CN107123796A - A kind of violent sodium composite of carbon coating vanadium phosphate and preparation method thereof and the application in sodium-ion battery - Google Patents

A kind of violent sodium composite of carbon coating vanadium phosphate and preparation method thereof and the application in sodium-ion battery Download PDF

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CN107123796A
CN107123796A CN201710330057.1A CN201710330057A CN107123796A CN 107123796 A CN107123796 A CN 107123796A CN 201710330057 A CN201710330057 A CN 201710330057A CN 107123796 A CN107123796 A CN 107123796A
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mnv
sodium
composite
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manganese
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张治安
陈晓彬
赖延清
肖志伟
李煌旭
尚国志
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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
    • H01M4/366—Composites as layered products
    • 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
    • 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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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a kind of Na4MnV(PO4)3/ C composite and preparation method thereof and the application in sodium-ion battery, Na4MnV(PO4)3/ C composite is by carbon coating Na4MnV(PO4)3Particle is constituted；Its synthetic method is to serve as reducing agent and carbon source using organic matter, using cheap sodium source, manganese source and vanadium source, passes through a step solid phase method, synthesis carbon coating Na4MnV(PO4)3Composite positive pole, the preparation method is simple and easy to apply, mild condition, and yield is high, when the composite of preparation is applied as sodium-ion battery positive material, shows height ratio capacity, high working voltage, good stable circulation performance and excellent high rate performance.

Description

A kind of violent sodium composite of carbon coating vanadium phosphate and preparation method thereof and sodium ion electricity Application in pond
Technical field
The present invention relates to a kind of sodium-ion battery positive material, more particularly to a kind of carbon coating Na4MnV(PO4)3Constitute Composite and synthesis in solid state Na4MnV(PO4)3/ C method, and Na4MnV(PO4)3/ C should as sodium ion positive electrode With belonging to sodium-ion battery field.
Background technology
As lithium ion battery has achieved fast development in 3C Product and electric automobiles, and show good hair While exhibition prospect, because metal lithium resource is in the scarcity of crustal abundance, lithium ion battery is difficult to meet in large-scale energy storage field In large-scale application, its manufacturing cost also will be in the trend that constantly rises with the scarcity of lithium resource.Compared with elemental lithium, sodium member Element rich reserves and source is more extensive in the earth's crust, and sodium element is in same main group with lithium in the periodic table of elements, so There is similar physicochemical property to lithium.Therefore, the manufacturing cost of relative moderate and the sodium ion electricity compared favourably with lithium ion battery Pond turns into a kind of usable battery system of storage on a large scale of most potential achievable industry.However, due to the ion of sodium ion Radius is bigger than the ionic radius of lithium ion so that in kinetically sodium ion, lithium ion is compared in embedded and abjection in electrode material It is more difficult, and sodium ion is with respect to the oxidation-reduction potential and larger atomic mass of calibration so that sodium-ion battery positive pole material The low voltage of material, energy density is not high.Therefore, improve sodium-ion battery positive material voltage and turning into for energy density is studied Emphasis.
Similar with lithium ion battery, in sodium-ion battery positive material, relatively more representational is P2 types and O3 types layer Shape oxide system, such as P2-Na2/3[Fe1/2Mn1/2]O2, O3-NaFe0.5Co0.5O2, but stratified material in organic electrolyte not It is stable, easily decompose under high voltages, cause cycle performance of battery poor.In polyanionic positive electrode system, Na2Fe2(SO4)3Theoretical plates with 3.8V, with the platform compared favourably with lithium ion battery but due to sulfate system tool There is hygroscopicity easily to cause material surface poisoning effect, result in material preparation process and harsh, material is required to production environment Can be unstable the problems such as.Phosphate system has three-dimensional crystalline structure, with good heat endurance and electrochemical stability, but Be material voltage it is relatively low relative to sulfate system.Vanadium source is expensive, and crustal abundance is low, and the manganese source that compares has price low It is honest and clean, wide material sources.The manufacturing cost of sodium-ion battery can be effectively reduced using the phosphate cathode material of manganese base.
