution dissolved with carbon source, obtain mixing molten Liquid；
(2) gained mixed solution is placed in autoclave, carries out hydro-thermal reaction in 100 DEG C~300 DEG C, cool down, Gu Liquid separates, and is washed to eluate in neutrality, dried, gained solid product is Na with absolute ethyl alcohol2-2xFe1+xP2O7/ carbon is compound The presoma of material；
(3) presoma obtained by step (2) is first sintered under inert atmosphere protection at 250~350 DEG C, then be warming up to 500~700 DEG C of sintering, produce Na2-2xFe1+xP2O7/ carbon composite.
Sodium source described in step (1) is sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium nitrate, sodium sulphate, citric acid At least one of sodium or sodium thiosulfate；The source of iron be ferric nitrate, iron chloride, ferrous oxalate, ferrous sulfate, ferric sulfate, At least one of ironic citrate, ferric citrate, ferric ammonium sulfate or iron ammonium sulfate；Phosphorus source be ammonium dihydrogen phosphate, At least one of diammonium hydrogen phosphate, phosphoric acid or pyrophosphoric acid；The carbon source is citric acid, ascorbic acid, glucose, sucrose, poly- At least one of vinyl alcohol or polyethylene glycol.
The preparation method of the present invention further comprises following preferred scheme：
In preferable scheme, the combination of the carbon source is typical but non-limitative example has：The combination of citric acid and glucose, The combination of sucrose and glucose, the combination of ascorbic acid, polyethylene alcohol and glucose, particularly preferably citric acid, glucose, gather At least one of vinyl alcohol.
In preferable scheme, the combination of the sodium source is typical but non-limitative example has：The group of sodium carbonate and sodium acid carbonate Close, the combination of sodium sulphate and sodium carbonate, the combination of sodium acetate, sodium citrate and sodium oxalate.Particularly preferably sodium citrate, carbonic acid At least one of sodium, sodium acetate.
In preferable scheme, the combination of the source of iron is typical but non-limitative example has：The group of ferric nitrate and ironic citrate Close, the combination of iron chloride and ferric sulfate, the combination of iron ammonium sulfate, ferric citrate and ironic citrate, particularly preferably lemon At least one of sour iron ammonium, ferric ammonium sulfate.
In preferable scheme, the combination of phosphorus source is typical but non-limitative example has：Ammonium dihydrogen phosphate and phosphoric acid hydrogen two The combination of the combination of ammonium, phosphoric acid and pyrophosphoric acid, particularly preferably ammonium dihydrogen phosphate, at least one of diammonium hydrogen phosphate.
In preferable scheme, in step (1), sodium element in the sodium source, source of iron and phosphorus source, ferro element and P elements rub You are than being 2~2.2:0.8~1.05:2.0.More preferably 2.05~2.1:0.95:2.0.
In preferable scheme, in step (1), the quality and Na of the carbon source2-2xFe1+xP2O7Mass ratio for 0.05~ 1.05:1, most preferably 0.05~0.2:1.
In preferable scheme, in step (1), the alcoholic solution is methanol aqueous solution, ethanol water, glycol water Or at least one of glycerin solution.
In preferable scheme, the volume ratio of alcohol and deionized water is 1 in alcoholic solution:0.5~2.
The volume ratio of most preferably glycol water, alcohol and deionized water is 1:1.
In preferable scheme, 6~12h is first sintered under the conditions of 250~350 DEG C, then be warming up under the conditions of 500~700 DEG C Sinter 12~24h.
In preferable scheme, the time of hydro-thermal reaction is 5~36h in the step (2).
In preferable scheme, in step (2), reaction is carried out preferably in stainless steel cauldron.The reactor can use Free-standing monomer reaction kettle and integral type temperature control stirring reactor.Wherein free-standing monomer reaction kettle is placed on vacuum drying oven It is interior, with maintenance reaction in 100~300 DEG C of progress.
It is preferred that integral type reactor, the accurate control of temperature can be achieved, be stirred continuously during simultaneous reactions can improve it is molten Matter and product dispersing uniformity, be advantageous to obtain the superfines of uniform particle sizes.
