CN115159581A - Na 2 Fe(SO 4 ) 2 Preparation method of/C as composite positive electrode material of sodium-ion battery - Google Patents

Na 2 Fe(SO 4 ) 2 Preparation method of/C as composite positive electrode material of sodium-ion battery Download PDF

Info

Publication number
CN115159581A
CN115159581A CN202210916572.9A CN202210916572A CN115159581A CN 115159581 A CN115159581 A CN 115159581A CN 202210916572 A CN202210916572 A CN 202210916572A CN 115159581 A CN115159581 A CN 115159581A
Authority
CN
China
Prior art keywords
sodium
ion battery
positive electrode
electrode material
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210916572.9A
Other languages
Chinese (zh)
Inventor
张维民
邹伟民
康书文
王亿周
房志敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Zhiwei Electronic Technology Co ltd
Original Assignee
Jiangsu Zhiwei Electronic Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Zhiwei Electronic Technology Co ltd filed Critical Jiangsu Zhiwei Electronic Technology Co ltd
Priority to CN202210916572.9A priority Critical patent/CN115159581A/en
Publication of CN115159581A publication Critical patent/CN115159581A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/16—Evaporating by spraying
    • B01D1/18—Evaporating by spraying to obtain dry solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention belongs to the technical field of sodium ion battery preparation, and particularly relates to Na 2 Fe(SO 4 ) 2 A preparation method of the composite positive electrode material of the sodium-ion battery; dispersing nano graphite in deionized water to obtain a mixed suspension; mixing sodium sulfate pentahydrate, ferrous sulfate heptahydrate and ascorbic acid according to a certain proportion, and spray-drying the nano graphite and Na 2 Fe(SO 4 ) 2 ·2H 2 O is tightly combined, the electrochemical performance of the material is greatly improved, the composite material is well coated by using a spray drying method, the conductivity of the material is improved, a precursor is synthesized by using a one-step method, the nano graphite and the precursor are mixed and spray dried, a three-dimensional spherical structure with uniform size is formed after spray drying, and the used medicine has the advantages of rich raw materials, low price and simple synthesis method.