The content of the invention
The defect existed for sodium-ion battery material in the prior art, it is an object of the invention to provide one kind cladding is equal Even, property is stable, the Na that crystalline phase is single and electro-chemical activity is high4MnV(PO4)3/ C composite.
Another object of the present invention is to provide a kind of mild condition, preparation Na simple to operate, with low cost4MnV (PO4)3The method of/C composite, this method can realize large-scale production.
Third object of the present invention is to be to provide the Na4MnV(PO4)3/ C composite is applied as sodium ion electricity The application of pond positive electrode, sodium-ion battery show high-energy-density, high working voltage, good stable circulation performance and Excellent high rate performance.
In order to realize above-mentioned technical purpose, the invention provides a kind of Na4MnV(PO4)3/ C composite, it is by carbon coating Na4MnV(PO4)3Particle is constituted.Technical scheme produces carbon original position by organic matter pyrolysis and is evenly coated at Na4MnV (PO4)3Particle surface, improves Na4MnV(PO4)3The electron conduction of granular material surface, makes composite have well High rate performance.Meanwhile, carbon coating improves the interface stability between active material and electrolyte, can effectively improve battery Cycle life.
It is preferred that scheme, Na4MnV(PO4)3Grain diameter is 70~2000nm.
It is preferred that scheme, Na4MnV(PO4)3The carbon coating layer thickness of particle is 3~50nm.
It is preferred that scheme, Na4MnV(PO4)3With trigonal system, space group is R3c.Na with the crystal structure4MnV (PO4)3For NASICON (fast-ionic conductor) type, the quick transmission of sodium ion can be realized, so that with good high rate performance.
Present invention also offers a kind of Na4MnV(PO4)3The preparation method of/C composite, this method is by sodium source, phosphorus After source, vanadium source, manganese source and carbon source ball milling mixing, it is placed in protective atmosphere, is first warming up to 350~450 DEG C of sintering, then be warming up to 700~850 DEG C of sintering, are produced.
It is preferred that scheme, sodium source, phosphorus source, the consumption of vanadium source and manganese source press Na:P:V:Mn mol ratio is 3.5~4.2:3: 0.8~1.2:0.8~1.2 metering.Preferred mol ratio is 3.9~4.05:3:1:1.
It is preferred that scheme, the consumption of the carbon source for generation Na4MnV(PO4)3The 5% of/C composite quality~ 300%；More preferably 5%~150%.The consumption of carbon source decides the thickness of carbon coating layer, and coating thickness is in suitable model In enclosing, be conducive to obtaining that stability is good, electrochemical performance Na4MnV(PO4)3/ C composite.
It is preferred that scheme, the sodium source include sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium nitrate, sodium sulphate, sulphur At least one of sour hydrogen sodium, sodium citrate.Preferred sodium source is sodium carbonate.
It is preferred that scheme, phosphorus source include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, disodium hydrogen phosphate, biphosphate At least one of sodium.Preferred phosphorus source is ammonium dihydrogen phosphate.
It is preferred that scheme, the vanadium source include vanadic anhydride, ammonium metavanadate, vanadium acetylacetonate, vanadyl acetylacetonate in It is at least one.Preferred vanadium source is vanadic anhydride.
It is preferred that scheme, the manganese source include manganese monoxide, manganese dioxide, mangano-manganic oxide, manganese sulfate, protochloride manganese, At least one of manganese oxalate, manganese nitrate.Preferred manganese source is manganese dioxide.
It is preferred that scheme, the carbon source include glucose, starch, citric acid, ascorbic acid, polyvinyl alcohol, polyoxyethylene At least one of alkene, poly-dopamine, polyacrylonitrile.