In preferable scheme, in step (2), the method that separation of solid and liquid collects product is suction method, spray drying process, centrifugation Method.Wherein spray drying process can directly obtain dry spherical products, and uniform particle sizes, good dispersion can direct sintering.And filter Method is most simple, and the separation of product and solution can be achieved after suction filtration, be placed in 50~100 DEG C of vacuum drying chambers, toasts, is done Dry product.Centrifugal process uses planet centrifuge, and high-speed rotation realizes the separation of product and solution, need also exist for being placed on 50~ 12~24h of baking, obtains desciccate in 100 DEG C of vacuum drying chambers.Preferably, product is typically collected using suction method.
In preferable scheme, in step (3), the inert atmosphere is argon gas or nitrogen.
The present invention further comprises the Na2-2xFe1+xP2O7/ carbon composite is applied and is used as sodium ion positive electrode.
Na prepared by the present invention2-2xFe1+xP2O7The sodium-ion battery performance test methods of/carbon composite：Weigh above-mentioned Na2-2xFe1+xP2O7/ carbon composite, add 10wt.% conductive carbon blacks as conductive agent, 10wt.%PVDF as binding agent, Ground fully adding a small amount of deionized water is mixed to form uniform black paste slurry afterwards, and these slurries are coated in into aluminium foil As test electrode on collector, with metallic sodium piece, electrode assembling turns into button cell as a comparison, and it uses electrolyte system For 1M NaClO4/EC:PC(1:1).Charging and discharging currents density used in test loop performance is 100mAh g-1(1C multiplying powers).
The present invention uses hydro-thermal method, and resulting material has that dephasign is less, and the presoma calcination temperature of synthesis is lower.
Compared with prior art, it is an advantage of the invention that：
(1) cheap sodium source, source of iron, carbon source is used to reduce cost, the present invention can prevent material from preparing as raw material The ferrous ion of process aoxidizes, and causes dephasign.The carbon net clad structure of formation improves the electric conductivity of material, improves material The chemical property of material.
(2) after each raw material used in the present invention dissolves respectively, by strictly controlling dropwise addition order, not only avoid too early Ground precipitates, and reduces the generation of dephasign, the coordinated further controlled by other specification, has reached control crystal nucleation With the speed grown up, the beneficial effect of pattern is adjusted.
(3) dephasign is few in the presoma that the present invention is prepared, and activity is high, compared with the conventional method, can be in lower temperature Lower sintering obtains the Na of pure phase2-2xFe1+xP2O7/ carbon composite.
(4) the carbonaceous conductive net formed in the present invention significantly improves the electric conductivity of material, reduces polarization, improves again Rate performance.
(5) Na that the present invention obtains2-2xFe1+xP2O7/ carbon composite has excellent chemical property, 1C discharge-rates Under, specific discharge capacity reaches 95mAh g-1。
(6) instant invention overcomes the Na that this laboratory is prepared before2+2xFe2-x(SO4)3Voltage platform is unstable, tool There is hygroscopicity, it is very sensitive to the moisture of production environment in actual production process, " poisoning " easily occurs, heat endurance Difference, easily decompose the defects of generating sulfur dioxide.The present invention is the further optimization to scheme before, is obtained by the present invention Na2-2xFe1+xP2O7/ carbon composite has that voltage is moderate (reaching 3.0V), and voltage platform is stable, and cycle performance is good, and chemistry is steady Qualitative and heat endurance is more preferable, preparation process energy-conserving and environment-protective, the advantages that easy industrialization.
Brief description of the drawings
【Fig. 1】It is X-ray diffractogram prepared by embodiment 1.
【Fig. 2】It is Na prepared by embodiment 12-2xFe1+xP2O7The scanning electron microscope diagram of/carbon composite.
【Fig. 3】It is Na prepared by embodiment 12-2xFe1+xP2O7The charging and discharging curve figure of/carbon composite.
【Fig. 4】It is Na prepared by embodiment 12-2xFe1+xP2O7Efficiency for charge-discharge under the 1C discharge-rates of/carbon composite Figure.
【Fig. 5】It is Na prepared by reference examples 22-2xFe1+xP2O7Scanning electron microscope diagram.
Embodiment
Following examples are intended to be described in further details present invention；And the protection domain of the claims in the present invention It is not limited by the example.
