CN106920965A - A kind of new sodium ion positive electrode NaFeSO4The preparation method of F - Google Patents

A kind of new sodium ion positive electrode NaFeSO4The preparation method of F Download PDF

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Publication number
CN106920965A
CN106920965A CN201710325999.0A CN201710325999A CN106920965A CN 106920965 A CN106920965 A CN 106920965A CN 201710325999 A CN201710325999 A CN 201710325999A CN 106920965 A CN106920965 A CN 106920965A
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positive electrode
sodium ion
nafeso
mixture
ion positive
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CN201710325999.0A
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Inventor
张建波
胡涛涛
靳鸣
靳一鸣
邬善江
李勇
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Jiangxi University of Science and Technology
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Jiangxi University of Science and 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
    • H01M4/58—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
    • H01M4/582—Halogenides
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a kind of new sodium ion positive electrode NaFeSO4The preparation method of F, belongs to technical field of chemical power, comprises the following steps that：By FeSO4·7H2O is placed in inert atmosphere carries out the pretreatment reaction removing crystallization water, obtains FeSO4·H2O sources of iron；By NaF and FeSO4·H2O sources of iron are placed in container and are well mixed, and obtain salt-mixture, and mixing salt solution is made into during organic solvent is added into salt-mixture；Mixing salt solution is placed in ball milling in ball mill by wet process, mixture is obtained；Mixture is placed in the reactor of sealing, and mixed liquor is made into organic solvent to being added in reactor；The reactor that mixed liquor will be filled is placed in heating and thermal insulation in baking oven, obtains final product sodium ion positive electrode NaFeSO4F semi-finished product；By sodium ion positive electrode NaFeSO4F semi-finished product are centrifuged, dried process, obtain final product sodium ion positive electrode NaFeSO4F.Preparation method in the present invention has the advantages that process is simple and is easily achieved industrialized production.

