CN105720247B - A kind of preparation method of lithium sodium hybrid ionic battery composite anode material - Google Patents

A kind of preparation method of lithium sodium hybrid ionic battery composite anode material Download PDF

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CN105720247B
CN105720247B CN201610076388.2A CN201610076388A CN105720247B CN 105720247 B CN105720247 B CN 105720247B CN 201610076388 A CN201610076388 A CN 201610076388A CN 105720247 B CN105720247 B CN 105720247B
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lithium
feo
anode material
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CN105720247A (en
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张旭东
何文
徐小龙
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Qilu University of Technology
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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
    • 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
    • H01M4/5825—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
    • H01M4/36—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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 present invention relates to a kind of preparation method of lithium sodium hybrid ionic battery composite anode material, this method uses high energy phosphate compound Na2ATP is stay in place form and introduces sodium source, phosphorus source and carbon source, and a kind of new composite L i has been synthesized by biochemistry synthetic method, Freeze Drying Technique and carbon thermal reduction technology3V2(PO4)3/Na4FeO3/C60.The material not only has good chemical property, and can be used for lithium sodium hybrid ionic battery as positive electrode from increased characteristic with overdischarge self-shield and high rate cyclic specific capacity.

Description

A kind of preparation method of lithium-sodium hybrid ionic battery composite anode material
Technical field
The present invention relates to one kind to have good chemical property and overdischarge self-shield and high-multiplying power discharge specific capacity from increasing Phosphoric acid vanadium lithium/(Li of sodium ferrite/carbon 60 of additivity energy3V2(PO4)3/Na4FeO3/C60) lithium-sodium hybrid ionic cell positive material Preparation method, belong to lithium-sodium hybrid ionic cell positive material technical field.
Background technology
Phosphoric acid vanadium lithium is NASICON structures, has two kinds of crystal formations of monocline and rhombus.Phosphoric acid vanadium lithium structure is by vanadium oxygen octahedra Sharing oxygen atom with phosphoric acid tetrahedron, summit link forms altogether, and the connected mode of two kinds of structures and the position of lithium ion are present Difference.In rhombus vanadium phosphate crystalline lithium structure, lithium ion occupies two different positions：When the lithium ion content in structure compared with When low, lithium ion occupies a tetrahedron space A (1)；When lithium ion content is higher, lithium ion can optionally occupy A (1) Or other three octahedra spaces.Unlimited 3d space structure can make lithium ion freely between A (1) and A (2) position Migration.In monoclinic lithium vanadium phosphate structure, each vanadium oxygen octahedra is surrounded by six phosphorus oxygen tetrahedrons, and each phosphorus oxygen tetrahedron is by four Individual vanadium oxygen octahedra surrounds, and this configuration forms a tridimensional network using A2B3 as unit, and lithium is embedded in the hole of framework In.Include three PO in phosphoric acid vanadium lithium molecule4Tetrahedron, two VO6Octahedra and three lithium ions, wherein Li (1) occupy one Individual tetrahedral interstice, Li (2) and Li (3) are in occupation of the tetrahedral interstice of serious distortion in framework, because this tetrahedron possesses One longer Li-O key.
Sodium ferrite (Na4FeO3) there is good heat endurance, its synthesis in solid state temperature is 450 DEG C, less than phosphoric acid vanadium lithium Form temperature.Sodium ferrite and phosphoric acid vanadium lithium are subjected to the compound thermostabilization for improving cell positive material in charge and discharge process Property.Due to Fe2+Presence cause battery material Fe in charge and discharge process2+/Fe3+Redox reaction occurs for redox couple, Therefore sodium ferrite also has certain charge/discharge capacity.
M.S.KLochko etc. (Low Temp.Phys., 2015,41,488) has reported C60Due to its unique molecular structure It is high and the advantages of electron conduction is good with electro-chemical activity with quantum size effect.C60As a kind of crystal carbon material, by There is good electron conduction in the presence of pi bond, can be effectively by improving anode material in battery charge and discharge process The electric conductivity of material and reduce the activation polarization of electrode.C.X.Cui etc. (J.Phys.Chem.A, 2015,119,3098) is demonstrated Metal ion can be embedded in C60Nanocages, C60Nanocages can be opened and carry out the storage of lithium ion and sodium ion, further Improve the charging and discharging capacity of material.