It is preferred that scheme, the condition of the ball milling is：Ball material mass ratio is 30~100:1；Engine speed be 300~ 1200r/min, Ball-milling Time is 6~24h.Preferred ball material mass ratio is 50~70:1.Preferred engine speed is 400 ~800r/min, Ball-milling Time is 8~14h.
More preferably scheme, described ball milling is carried out in organic solvent medium.More preferably acetone, absolute ethyl alcohol etc., These organic solvents have more preferable wetability to various solid principles, ball milling mixing effect are improved, so that it is more preferable to obtain purity Product.
It is preferred that scheme, after sodium source, phosphorus source, vanadium source, manganese source and carbon source ball milling mixing, done at a temperature of being placed in 80~120 DEG C It is dry, 100~400 mesh sieves are crossed, take minus sieve powder to be sintered.
It is preferred that scheme, be 3~6h in the times of 350~450 DEG C of sintering, 700~850 DEG C of sintering times for 9~ 24h, heating rate is 2~10 DEG C/min.Preferred scheme, 3~5h is sintered at 350~400 DEG C, in 750~800 DEG C of sintering Time be 10~14h, heating rate be 4~6 DEG C/min.By controlling sintering temperature and time and heating rate, it can obtain Dephasign is less, perfect crystalline, the moderate Na of particle size3MnV(PO4)3/ C composite, is conducive to improving leading for composite Electrical and other electric properties.
The protective atmosphere of the present invention can be high pure nitrogen or high-purity argon gas or their mixed gas.
Present invention also offers Na4MnV(PO4)3The application of/C composite, as sodium ion positive electrode application.
The Na of the present invention4MnV(PO4)3/ C composite is applied and used prior approach to as sodium-ion battery positive material Sodium-ion battery is assembled into, and its performance is tested：Weigh above-mentioned Na4MnV(PO4)3/ C composite, adds 10wt.% Conductive carbon black as conductive agent, 10wt.%PVDF as binding agent, it is ground fully after add a small amount of NMP and be mixed to form Even black paste slurry, these slurries is coated in aluminum foil current collector as electrode is tested, with metallic sodium piece as a comparison Electrode assembling turns into button cell, and it uses electrolyte system for 1M NaClO4/PC.Discharge and recharge electricity used in test loop performance Current density is 100mAh g-1(1C multiplying powers).
Compared with prior art, the advantageous effects that technical scheme is brought：
The Na of the present invention4MnV(PO4)3/ C composite has special carbon coating structure, makes Na4MnV(PO4)3Material is steady Qualitative to improve, electric conductivity increase improves its electro-chemical activity.
The Na of the present invention4MnV(PO4)3Active material Na in/C composite4MnV(PO4)3Tripartite's phase with high-purity, Stability is good, and electro-chemical activity is high.
The Na of the present invention4MnV(PO4)3/ C composite uses Solid phase synthesis, using ball milling mixing combination sinter molding Method synthesis Na4MnV(PO4)3/ C composite, improves the contact between solid material by high-energy ball milling, makes reaction more Plus fully, the generation of impurities phase is reduced, it is molded by the method for step sintering, is conducive to improving plane of crystal performance, improves brilliant Body integrality, while improving being evenly coated property, granular size homogeneity.
The Na of the present invention4MnV(PO4)3Na in the preparation method of/C composite4MnV(PO4)3With the generation of carbon, and carbon To Na4MnV(PO4)3Cladding, the one-step shaping in sintering process enormously simplify processing step.
The Na of the present invention4MnV(PO4)3/ C composite has good high rate performance and excellent cycle performance, 3.4V Make material that there is higher power density with two discharge platforms of 3.6V.
The Na of the present invention4MnV(PO4)3The preparation process of/C composite uses cheap sodium source, phosphorus source, titanium source, manganese source And carbon source is prepared for pure phase Na as raw material by solid-phase ball milling4MnV(PO4)3/ C composite, reduces cost.