Description

A kind of new sodium ion positive electrode NaFeSO4The preparation method of F
Technical field
The present invention relates to technical field of chemical power, more particularly to a kind of new sodium ion positive electrode NaFeSO4The system of F Preparation Method.
Background technology
In the structure composition of sodium-ion battery, positive electrode, as the main part for storing up sodium, is to determine sodium-ion battery peace The key factor of full performance, chemical property and future development.Polyanionic positive electrode is in sodium-ion battery positive material Research in occupy an important position.Because included in the frame structure of polyanionic material strong covalent bond it is poly- cloudy from Son, it has good heat endurance, can provide a more preferable safety assurance to battery.In numerous candidate materials, Iron-based polyanion positive electrode is receiving more concerns recently, because crystal structure research shows this kind of material inherently With opening frame structure, and they also have more preferable friendly, generally nature mineral material to environment, originate rich Richness, is a kind of one of potential candidate material with huge advantage.
Fluorine-containing polysulfide acid group sections base (FeSO4F-) sodium-ion battery positive material, its theoretical charge and discharge platform is up to 3.3V (vs.Na), based on Fe2+/Fe3+Redox reaction, highest specific discharge capacity during its safe handling can reach 1 × (1 ÷ 193.9) × 96500 × 0.2778=138.3mAh/g.Based on above gross data, fluorine-containing polysulfide acid group sections base anode material (NaFeSO4F) it is the energy storage material with the alternative current lithium electricity system of potentiality.Closed for existing sodium-ion battery positive material Into the deficiency of technology, the present invention provides a kind of side for closing the hot inexpensive sodium ion positive electrode NaFeSO4F of method preparation of series solvent Method.
The content of the invention
The technical problem to be solved in the present invention is to provide the new sodium ion positive pole of a kind of preparation process is simple and low cost Material NaFeSO4The preparation method of F.The present invention is by pretreated FeSO4·7H2O sources of iron are with NaF according to certain chemistry meter Amount ratio carries out ball milling wet-mixing, and mixed raw material is placed in the reactor of sealing, and a timing is reacted at a certain temperature Between can prepare NaFeSO4F positive electrodes.
In order to solve the above-mentioned technical problem, the invention provides a kind of new sodium ion positive electrode NaFeSO4The preparation of F Method, comprises the following steps that：
(1) by FeSO4·7H2O is placed in carries out pretreatment reaction removing in less than 500 DEG C of inert atmosphere or reducing atmosphere The crystallization water, obtains final product FeSO4·H2O sources of iron；
(2) FeSO that will be prepared in NaF and step (1)4·H2O sources of iron are placed in container and are well mixed, and obtain final product salt-mixture, Mixing salt solution is made into during high boiling organic solvent is added into salt-mixture；
(3) mixing salt solution prepared in step (2) is placed in rotating speed in the ball mill by wet process of 100~500r/min 2~20h of ball milling, obtains final product mixture；
(4) mixture prepared in step (3) is placed in the reactor of sealing, and is added and step in reactor (2) identical high boiling organic solvent is made into mixed liquor；
(5) reactor that will fill mixed liquor is placed in temperature 8~50h of heating and thermal insulation in 160~220 DEG C of baking oven, Obtain final product sodium ion positive electrode NaFeSO4F semi-finished product；
(6) the sodium ion positive electrode NaFeSO that will be prepared in step (5)4F semi-finished product are centrifuged, dried process, i.e., Obtain sodium ion positive electrode NaFeSO4F。
Further, the inert atmosphere or reducing atmosphere in the step (1) are N2Or Ar or N2, Ar and H2Mixture.
Further, FeSO in the step (2)4·7H2O sources of iron are 1 with the mol ratio of NaF:1~2.
Further, high boiling organic solvent is ethylene glycol or glycerine or N, N- dimethyl formyl in the step (2) Amine；The mass ratio of the salt-mixture and high boiling organic solvent is between 1:2 and 5:Between 1.
Further, in the step (4) mass ratio of mixture and high boiling organic solvent between 1:10 and 1:50 it Between.
Compared with prior art, the beneficial effect that the present invention is reached：
(1) the new sodium ion positive electrode NaFeSO prepared in the present invention4F first reversible capacity up to 140mAh/g, And with good cycle performance；Therefore, the new sodium ion positive electrode NaFeSO for being prepared in the present invention4F has extensive Application prospect.
(2) new sodium ion positive electrode NaFeSO is prepared in the present invention4The raw material sources of F extensively, and are prepared new Sodium ion positive electrode NaFeSO4The technique of F is extremely simple, it is easy to accomplish industrialized production.
(3) by FeSO in the present invention4·7H2O is placed in inert atmosphere or reducing atmosphere and is pre-processed；In inert atmosphere Or it is in order to prevent oxygen oxidation of ferrous iron to ferric iron, so as to ensure the purity of raw material that pretreatment is carried out in reducing atmosphere.
In sum, new sodium ion positive electrode NaFeSO is prepared in the present invention4The method of F have process is simple, into The advantages of this low, positive electrode thing is mutually stablized and size is controllable, therefore, the preparation method is adapted to be pushed away in technical field of chemical power Wide and application.
Brief description of the drawings
The present invention is described in further detail below in conjunction with the drawings and the specific embodiments.
Fig. 1 is sodium ion positive electrode NaFeSO in the present invention4The X-ray diffraction material phase analysis figure of F；