Embodiment 1
The present embodiment comprises the following steps：
(1) the present embodiment design generation 0.03mol target products Na2-2xFe1+xP2O7, prepare solution 100mL：Weigh 0.827 g glucose be dissolved in 40mL ethylene glycol solutions (ratio of ethylene glycol and deionized water be 1:1), weigh respectively 0.06mol ammonium dihydrogen phosphate, 0.03mol ferric nitrate, 0.0315mol sodium carbonate, it is dissolved separately in 20mL deionization In water, stirring and dissolving.It is added dropwise to successively in the alcoholic solution of glucose according to phosphorus source, source of iron, the order of sodium source, liquid feeding speed For 15 mL/min, while it is aided with and is stirred vigorously, still aging 24h after the completion of addition；
(2) mixed emulsion handled through step (1) is poured into stainless steel cauldron, reactor volume 150mL, filled Measure as 66.67%, stainless steel cauldron is put into 150 DEG C of thermostatic drying chambers and is incubated 18h, reaction naturally cools to room after terminating Temperature, reactor is taken out, separation of solid and liquid is carried out using sand core funnel.Obtained solid powder is Na2-2xFe1+xP2O7/ carbon is compound The precursor product of material；
(3) gained presoma solid product is placed in 80 DEG C of thermostatic drying chambers, obtains dry powder, will be powdered Product is transferred in crucible, under the protection of argon gas atmosphere, is warming up to 300 DEG C, is sintered 6h, then is warming up to 600 DEG C, is sintered 12h, 5 DEG C/min of programming rate, that is, obtain Na2-2xFe1+xP2O7/ carbon composite.
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, its material table Chemical property seek peace as shown in the figure：
Fig. 1 shows to successfully synthesize Na2-2xFe1+xP2O7/ carbon composite.
The Na of the visible synthesis of Fig. 22-2xFe1+xP2O7/ carbon composite, particle diameter distribution is uniform, favorable dispersibility.Particle diameter is 200nm, carbon thickness of net are 10nm.
Fig. 3 is Na2-2xFe1+xP2O7/ carbon composite is assembled into button cell with sodium piece 94mAh g-1, specific discharge capacity is 95mAh g-1。
Fig. 4 is Na2-2xFe1+xP2O7/ carbon composite is assembled into button cell 10 circulations under 1C multiplying powers with sodium piece Efficiency for charge-discharge is maintained at 96% or so.
Embodiment 2
The present embodiment comprises the following steps：
(1) the present embodiment design generation 0.03mol target products Na2-2xFe1+xP2O7/ carbon composite, prepare solution 100 mL：Weigh 1.634g citric acid be dissolved in 40mL ethylene glycol solutions (ratio of ethylene glycol and deionized water be 1:1), claim respectively Take 0.06mol ammonium dihydrogen phosphate, 0.03mol ferric nitrate, 0.0315mol sodium carbonate, be dissolved separately in 20mL go from In sub- water, stirring and dissolving.It is added dropwise to successively in the alcoholic solution of citric acid according to phosphorus source, source of iron, the order of sodium source, liquid feeding speed Spend for 15mL/min, while be aided with and be stirred vigorously, still aging 24h after the completion of addition；
(2) mixed emulsion handled through step (1) is poured into stainless steel cauldron, reactor volume 150mL, filled Measure as 66.67%, stainless steel cauldron is put into 150 DEG C of thermostatic drying chambers and is incubated 18h, reaction naturally cools to room after terminating Temperature, reactor is taken out, separation of solid and liquid is carried out using sand core funnel.Obtained solid powder is Na2-2xFe1+xP2O7/ carbon is compound The precursor product of material；
(3) gained presoma solid product is placed in 80 DEG C of thermostatic drying chambers, obtains dry powder, will be powdered Product is transferred in crucible, under the protection of argon gas atmosphere, is warming up to 300 DEG C, is sintered 6h, then is warming up to 600 DEG C, is sintered 12h, 5 DEG C/min of programming rate, that is, obtain Na2-2xFe1+xP2O7/ carbon composite.
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, Na2-2xFe1+xP2O7/ carbon is compound Material particle size is 250nm, and carbon thickness of net is 15nm.Initial charge specific capacity is 93mAh g-1, specific discharge capacity is 92mAh g-1, the efficiency for charge-discharge of 10 circulations is maintained at 94% or so under 1C multiplying powers.