Although lithium ion battery has been commercially produced at present, also there is cost height, there must be special protection Circuit, to prevent from overcharging or cross the deficiencies of putting；And the sodium-ion battery just risen cost compared with lithium ion battery is low, security It is good, but with the shortcomings that reversible capacity is low, energy density is low, cyclical stability is poor.According to the market demand of secondary cell, it is badly in need of New positive electrode is researched and developed, further improves the chemical property of phosphoric acid vanadium lithium, reduces cost, improves material in use Security, so as to meet needs of the new energy field to secondary battery material.
The content of the invention
For insufficient existing for existing lithium ion battery material and sodium-ion battery material, the present invention provides a kind of with good Good chemical property and overdischarge self-shield and high rate capability are from increased lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method.The present invention is to use immature earthen sites, passes through freeze-drying and carbon thermal reduction Technology will contain lithium ion phase and be carried out with sodium ion phase and carbon 60 compound, and the composite of synthesis can be used as lithium-sodium hybrid ionic The positive electrode of battery.
Term explanation
Lithium-sodium hybrid ionic battery：Existing lithium ion deintercalation has sodium ion deintercalation again on electrode in charge and discharge process Battery.
High energy phosphate compound：Refer to that the energy that discharges is in more than 20.92kJ/moL phosphate cpd during hydrolysis.
Technical scheme is as follows：
A kind of lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including Step is as follows：
(1) the high energy phosphate compound aqueous solution is cultivated under the conditions of 30~50 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1:(1/2~2), solution source of iron solution being added to obtained by step (1) In, pH=2~4 are adjusted, are stirred, is centrifuged after still aging, obtains sediment；
(3) deionized water is added in the sediment obtained to step (2), according to mol ratio Fe:V=1:(1/3~3), Vanadium source is added under stirring condition, stirs, obtains turbid；
(4) the turbid low temperature drying for obtaining step (3), obtains powder；According to mol ratio Fe:Li=1:(1/4~2) is to powder Lithium source is added in end, according to mol ratio Fe:C=(5~2)：1 adds carbon source, mixing and ball milling, obtains presoma；
(5) by presoma made from step (4) under nitrogen protection, 600~800 DEG C are warming up to and is heat-treated, at heat Natural cooling after the completion of reason, produce lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60。
, according to the invention it is preferred to, the high energy phosphate compound described in step (1) is trinosin (Na2ATP), the concentration of the high energy phosphate compound aqueous solution is 0.017moL/L；
Preferably, incubation time is 20~60min.Na2ATP introduces sodium ion, there is provided phosphorus source, carbon source, and be used as and receive The template of rice self-assembled structures.
, according to the invention it is preferred to, the source of iron described in step (2) is iron chloride, and the concentration of source of iron solution is 0.496mol/L；
Preferably, described Fe3+:PO4 3-Mol ratio be 1:1；
Preferably, the raw materials used HCl for 1mol/L of pH are adjusted.PH=2~4 are adjusted, ecru is obtained after stirring Turbid, centrifuged after still aging and obtain beige precipitate thing.
, according to the invention it is preferred to, the Fe described in step (3):V mol ratios are 1：1, vanadium source is ammonium metavanadate.Add Vanadium source, stirs, and obtains yellow turbid.
, according to the invention it is preferred to, the lithium source described in step (4) is lithium carbonate, and described carbon source is glucose；
Preferably, Fe:Li mol ratio=1:1, Fe:C mol ratio=4：1；
Preferably, low temperature drying mode is freeze-drying, and further preferred drying condition is -50 DEG C, 28Pa；Low temperature is done The dry time is 12h, and the mixing and ball milling time is 2h.Vanadium source is added, stirs, obtains foresythia turbid, cadmium yellow is obtained after low temperature drying Color powder.
, according to the invention it is preferred to, heat treatment temperature is 700 DEG C in step (5), heat treatment time 8h.
The Li that step (6) of the present invention obtains3V2(PO4)3/Na4FeO3/C60Positive electrode as hybrid ionic battery is carried out Using specific application process is as follows：
(1) by Li3V2(PO4)3/Na4FeO3/C60It is fully ground with conductive agent and binding agent after mixing, adds N- methyl pyrroles Pyrrolidone solvent, obtain precoating refined slurries after stirring；
(2) above-mentioned precoating is refined into slurries to be coated on aluminium foil, lithium-sodium mixing then will be produced after electrode slice drying process Ion battery anode electrode piece, gained lithium-sodium hybrid ionic anode electrode slice are used for button-type battery lithium-sodium hybrid ionic Battery.