Fig. 2 is sodium ion positive electrode NaFeSO in the present invention4The SEM figures of F.
Specific embodiment
Following examples are merely to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
A kind of new sodium ion positive electrode NaFeSO4The preparation method of F, comprises the following steps that：
(1) by FeSO4·7H2O is placed in less than 500 DEG C of N2In carry out pretreatment reaction remove the crystallization water, obtain final product FeSO4·H2O sources of iron；
(2) FeSO prepared in NaF the and 3.4g steps (1) of 0.1g is weighed4·H2O sources of iron are placed in container and are well mixed, Salt-mixture is obtained final product, mixing salt solution is made into during the ethylene glycol of 10mL is added into salt-mixture；
(3) mixing salt solution prepared in step (2) is placed in ball milling 2h in the ball mill by wet process that rotating speed is 100r/min, Obtain final product mixture；
(4) mixture prepared in step (3) is placed in the reactor of sealing, and is matched somebody with somebody to addition ethylene glycol in reactor Into the mixed liquor of 50mL；
(5) reactor that will fill mixed liquor is placed in heating and thermal insulation 8h in the baking oven that temperature is 160 DEG C, is obtaining final product sodium ion just Pole material NaFeSO4F semi-finished product；
(6) the sodium ion positive electrode NaFeSO that will be prepared in step (5)4F semi-finished product are centrifuged, dried process, i.e., Obtain sodium ion positive electrode NaFeSO4F。
Embodiment 2
A kind of new sodium ion positive electrode NaFeSO4The preparation method of F, comprises the following steps that：
(1) by FeSO4·7H2O is placed in less than 500 DEG C of Ar carries out the pretreatment reaction removing crystallization water, obtains final product FeSO4·H2O sources of iron；
(2) FeSO prepared in NaF the and 3.4g steps (1) of 0.1g is weighed4·H2O sources of iron are placed in container and are well mixed, Salt-mixture is obtained final product, mixing salt solution is made into during the glycerine of 10mL is added into salt-mixture；
(3) mixing salt solution prepared in step (2) is placed in ball milling in the ball mill by wet process that rotating speed is 300r/min 10h, obtains final product mixture；
(4) mixture prepared in step (3) is placed in the reactor of sealing, and is matched somebody with somebody to addition glycerine in reactor Into the mixed liquor of 50mL；
(5) reactor that will fill mixed liquor is placed in heating and thermal insulation 30h in the baking oven that temperature is 200 DEG C, obtains final product sodium ion Positive electrode NaFeSO4F semi-finished product；
(6) the sodium ion positive electrode NaFeSO that will be prepared in step (5)4F semi-finished product are centrifuged, dried process, i.e., Obtain sodium ion positive electrode NaFeSO4F。
Embodiment 3
A kind of new sodium ion positive electrode NaFeSO4The preparation method of F, comprises the following steps that：
(1) by FeSO4·7H2O be placed in less than 500 DEG C by N2, Ar and H2Carry out pre-processing instead in the mixed gas of composition The crystallization water should be removed, FeSO is obtained final product4·H2O sources of iron；
(2) FeSO prepared in NaF the and 3.4g steps (1) of 0.1g is weighed4·H2O sources of iron are placed in container and are well mixed, Salt-mixture is obtained final product, mixing salt solution is made into during DMF is added into salt-mixture；
(3) mixing salt solution prepared in step (2) is placed in ball milling in the ball mill by wet process that rotating speed is 500r/min 20h, obtains final product mixture；
(4) mixture prepared in step (3) is placed in the reactor of sealing, and to adding N, N- diformazans in reactor Base formamide is made into the mixed liquor of 50mL；
(5) reactor that will fill mixed liquor is placed in heating and thermal insulation 50h in the baking oven that temperature is 220 DEG C, obtains final product sodium ion Positive electrode NaFeSO4F semi-finished product；
(6) the sodium ion positive electrode NaFeSO that will be prepared in step (5)4F semi-finished product are centrifuged, dried process, i.e., Obtain sodium ion positive electrode NaFeSO4F。
Sodium ion positive electrode NaFeSO prepared by embodiment 24F is placed on X-ray diffractometer, and angle with 2 θ is swept Retouch whole diffraction region, you can obtain X-ray diffraction spectrum as shown in Figure 1；With SEM prepared by embodiment 2 Sodium ion positive electrode NaFeSO4F is observed and processed, you can obtain SEM figures as shown in Figure 2.
Sodium ion positive electrode NaFeSO prepared by embodiment 24F carries out electrochemical property test, and test result shows, Sodium ion positive electrode NaFeSO4Reversible discharge specific capacity reaches 140mAh/g to F first；Its cycle performance is surveyed simultaneously Examination, test result shows that the specific discharge capacity after 100 circulations is maintained at the 93% of initial discharge capacity.By commercially available sodium from Sub- positive electrode carries out electrochemical property test, and test result shows, commercially available sodium ion positive electrode reversible discharge ratio first Capacity is 85mAh/g；Its cycle performance is tested simultaneously, test result shows, the specific discharge capacity after 100 circulations is protected Hold 43% in initial discharge capacity.
In sum, the sodium ion positive electrode NaFeSO prepared by the present invention4F has low cost, capacity high and circulates The advantages of good stability, therefore, the preparation method in the present invention is adapted in field of chemical power source promotion and application.
Those of ordinary skill in the art it should be appreciated that the embodiment of the above be intended merely to explanation the present invention, And be not used as being limitation of the invention, as long as in spirit of the invention, the change to embodiment described above Change, modification will all fall in scope of the presently claimed invention.