The Na of the present invention4MnV(PO4)3/ C composite is evenly coated, and cladding thickness is moderate, and cladding means are simple.
The Na of the present invention4MnV(PO4)3When/C composite is applied as sodium-ion battery positive material, high energy is shown Metric density, high working voltage, good stable circulation performance and excellent high rate performance.
Brief description of the drawings
【Fig. 1】It is Na prepared by embodiment 14MnV(PO4)3The X-ray diffractogram of/C composite；
【Fig. 2】It is Na prepared by embodiment 14MnV(PO4)3The scanning electron microscope (SEM) photograph of/C composite；
【Fig. 3】It is Na prepared by embodiment 14MnV(PO4)3The charging and discharging curve figure of/C composite.
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：
Step (1)：The present embodiment design generation 0.03mol target products Na4MnV(PO4)3/ C composite, will 0.06075mol sodium carbonate, 0.09mol ammonium dihydrogen phosphates, 0.015mol vanadic anhydrides, 0.03mol manganese dioxide, 1.45g Portugals Grape sugar, adds 1400g zirconium oxide ball milling pearls, adds a certain amount of acetone and is used as abrasive media；
Step (2)：The ball milling 12h under rotating speed 600r/min, is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~ 400 mesh sieves, obtain Na4MnV(PO4)3/ C composite presoma；
Step (3)：Presoma obtained by step (2) is sintered into 4h under 350 DEG C, high-purity argon gas atmosphere, then is warming up to 750 DEG C sintering 12h, programming rate：5 DEG C/min, Na can be obtained after natural cooling4MnV(PO4)3/ C composite；
Button cell is assembled into using sodium-ion battery composite positive pole manufactured in the present embodiment and sodium piece, its material list Chemical property seek peace as shown in the figure：
Fig. 1 shows to successfully synthesize Na4MnV(PO4)3/ C composite.
The Na of the visible synthesis of Fig. 24MnV(PO4)3/ C composite, particle diameter distribution is uniform, and average grain diameter is 800nm, carbon bag Coating thickness about 10nm.
Fig. 3 is Na4MnV(PO4)3/ C composite is assembled into button cell charge specific capacity under 1C multiplying powers with sodium piece 70mAh g-1, specific discharge capacity is 68mAh g-1。
Embodiment 2
The present embodiment comprises the following steps：
Step (1)：The present embodiment design generation 0.03mol target products Na4MnV(PO4)3/ C composite, will 0.06mol sodium carbonate, 0.09mol ammonium dihydrogen phosphates, 0.015mol vanadic anhydrides, 0.03mol manganese dioxide, 1.45g grapes Sugar, adds 1400g zirconium oxide ball milling pearls, adds a certain amount of acetone and is used as abrasive media；
Step (2)：The ball milling 12h under rotating speed 600r/min, is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~ 400 mesh sieves, obtain Na4MnV(PO4)3/ C composite presoma；
Step (3)：Presoma obtained by step (2) is sintered into 4h under 350 DEG C, high-purity argon gas atmosphere, then is warming up to 800 DEG C sintering 12h, programming rate：5 DEG C/min, Na can be obtained after natural cooling4MnV(PO4)3/ C composite；
The battery assembling of the present embodiment resulting materials and method of testing are same as Example 1, Na4MnV(PO4)3/ C composite woods Material average grain diameter is 800nm, carbon coating layer thickness about 11nm.Initial charge specific capacity is 71mAh g-1, specific discharge capacity is 69mAh g-1。
Embodiment 3
Step (1)：The present embodiment design generation 0.03mol target products Na4MnV(PO4)3/ C composite, will 0.12mol sodium acid carbonates, 0.09mol ammonium dihydrogen phosphates, 0.014mol vanadic anhydrides, 0.03mol manganese dioxide, 1.45g Portugals Grape sugar, adds 1400g zirconium oxide ball milling pearls, adds a certain amount of acetone and is used as abrasive media；
Step (2)：The ball milling 12h under rotating speed 600r/min, is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~ 400 mesh sieves, obtain Na4MnV(PO4)3/ C composite presoma；
Step (3)：Presoma obtained by step (2) is sintered into 6h under 400 DEG C, high-purity argon gas atmosphere, then is warming up to 750 DEG C sintering 18h, programming rate：5 DEG C/min, Na can be obtained after natural cooling4MnV(PO4)3/ C composite.