Embodiment 3
The present embodiment comprises the following steps：
(1) the present embodiment design generation 0.03mol target products Na2-2xFe1+xP2O7/ carbon composite, prepare solution 10 0mL：Weigh 1.634g glucose be dissolved in 40mL ethylene glycol solutions (ratio of ethylene glycol and deionized water be 1:1), respectively 0.06mol ammonium dihydrogen phosphate is weighed, 0.03mol ferric nitrate, 0.0315mol sodium carbonate, is dissolved separately in going for 20mL In ionized water, stirring and dissolving.It is added dropwise to successively in the alcoholic solution of glucose according to phosphorus source, source of iron, the order of sodium source, liquid feeding Speed is 15mL/min, while is aided with and is stirred vigorously, still aging 24h after the completion of addition；
(2) mixed emulsion handled through step (1) is poured into stainless steel cauldron, reactor volume 150mL, filled Measure as 66.67%, stainless steel cauldron is put into 150 DEG C of thermostatic drying chambers and is incubated 18h, reaction naturally cools to room after terminating Temperature, reactor is taken out, separation of solid and liquid is carried out using sand core funnel.Obtained solid powder is Na2-2xFe1+xP2O7/ carbon is compound The precursor product of material；
(3) gained presoma solid product is placed in 80 DEG C of thermostatic drying chambers, obtains dry powder, will be powdered Product is transferred in crucible, under the protection of argon gas atmosphere, is warming up to 300 DEG C, is sintered 6h, then is warming up to 650 DEG C, is sintered 12h, 5 DEG C/min of programming rate, that is, obtain Na2-2xFe1+xP2O7/ carbon composite.
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, Na2FeP2O7/ carbon composite woods Material, particle diameter 220nm, carbon thickness of net is 20nm.Initial charge specific capacity is 94mAh g-1, specific discharge capacity is 93mAh g-1, The efficiency for charge-discharge of 10 circulations is maintained at 96% or so under 1C multiplying powers.
Embodiment 4
The present embodiment comprises the following steps：
(1) the present embodiment design generation 0.03mol target products Na2-2xFe1+xP2O7/ carbon composite, prepare solution 100 mL：Weigh 1.634g glucose be dissolved in 40mL glycerin solutions (ratio of glycerine and deionized water be 1:1), claim respectively 0.06mol ammonium dihydrogen phosphate is taken, 0.03mol ferric nitrate, 0.0315mol sodium acid carbonate, is dissolved separately in going for 20mL In ionized water, stirring and dissolving.It is added dropwise to successively in the alcoholic solution of glucose according to phosphorus source, source of iron, the order of sodium source, liquid feeding Speed is 20mL/min, while is aided with and is stirred vigorously, still aging 24h after the completion of addition；
(2) mixed emulsion handled through step (1) is poured into stainless steel cauldron, reactor volume 150mL, filled Measure as 66.67%, stainless steel cauldron is put into 150 DEG C of thermostatic drying chambers and is incubated 18h, reaction naturally cools to room after terminating Temperature, reactor is taken out, separation of solid and liquid is carried out using sand core funnel.Obtained solid powder is Na2-2xFe1+xP2O7/ carbon is compound The precursor product of material；
(3) gained presoma solid product is placed in 80 DEG C of thermostatic drying chambers, obtains dry powder, will be powdered Product is transferred in crucible, under the protection of argon gas atmosphere, is warming up to 300 DEG C, is sintered 6h, then is warming up to 620 DEG C, is sintered 12h, 5 DEG C/min of programming rate, that is, obtain Na2-2xFe1+xP2O7/ carbon composite.
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, Na2-2xFe1+xP2O7/ carbon is compound Material, particle diameter 250nm, carbon thickness of net are 10nm.Initial charge specific capacity is 96mAh g-1, specific discharge capacity is 93mAh g-1, the efficiency for charge-discharge of 10 circulations is maintained at 93% or so under 1C multiplying powers.