Claims (5)

1. a kind of new sodium ion positive electrode NaFeSO4The preparation method of F, it is characterised in that comprise the following steps that：
(1) by FeSO4·7H2O is placed in less than 500 DEG C of inert atmosphere or reducing atmosphere carries out pretreatment reaction except decrystallizing Water, obtains final product FeSO4·H2O sources of iron；
(2) FeSO that will be prepared in NaF and step (1)4·H2O sources of iron are placed in container and are well mixed, and salt-mixture are obtained final product, by height Boiling point organic solvent is made into mixing salt solution in adding salt-mixture；
(3) mixing salt solution prepared in step (2) is placed in rotating speed ball milling in the ball mill by wet process of 100~500r/min 2~20h, obtains final product mixture；
(4) mixture prepared in step (3) is placed in the reactor of sealing, and is added and step (2) phase in reactor Same high boiling organic solvent is made into mixed liquor；
(5) reactor that will fill mixed liquor is placed in temperature 8~50h of heating and thermal insulation in 160~220 DEG C of baking oven, obtains final product Sodium ion positive electrode NaFeSO4F semi-finished product；
(6) the sodium ion positive electrode NaFeSO that will be prepared in step (5)4F semi-finished product are centrifuged, dried process, obtain final product sodium from Sub- positive electrode NaFeSO4F。
2. a kind of new sodium ion positive electrode NaFeSO according to claim 14The preparation method of F, it is characterised in that Inert atmosphere or reducing atmosphere in the step (1) are N2Or Ar or N2, Ar and H2Mixture.
3. a kind of new sodium ion positive electrode NaFeSO according to claim 14The preparation method of F, it is characterised in that FeSO in the step (2)4·H2O sources of iron are 1 with the mol ratio of NaF:1~2.
4. a kind of new sodium ion positive electrode NaFeSO according to claim 14The preparation method of F, it is characterised in that High boiling organic solvent is ethylene glycol or glycerine or DMF in the step (2)；The salt-mixture and height The mass ratio of boiling point organic solvent is between 1:2 and 5:Between 1.
5. a kind of new sodium ion positive electrode NaFeSO according to claim 14The preparation method of F, it is characterised in that The mass ratio of mixture and high boiling organic solvent is between 1 in the step (4):10 and 1:Between 50.
CN201710325999.0A 2017-05-10 2017-05-10 A kind of new sodium ion positive electrode NaFeSO4The preparation method of F Pending CN106920965A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116081594A (en) * 2023-02-23 2023-05-09 武汉工程大学 Preparation method of sodium ion battery anode material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101935072A (en) * 2010-08-26 2011-01-05 中国科学院化学研究所 Ferrous lithium sulphate fluoride as well as preparation method and application thereof
CN103078111A (en) * 2011-10-26 2013-05-01 江苏海四达电源股份有限公司 Preparation methods of monoclinic-phase FeSO4.H2O and triclinic-phase NaFe1-xMxSO4F (M=Co, Ni)
CN103078110A (en) * 2011-10-26 2013-05-01 江苏海四达电源股份有限公司 Monoclinic FeSO4·H2O and triclinic LifeXM1-XSO4F (M=Co, ni,0≤X≤1) preparation methods

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101935072A (en) * 2010-08-26 2011-01-05 中国科学院化学研究所 Ferrous lithium sulphate fluoride as well as preparation method and application thereof
CN103078111A (en) * 2011-10-26 2013-05-01 江苏海四达电源股份有限公司 Preparation methods of monoclinic-phase FeSO4.H2O and triclinic-phase NaFe1-xMxSO4F (M=Co, Ni)
CN103078110A (en) * 2011-10-26 2013-05-01 江苏海四达电源股份有限公司 Monoclinic FeSO4·H2O and triclinic LifeXM1-XSO4F (M=Co, ni,0≤X≤1) preparation methods

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RAJESH TRIPATHI等: ""Scalable Synthesis of Tavorite LiFeSO4F and NaFeSO4F Cathode Materials"", 《ANGEW. CHEM. INT. ED》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116081594A (en) * 2023-02-23 2023-05-09 武汉工程大学 Preparation method of sodium ion battery anode material

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