The battery assembling of this present embodiment resulting materials and method of testing are same as Example 1, Na4MnV(PO4)3/ C is combined Material average grain diameter is 1000nm, carbon coating layer thickness about 9nm.Initial charge specific capacity is 68mAh g-1, specific discharge capacity is 66mAh g-1。
Embodiment 4
The present embodiment comprises the following steps：
Step (1)：The present embodiment design generation 0.03mol target products Na4MnV(PO4)3/ C composite, will 0.06075mol sodium carbonate, 0.09mol ammonium dihydrogen phosphates, 0.015mol vanadic anhydrides, 0.03mol manganese dioxide, 1.45g gather Acrylonitrile, adds 1400g zirconium oxide ball milling pearls, adds a certain amount of acetone and is used as abrasive media；
Step (2)：The ball milling 12h under rotating speed 600r/min, is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~ 400 mesh sieves, obtain Na4MnV(PO4)3/ C composite presoma；
Step (3)：Presoma obtained by step (2) is sintered into 4h under 350 DEG C, high-purity argon gas atmosphere, then is warming up to 850 DEG C sintering 12h, programming rate：5 DEG C/min, Na can be obtained after natural cooling4MnV(PO4)3/ C composite；
The battery assembling of this present embodiment resulting materials and method of testing are same as Example 1, Na4MnV(PO4)3/ C is combined Material average grain diameter is 1200nm, carbon coating layer thickness about 12nm.Initial charge specific capacity is 63mAh g-1, specific discharge capacity is 58mAh g-1。
Comparative example 1
Starting material element content is adjusted to Na:P:V:Mn mol ratio is 5.33:3:1:1
Step (1)：The present embodiment design generation 0.03mol target products Na4MnV(PO4)3/ C composite, will 0.08mol sodium carbonate, 0.09mol ammonium dihydrogen phosphates, 0.015mol vanadic anhydrides, 0.03mol manganese dioxide, 1.45g grapes Sugar, adds 1400g zirconium oxide ball milling pearls, adds a certain amount of acetone and is used as abrasive media；
Step (2)：The ball milling 12h under rotating speed 600r/min, is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~ 400 mesh sieves, obtain Na4MnV(PO4)3/ C composite presoma；
Step (3)：Presoma obtained by step (2) is sintered into 4h under 350 DEG C, high-purity argon gas atmosphere, then is warming up to 750 DEG C sintering 12h, programming rate：5 DEG C/min, Na can be obtained after natural cooling4MnV(PO4)3/ C composite.
This comparative example resulting materials have a variety of phosphate dephasigns, and material electrochemical performance is poor, initial charge specific capacity For 28mAh g-1, specific discharge capacity is 24mAh g-1。
Comparative example 2
Sintering schedule is changed into：4h is sintered under 350 DEG C of high-purity argon gas atmosphere, then is warming up to 600 DEG C of sintering 12h, heating Speed：5℃/min
Step (1)：The present embodiment design generation 0.03mol target products Na4MnV(PO4)3/ C composite, will 0.06mol sodium carbonate, 0.09mol ammonium dihydrogen phosphates, 0.015mol vanadic anhydrides, 0.03mol manganese dioxide, 1.45g grapes Sugar, adds 1400g zirconium oxide ball milling pearls, adds a certain amount of acetone and is used as abrasive media；
Step (2)：The ball milling 12h under rotating speed 600r/min, is placed in 80 DEG C of baking ovens and dries, excessively 100 after crushing grinding~ 400 mesh sieves, obtain Na4MnV(PO4)3/ C composite presoma；
Step (3)：Presoma obtained by step (2) is sintered into 4h under 350 DEG C, high-purity argon gas atmosphere, then is warming up to 600 DEG C sintering 12h, programming rate：5 DEG C/min, Na can be obtained after natural cooling4MnV(PO4)3/ C composite.