Embodiment 5
The present embodiment comprises the following steps：
(1) the present embodiment design generation 0.03mol target products Na2-2xFe1+xP2O7/ carbon composite, prepare solution 100 mL：Weigh 1.634g glucose be dissolved in 40mL glycerin solutions (ratio of glycerine and deionized water be 1:1), claim respectively 0.06mol ammonium dihydrogen phosphate is taken, 0.03mol ferric sulfate, 0.0315mol sodium acid carbonate, is dissolved separately in going for 20mL In ionized water, stirring and dissolving.It is added dropwise to successively in the alcoholic solution of glucose according to phosphorus source, source of iron, the order of sodium source, liquid feeding Speed is 20mL/min, while is aided with and is stirred vigorously, still aging 24h after the completion of addition；
(2) mixed emulsion handled through step (1) is poured into stainless steel cauldron, reactor volume 150mL, filled Measure as 66.67%, stainless steel cauldron is put into 150 DEG C of thermostatic drying chambers and is incubated 18h, reaction naturally cools to room after terminating Temperature, reactor is taken out, separation of solid and liquid is carried out using sand core funnel.Obtained solid powder is Na2-2xFe1+xP2O7/ carbon is compound The precursor product of material；
(3) gained presoma solid product is placed in 80 DEG C of thermostatic drying chambers, obtains dry powder, will be powdered Product is transferred in crucible, under the protection of argon gas atmosphere, is warming up to 300 DEG C, is sintered 6h, then is warming up to 600 DEG C, is sintered 12h, 5 DEG C/min of programming rate, that is, obtain Na2-2xFe1+xP2O7/ carbon composite.
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, Na2-2xFe1+xP2O7/ carbon is compound The particle diameter of material is 230nm, and carbon thickness of net is 13nm.Initial charge specific capacity is 94mAh g-1, specific discharge capacity 92mAh g-1, the efficiency for charge-discharge of 10 circulations is maintained at 92% or so under 1C multiplying powers.
Reference examples 1
This reference examples design generation 0.03mol target products Na2-2xFe1+xP2O7, using traditional solid-phase synthesis：Respectively 0.06mol ammonium dihydrogen phosphate is weighed, 0.03mol ferric nitrate, 0.0315mol sodium carbonate, each raw material is put into ball grinder In, ratio of grinding media to material 6:1, using acetone as abrasive media, the ball milling 6h under conditions of 550r/min, obtained slurry is in 80 DEG C of baking ovens Middle drying, after grinding sieving, it is transferred in crucible, is warming up at 660 DEG C and sinters 12h, obtained black powder is Na2- 2xFe1+xP2O7。
The battery assembling of this reference examples resulting materials and method of testing are same as Example 1, and resulting materials particle diameter is 400nm.Initial charge specific capacity is 60mAh g-1, specific discharge capacity is 65mAh g-1, the charge and discharge of 10 circulations under 1C multiplying powers Electrical efficiency is maintained at 91% or so.
Reference examples 2
(1) this reference examples design generation 0.03mol target products Na2-2xFe1+xP2O7, prepare solution 100mL：Weigh respectively 0.06mol ammonium dihydrogen phosphate, 0.03mol ferric nitrate, 0.0315mol sodium carbonate, it is dissolved separately in 20mL deionization In water, stirring and dissolving.Phosphorus source, sodium source solution are added dropwise in source of iron solution successively, are settled to 100mL, while be aided with play Strong stirring, still aging 24h after the completion of addition；
(2) mixed emulsion handled through step (1) is poured into stainless steel cauldron, reactor volume 150mL, filled Measure as 66.67%, stainless steel cauldron is put into 150 DEG C of thermostatic drying chambers and is incubated 18h, reaction naturally cools to room after terminating Temperature, reactor is taken out, separation of solid and liquid is carried out using sand core funnel.
(3) gained presoma solid product is placed in 80 DEG C of thermostatic drying chambers, obtains dry powder, will be powdered Product is transferred in crucible, under the protection of argon gas atmosphere, is warming up to 300 DEG C, is sintered 6h, then is warming up to 600 DEG C, is sintered 12h, 5 DEG C/min of programming rate, is produced.
The battery assembling of this reference examples resulting materials and method of testing are same as Example 1, and resulting materials particle diameter is 400nm.Initial charge specific capacity is 65mAh g-1, specific discharge capacity is 50mAh g-1, the charge and discharge of 10 circulations under 1C multiplying powers Electrical efficiency is maintained at 80% or so.
Reference examples 3
This reference examples comprises the following steps：
(1) the present embodiment design generation 0.03mol target products Na2-2xFe1+xP2O7, prepare solution 100mL：Weigh 0.827 g glucose be dissolved in 40mL ethylene glycol solutions (ratio of ethylene glycol and deionized water be 1:1), weigh respectively 0.06mol ammonium dihydrogen phosphate, 0.03mol ferric nitrate, 0.0315mol sodium carbonate, it is dissolved separately in 20mL deionization In water, stirring and dissolving.It is added dropwise to successively in the alcoholic solution of glucose according to sodium source, source of iron, the order of phosphorus source, liquid feeding speed For 15 mL/min, while it is aided with and is stirred vigorously, still aging 24h after the completion of addition；
(2) mixed emulsion handled through step (1) is poured into stainless steel cauldron, reactor volume 150mL, filled Measure as 66.67%, stainless steel cauldron is put into 150 DEG C of thermostatic drying chambers and is incubated 18h, reaction naturally cools to room after terminating Temperature, reactor is taken out, separation of solid and liquid is carried out using sand core funnel.