Lithium-sodium hybrid ionic battery composite anode material Li prepared by the inventive method3V2(PO4)3/Na4FeO3/C60, Charging/discharging voltage be 2.5~4.2V and 10.0C multiplying powers under first discharge specific capacity be 78.5mAh/g, circulation 300 times after Specific discharge capacity be 98.4mAh/g (pure phosphoric acid vanadium lithium is generally 80mAh/g or so).In 2.5~4.2V and 1.0C multiplying powers After lower charging, the battery of overdischarge more than 90% remains to normal circulation.
Beneficial effects of the present invention are as follows：
The present invention uses high energy phosphate compound Na2ATP is stay in place form and introduces sodium source, phosphorus source and carbon source, passes through life Thing-chemical synthesis, Freeze Drying Technique and carbon thermal reduction technology have synthesized a kind of new composite L i3V2(PO4)3/ Na4FeO3/C60, not only with good chemical property, and with overdischarge self-shield and high rate cyclic specific capacity certainly Increased characteristic, lithium-sodium hybrid ionic battery can be used for as positive electrode.
Brief description of the drawings
Fig. 1 is lithium-sodium hybrid ionic battery composite anode material Li that the embodiment of the present invention 1 synthesizes3V2(PO4)3/ Na4FeO3/C60XRD, wherein ordinate is diffracted intensity, and abscissa is angle of diffraction (2 θ).
Fig. 2 is lithium-sodium hybrid ionic battery composite anode material Li that the embodiment of the present invention 1 synthesizes3V2(PO4)3/ Na4FeO3/C60Electrochemistry cycle performance figure.
Embodiment
Below by specific embodiment and with reference to accompanying drawing, the present invention will be further described, but not limited to this.
Raw materials used in embodiment is convenient source.
Embodiment 1
A kind of lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including Step is as follows：
(1) by 200mL 0.017mol/L Na2The ATP aqueous solution cultivates 30min under the conditions of 40 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1：1 by 20mL 0.496mol/L FeCl3Solution is slowly added into above-mentioned In solution, pH=3 is adjusted with 1mol/L HCl, stirs 2h, obtained ecru turbid, centrifuged after still aging 4h and obtain cream colour Color sediment；
(3) and then into beige precipitate thing add deionized water to be diluted to turbid and be settled to 200mL, according to mol ratio Fe:V=1:Stirring 2h obtains foresythia turbid after 1 addition 1.1688g ammonium metavanadates；
(4) foresythia turbid is freeze-dried into bright-yellow powder under the conditions of -50 DEG C, 28Pa；According to mol ratio Fe:Li =1:1 and Fe:C=4:1 adds 0.3664g lithium carbonates and 0.0744g glucose, mixing and ball milling into bright-yellow powder respectively 2h, presoma is made；
(5) by obtained presoma under nitrogen protection, 700 DEG C of heat treatment 8h are warming up to, after natural cooling, Li is made3V2 (PO4)3/Na4FeO3/C60Composite positive pole, its XRD are as shown in Figure 1.
Electrochemical property test
By lithium made from the embodiment-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60It is used as Lithium-sodium hybrid ionic battery, electrode is prepared using rubbing method.By lithium-sodium hybrid ionic battery composite anode material Li3V2 (PO4)3/Na4FeO3/C60, acetylene black and Kynoar (PVDF) press 80:10:10 mass ratio is fully ground mixing, adds Obtain precoating refined slurries after 1-METHYLPYRROLIDONE stirring solvent is uniform；Above-mentioned precoating is refined into slurries to be coated on aluminium foil, 6h and 120 DEG C of vacuum drying 12h is dried through 60 DEG C, diameter 15cm disk is cut into after natural cooling using sheet-punching machine, that is, is made Lithium-sodium hybrid ionic anode electrode slice.
According to anode cover-electrode slice-electrolyte-barrier film-electrolyte-lithium piece-pad-spring leaf-negative electrode casing order according to Secondary assembling, sealing machine is recycled by cell sealing, you can CR2032 type button half-cells are made.Finally in A713-2008S- 3TGF-A types high accuracy discharge and recharge instrument carries out constant current charge-discharge test to battery.