This comparative example resulting materials are not Na4MnV(PO4)3Phase, material electrochemical performance is poor, it is impossible to 3.6V and 3.4V occur Characteristic discharge platform.

Claims (10)

1. a kind of Na4MnV(PO4)3/ C composite, it is characterised in that：By carbon coating Na4MnV(PO4)3Particle is constituted.
2. Na according to claim 14MnV(PO4)3/ C composite, it is characterised in that：Na4MnV(PO4)3Grain diameter For 70~2000nm, carbon coating layer thickness is 3~50nm, Na4MnV(PO4)3With trigonal system, space group is
3. the Na described in claim 1 or 24MnV(PO4)3The preparation method of/C composite, it is characterised in that：By sodium source, phosphorus After source, vanadium source, manganese source and carbon source ball milling mixing, it is placed in protective atmosphere, is first warming up to 350~450 DEG C of sintering, then be warming up to 700~850 DEG C of sintering, are produced.
4. Na according to claim 34MnV(PO4)3The preparation method of/C composite, it is characterised in that：Sodium source, phosphorus The consumption in source, vanadium source and manganese source presses Na:P:V:Mn mol ratio is 3.5~4.2：3:0.8~1.2：0.8~1.2 metering；
The consumption of the carbon source is the Na of generation4MnV(PO4)3The 5%~300% of/C composite quality.
5. Na according to claim 44MnV(PO4)3The preparation method of/C composite, it is characterised in that：The sodium source Including at least one of sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium nitrate, sodium sulphate, niter cake, sodium citrate；
Phosphorus source includes at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, disodium hydrogen phosphate, sodium dihydrogen phosphate；
The vanadium source includes at least one of vanadic anhydride, ammonium metavanadate, vanadium acetylacetonate, vanadyl acetylacetonate；The manganese Source includes at least one of manganese monoxide, manganese dioxide, mangano-manganic oxide, manganese sulfate, protochloride manganese, manganese oxalate, manganese nitrate；
The carbon source includes glucose, starch, citric acid, ascorbic acid, polyvinyl alcohol, polyethylene glycol oxide, poly-dopamine, poly- third At least one of alkene nitrile.
6. the Na according to any one of claim 3~54MnV(PO4)3The preparation method of/C composite, it is characterised in that： The condition of the ball milling is：Ball material mass ratio is 30~100:1；Engine speed be 300~1200r/min, Ball-milling Time be 6~ 24h。
7. Na according to claim 64MnV(PO4)3The preparation method of/C composite, it is characterised in that：Described ball Mill is carried out in organic solvent medium.
8. the Na according to claim 3~5,7 any one4MnV(PO4)3The preparation method of/C composite, its feature exists In：After sodium source, phosphorus source, vanadium source, manganese source and carbon source ball milling mixing, dried at a temperature of being placed in 80~120 DEG C, cross 100~400 mesh Sieve, takes minus sieve powder to be sintered.
9. the Na according to claim 3~5,7 any one4MnV(PO4)3The preparation method of/C composite, its feature exists In：350~450 DEG C sintering times be 3~6h, 700~850 DEG C sintering times be 9~24h, heating rate be 2~ 10℃/min。
10. the Na described in claim 1 or 24MnV(PO4)3The application of/C composite, it is characterised in that：As sodium ion just Pole materials application.