(3) gained presoma solid product is placed in 80 DEG C of thermostatic drying chambers, obtains dry powder, will be powdered Product is transferred in crucible, under the protection of argon gas atmosphere, is warming up to 300 DEG C, is sintered 6h, then is warming up to 600 DEG C, is sintered 12h, 5 DEG C/min of programming rate, is produced.
The battery assembling of this reference examples resulting materials and method of testing are same as Example 1, and resulting materials dephasign is more, first Charge specific capacity is 20mAh g-1, specific discharge capacity is 10mAh g-1。

Claims (9)

  1. A kind of 1. Na2-2xFe1+xP2O7The preparation method of/carbon composite, it is characterised in that comprise the following steps：
    (1) carbon source is dissolved in deionized water or alcoholic solution；Source of iron, phosphorus source, sodium source are dissolved separately in deionized water, stirred Mix uniformly, be added dropwise to successively according to source of iron, phosphorus source, the order of sodium source in the solution dissolved with carbon source, obtain mixed solution；
    (2) gained mixed solution is placed in autoclave, hydro-thermal reaction, cooling, solid-liquid point is carried out in 100 DEG C~300 DEG C From it is in neutrality to be washed with absolute ethyl alcohol to eluate, is dried, gained solid product is Na2-2xFe1+xP2O7/ carbon composite Presoma；
    (3) presoma obtained by step (2) is first sintered under inert atmosphere protection at 250~350 DEG C, then is warming up to 500~700 DEG C sintering, produce Na2-2xFe1+xP2O7/ carbon composite.
  2. 2. preparation method according to claim 1, it is characterised in that sodium source described in step (1) is sodium carbonate, bicarbonate At least one of sodium, sodium acetate, sodium oxalate, sodium nitrate, sodium sulphate, sodium citrate or sodium thiosulfate；The source of iron is nitre Sour iron, iron chloride, ferrous oxalate, ferrous sulfate, ferric sulfate, ironic citrate, ferric citrate, ferric ammonium sulfate or ferrous sulfate At least one of ammonium；Phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid or pyrophosphoric acid；It is described Carbon source is at least one of citric acid, ascorbic acid, glucose, sucrose, polyvinyl alcohol or polyethylene glycol.
  3. 3. preparation method according to claim 1, it is characterised in that sodium in sodium source, source of iron and phosphorus source described in step (1) The mol ratio of element, ferro element and P elements is 2~2.2:0.8~1.05:2.
  4. 4. preparation method according to claim 1, it is characterised in that the quality and Na of the carbon source2-2xFe1+xP2O7Matter Amount is than being 0.05~0.2:1.
  5. 5. preparation method according to claim 1, it is characterised in that alcoholic solution described in step (1) be methanol aqueous solution, At least one of ethanol water, glycol water or glycerin solution；The volume of alcohol and deionized water in alcoholic solution Than for 1:0.5~2.
  6. 6. preparation method according to claim 1, it is characterised in that in the step (2) time of hydro-thermal reaction be 5~ 36h。
  7. 7. according to the preparation method described in claim 1~6 any one, it is characterised in that the Na2-2xFe1+xP2O7/ carbon is multiple Condensation material is the Na of coated with carbon stratum reticulare2-2xFe1+xP2O7The scope of material, wherein x is 0~1.
  8. 8. preparation method according to claim 7, it is characterised in that the Na2-2xFe1+xP2O7/ carbon composite crystal formation For reddingite type, the particle diameter of composite is 10~500nm.
  9. 9. preparation method according to claim 7, it is characterised in that the thickness of the carbon stratum reticulare is 5~20nm.
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CN106340650B (en) * 2016-11-09 2019-05-03 中南大学 It a kind of preparation method of ferric sodium pyrophosphate and its is applied in sodium-ion battery
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CN108123129A (en) * 2018-01-04 2018-06-05 中南大学 A kind of carbon coating ferric sodium pyrophosphate material and preparation method thereof and the application as sodium-ion battery positive material
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