In the case where charging/discharging voltage is 2.5~4.2V and 10.0C multiplying powers, first discharge specific capacity is above-mentioned synthetic material 78.5mAh/g, the specific discharge capacity after circulating 300 times is 98.4mAh/g, and its electrochemistry cycle performance is as shown in Figure 2.
Embodiment 2
A kind of lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including Step is as follows：
(1) by 200mL 0.017mol/L Na2The ATP aqueous solution cultivates 30min under the conditions of 50 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1：1 by 20mL 0.496mol/L FeCl3Solution is slowly added into above-mentioned In solution, pH=2 is adjusted with 1mol/L HCl, stirs 2h, obtained ecru turbid, centrifuged after still aging 4h and obtain cream colour Color sediment；
(3) and then into beige precipitate thing add deionized water to be diluted to turbid and be settled to 200mL, according to mol ratio Fe:V=1:Stirring 2h obtains foresythia turbid after 1/2 addition 0.5844g ammonium metavanadates；
(4) foresythia turbid is freeze-dried into bright-yellow powder under the conditions of -50 DEG C, 28Pa；According to mol ratio Fe:Li =1:1 and Fe:C=4:1 adds 0.3664g lithium carbonates and 0.0744g glucose, mixing and ball milling 2h into bright-yellow powder respectively Presoma is made；
(5) by obtained presoma under nitrogen protection, 600 DEG C of heat treatment 8h are warming up to, after natural cooling, Li is made3V2 (PO4)3/Na4FeO3/C60Composite positive pole.
In the case where charging/discharging voltage is 2.5~4.2V and 10.0C multiplying powers, the first discharge specific capacity of synthetic material is 64.8mAh/g, the specific discharge capacity after charge and discharge cycles 300 times is 43.5mAh/g.
Embodiment 3
A kind of lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including Step is as follows：
(1) by 200mL 0.017mol/L Na2The ATP aqueous solution cultivates 30min under the conditions of 30 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1：1 by 20mL 0.496mol/L FeCl3Solution is slowly added into above-mentioned In solution, pH=4 is adjusted with 1mol/L HCl, stirs 2h, obtained ecru turbid, centrifuged after still aging 4h and obtain cream colour Color sediment；
(3) and then into beige precipitate thing add deionized water to be diluted to turbid and be settled to 200mL, according to mol ratio Fe:V=1:Stirring 2h obtains foresythia turbid after 2 addition 2.3376g ammonium metavanadates；
(4) foresythia turbid is freeze-dried into bright-yellow powder under the conditions of -50 DEG C, 28Pa；According to mol ratio Fe:Li =1:1 and Fe:C=4:1 adds 0.3664g lithium carbonates and 0.0744g glucose, mixing and ball milling 2h into bright-yellow powder respectively Presoma is made；
(5) by obtained presoma under nitrogen protection, 800 DEG C of heat treatment 8h are warming up to, after natural cooling, Li is made3V2 (PO4)3/Na4FeO3/C60Composite positive pole.
In the case where charging/discharging voltage is 2.5~4.2V and 10.0C multiplying powers, the first discharge specific capacity of synthetic material is 76.3mAh/g, the specific discharge capacity after charge and discharge cycles 300 times is 67.5mAh/g.
Embodiment 4
A kind of lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including Step is as follows：
(1) by 200mL 0.017mol/L Na2The ATP aqueous solution cultivates 30min under the conditions of 30 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1：1/2 by 40mL 0.496mol/L FeCl3Solution is slowly added into State in solution, adjust pH=4 with 1mol/L HCl, stir 2h, obtain ecru turbid, centrifuged after still aging 4h and obtain rice Yellow mercury oxide；
(3) and then into beige precipitate thing add deionized water to be diluted to turbid and be settled to 200mL, according to mol ratio Fe:V=1:Stirring 2h obtains foresythia turbid after 2 addition 2.3376g ammonium metavanadates；
(4) foresythia turbid is freeze-dried into bright-yellow powder under the conditions of -50 DEG C, 28Pa；According to mol ratio Fe:Li =1:1/4 and Fe:C=5:1 adds 0.0916g lithium carbonates and 0.0595g glucose, mixing and ball milling into bright-yellow powder respectively Presoma is made in 2h；
(5) by obtained presoma under nitrogen protection, 800 DEG C of heat treatment 8h are warming up to, after natural cooling, Li is made3V2 (PO4)3/Na4FeO3/C60Composite positive pole.