CN201710330057.1A 2017-05-11 2017-05-11 A kind of violent sodium composite of carbon coating vanadium phosphate and preparation method thereof and the application in sodium-ion battery Pending CN107123796A (en)

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CN107978743A (en) * 2017-11-20 2018-05-01 中南大学 A kind of sodium-ion battery positive material and preparation method thereof, sodium-ion battery
CN108063247A (en) * 2017-12-23 2018-05-22 清远佳致新材料研究院有限公司 A kind of method that compound manganese ore prepares manganate cathode material for lithium
CN109437142A (en) * 2018-10-16 2019-03-08 江西理工大学 A kind of richness sodium sodium-ion battery positive material and preparation method thereof
CN111747394A (en) * 2020-07-07 2020-10-09 同济大学 NASICON type high-performance fluorophosphate and sodium ion battery
CN112242525A (en) * 2020-10-19 2021-01-19 中南大学 Nitrogen-doped carbon-coated vanadium manganese sodium phosphate composite material and preparation method and application thereof
CN112421040A (en) * 2020-11-16 2021-02-26 中国科学院过程工程研究所 Phosphate anode material and preparation method and application thereof
CN112429712A (en) * 2020-11-03 2021-03-02 桂林理工大学 Phosphate Na4FeV (PO) with NASICON structure4)3Method for synthesizing material and application thereof
CN114156452A (en) * 2021-11-30 2022-03-08 上海瑞浦青创新能源有限公司 Sodium ion positive electrode material and preparation method and application thereof
CN114824216A (en) * 2022-04-28 2022-07-29 武汉工程大学 Multielement-doped sodium-ion battery positive electrode material and preparation method and application thereof
CN115084502A (en) * 2022-05-13 2022-09-20 福州大学 NASICON type structure ternary sodium ion battery positive electrode material, preparation method and application thereof
CN116741975A (en) * 2023-08-15 2023-09-12 北京理工大学 Double-carbon-layer heterogeneous composite positive electrode material, preparation method thereof and sodium ion battery

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107978743A (en) * 2017-11-20 2018-05-01 中南大学 A kind of sodium-ion battery positive material and preparation method thereof, sodium-ion battery
CN108063247A (en) * 2017-12-23 2018-05-22 清远佳致新材料研究院有限公司 A kind of method that compound manganese ore prepares manganate cathode material for lithium
CN109437142A (en) * 2018-10-16 2019-03-08 江西理工大学 A kind of richness sodium sodium-ion battery positive material and preparation method thereof
CN111747394A (en) * 2020-07-07 2020-10-09 同济大学 NASICON type high-performance fluorophosphate and sodium ion battery
CN112242525A (en) * 2020-10-19 2021-01-19 中南大学 Nitrogen-doped carbon-coated vanadium manganese sodium phosphate composite material and preparation method and application thereof
CN112429712A (en) * 2020-11-03 2021-03-02 桂林理工大学 Phosphate Na4FeV (PO) with NASICON structure4)3Method for synthesizing material and application thereof
CN112421040A (en) * 2020-11-16 2021-02-26 中国科学院过程工程研究所 Phosphate anode material and preparation method and application thereof
CN114156452A (en) * 2021-11-30 2022-03-08 上海瑞浦青创新能源有限公司 Sodium ion positive electrode material and preparation method and application thereof
CN114824216A (en) * 2022-04-28 2022-07-29 武汉工程大学 Multielement-doped sodium-ion battery positive electrode material and preparation method and application thereof
CN115084502A (en) * 2022-05-13 2022-09-20 福州大学 NASICON type structure ternary sodium ion battery positive electrode material, preparation method and application thereof
CN116741975A (en) * 2023-08-15 2023-09-12 北京理工大学 Double-carbon-layer heterogeneous composite positive electrode material, preparation method thereof and sodium ion battery
CN116741975B (en) * 2023-08-15 2023-12-01 北京理工大学 Double-carbon-layer heterogeneous composite positive electrode material, preparation method thereof and sodium ion battery

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