Embodiment 5
A kind of lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including Step is as follows：
(1) by 200mL 0.017mol/L Na2The ATP aqueous solution cultivates 30min under the conditions of 30 DEG C；
(2) according to mol ratio Fe3+:PO4 3-=1：2 by 10mL 0.496mol/L FeCl3Solution is slowly added into above-mentioned In solution, pH=4 is adjusted with 1mol/L HCl, stirs 2h, obtained ecru turbid, centrifuged after still aging 4h and obtain cream colour Color sediment；
(3) and then into beige precipitate thing add deionized water to be diluted to turbid and be settled to 200mL, according to mol ratio Fe:V=1:Stirring 2h obtains foresythia turbid after 2 addition 2.3376g ammonium metavanadates；
(4) foresythia turbid is freeze-dried into bright-yellow powder under the conditions of -50 DEG C, 28Pa；According to mol ratio Fe:Li =1:2 and Fe:C=2:1 adds 0.7328g lithium carbonates and 0.1488g glucose, mixing and ball milling 2h into bright-yellow powder respectively Presoma is made；
(5) by obtained presoma under nitrogen protection, 800 DEG C of heat treatment 8h are warming up to, after natural cooling, Li is made3V2 (PO4)3/Na4FeO3/C60Composite positive pole.

Claims (9)

  1. A kind of 1. lithium-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60Preparation method, including step It is rapid as follows：
    （1）The high energy phosphate compound aqueous solution is cultivated under the conditions of 30~50 DEG C, described high energy phosphate compound is Trinosin（Na2ATP）；
    （2）According to mol ratio Fe3+ : PO4 3- =1:（1/2~2）, source of iron solution is added to step（1）In resulting solution, PH=2~4 are adjusted, are stirred, is centrifuged after still aging, obtains sediment；
    （3）To step（2）Deionized water is added in obtained sediment, according to mol ratio Fe:V=1:(1/3~3), in stirring bar Vanadium source is added under part, vanadium source is ammonium metavanadate, stirs, obtains turbid；
    （4）By step（3）Obtained turbid low temperature drying, low temperature drying mode are freeze-drying, obtain powder；According to mol ratio Fe:Li=1:（1/4~2）Lithium source is added into powder, according to mol ratio Fe:C=（5~2）：1 adds carbon source, and described carbon source is Glucose, mixing and ball milling, obtain presoma；
    （5）By step（4）Obtained presoma under nitrogen protection, is warming up to 600~800 DEG C
    It is heat-treated, natural cooling after the completion of heat treatment, produces lithium-sodium hybrid ionic battery composite anode material Li3V2 (PO4)3/Na4FeO3/C60。
  2. 2. lithium according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60's Preparation method, it is characterised in that step（1）Described in the concentration of the high energy phosphate compound aqueous solution be 0.017moL/L.
  3. 3. lithium according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60's Preparation method, it is characterised in that step（2）Described in source of iron be iron chloride, the concentration of source of iron solution is 0.496mol/L.
  4. 4. lithium according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60's Preparation method, it is characterised in that step（2）Described in Fe3+ : PO4 3- Mol ratio be 1:1.
  5. 5. lithium according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60's Preparation method, it is characterised in that step（3）Described in Fe:V mol ratios are 1：1.
  6. 6. lithium according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60's Preparation method, it is characterised in that step（4）Described in lithium source be lithium carbonate.
  7. 7. lithium according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60's Preparation method, it is characterised in that step（4）Middle Fe:Li mol ratio=1:1, Fe:C mol ratio=4：1.
  8. 8. lithium according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60's Preparation method, it is characterised in that step（4）Freeze-drying condition is -50 DEG C, 28Pa.
  9. 9. lithium according to claim 1-sodium hybrid ionic battery composite anode material Li3V2(PO4)3/Na4FeO3/C60's Preparation method, it is characterised in that step（5）Middle heat treatment temperature is 700 DEG C,
    Heat treatment time is 8h.
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