Description

Na 2 Fe(SO 4 ) 2 Preparation method of/C as composite positive electrode material of sodium-ion battery
Technical Field
The invention belongs to the field of preparation of a positive electrode material of a sodium-ion battery, and particularly relates to Na 2 Fe(SO 4 ) 2 The preparation method of the composite positive electrode material of the sodium-ion battery with the/C.
Background
The demand for electrochemical energy storage devices for portable consumer electronics, hybrid vehicles and grid power storage continues to grow exponentially, which has led to a global effort to make better batteries, tailored to specific applications, whose design parameters are not necessarily limited to electrochemical performance, and also including cost, operational safety, sustainable use and recyclability.
Sodium Ion Batteries (SIBs) are considered to be one of the important potential large-scale energy storage systems due to their abundant available resources, economic efficiency and electrochemical characteristics similar to lithium ion batteries, however, achieving high performance and practical application still faces huge challenges before more suitable electrodes are found to meet the requirements of high energy density and long cycle life, and in batteries, the cathode is a key factor for evaluating the performance of the battery, and the cost accounts for more than 30%, so as part of determining the cost and performance, there is an urgent need to develop a high operating voltage cathode with rapid and stable sodium ion migration capability.
The synthesis method of the sodium ferric sulfate cathode material disclosed in the application number CN109192982A is used in the lithium ion battery, the synthesis method in the patent is simple, the added Fe2+ cannot ensure that the whole material is oxidized in the reaction and calcination process, and the final product cannot determine which compound is.
Graphene and/or acetylene black compounded Na disclosed in application number CN110336021A 2 Fe(SO 4 ) 2 Although ascorbic acid is used as a reducing agent in the preparation method of the/C electrode material, the synthesis precursor is freeze-dried, and the synthesized material has irregular shape.
The patent application number CN106848236A discloses a preparation method of a sodium ferrous sulfate/graphene composite cathode material for a sodium ion battery, and the steps of synthesizing the material are complicated.
The prior patents cannot determine a final product, cannot ensure that the synthesized material has irregular shape, and the steps for synthesizing the material are complicated, so that potential safety hazards exist, and therefore, na is provided 2 Fe(SO 4 ) 2 The preparation method of the composite positive electrode material of the sodium-ion battery with the/C.
Disclosure of Invention
The invention aims to provide a method for synthesizing a sodium-ion battery composite material, which has simple steps and safe operation;
another object of the present invention is to provide a method for preparing a spherical sodium ion composite positive electrode material having excellent electrochemical properties;
the invention utilizes spray drying to mix nano graphite with Na 2 Fe(SO 4 ) 2 ·2H 2 O is tightly combined, the electrochemical performance of the material is greatly improved, the composite material is well coated by using a spray drying method, the conductivity of the material is improved, in the invention, a precursor is synthesized by using a one-step method, then the nano graphite and the precursor are mixed and spray dried, and a three-dimensional spherical structure with uniform size is formed after spray dryingCompared with the composite material synthesized by other methods at present, the composite material synthesized by the patent has the advantages that the active substance and the conductive substrate are combined more tightly, and the spherical structure with uniform size is formed. The composite material has good appearance, can enhance the electronic conductivity of the material, effectively improves the electrochemical performance of the composite material, and has wide market prospect.
The purpose of the invention can be realized by the following technical scheme: na (Na) 2 Fe(SO 4 ) 2 The preparation method of the sodium-ion battery composite positive electrode material comprises the following steps:
the method comprises the following steps: dispersing nano graphite into deionized water, and performing ultrasonic treatment to obtain a nano graphite turbid liquid;
step two: mixing anhydrous sodium sulfate and ferrous sulfate heptahydrate in a certain proportion, adding a certain amount of ascorbic acid into the mixed solution, dissolving the ascorbic acid into deionized water, and stirring at normal temperature to obtain a mixed solution;
step three: adding the nano graphite turbid liquid into the mixed solution of the anhydrous sodium sulfate and the ferrous sulfate heptahydrate, stirring, and fully and uniformly mixing to obtain a precursor solution;
step four: spraying and drying the precursor solution by using a spray dryer to obtain a solid precursor;
step five: and calcining the solid precursor to obtain the composite positive electrode material of the sodium-ion battery.
Further, the amount of the nano graphite in the first step is 5-15wt%.
Further, the ultrasonic time in the step one is 30-40min.
Further, the molar ratio of the anhydrous sodium sulfate to the ferrous sulfate heptahydrate in the step two is 1:1.
further, the amount of the ascorbic acid in the second step is 1wt% to 5wt%.
Further, the stirring time in the step two is 6-10h.
Further, the stirring time in the third step is 20-30min.
Further, the inlet temperature of the spray drying in the fourth step is 150-190 ℃, the outlet temperature is 70-100 ℃, and the feeding speed is 200-600mL/h.
Further, the calcination in the fifth step is to place the spray-dried precursor in a porcelain boat, place the porcelain boat in a tube furnace for calcination, where the calcination atmosphere is an inert gas atmosphere, the calcination temperature rise rate is 1-5 ℃/min, the calcination temperature is 300-400 ℃, and the calcination time is 10-15h.
The invention has the beneficial effects that:
1. the composite positive electrode material of the sodium ion battery is synthesized by the methods such as a solvothermal method, a spray drying method, a high-temperature calcination method and the like, so that the battery has good electrochemical performance;
2. according to the invention, the precipitate is dried and then calcined at high temperature in the atmosphere of inert gas, so that the material is prevented from being oxidized, the material is protected, and an accurate target product is obtained; ascorbic acid is added as a reducing agent, so that the oxidation of ferrous ions can be effectively inhibited, and an accurate product is obtained;
3. according to the invention, the composite material is well coated by using a spray drying method, so that the obtained product is in a three-dimensional spherical structure with uniform size, and the conductivity of the material is improved; the conductive matrix and the active substance are tightly combined by forming a three-dimensional spherical structure with uniform size, so that a high-efficiency transfer path can be provided for electrons during charge and discharge so as to obtain good electrochemical performance;
4. the sodium ion battery has the advantages that due to the defect of electrochemical performance caused by irregular internal structure, the nano graphite is coated with the sodium ferrous sulfate creatively by a spray drying method to form a three-dimensional spherical structure, so that the electrochemical performance of the battery is greatly improved;
5. the invention successfully prepares the composite positive electrode material of the sodium-ion battery by coating the nano graphite with the sodium ferrous sulfate by a spray drying method; mixing anhydrous sodium sulfate and ferrous sulfate heptahydrate, adding ascorbic acid as an antioxidant, dissolving the anhydrous sodium sulfate, the ferrous sulfate heptahydrate and the ascorbic acid with deionized water, and fully stirring, mixing and reacting to obtain a precursor; dispersing in deionized water by ultrasound, adding the obtained precursor into the mixed solution, and stirring and uniformly mixing at a certain temperature to obtain a mixed suspension; after the mixed turbid liquid is subjected to spray drying, the precursor can be tightly coated by the nano graphite; calcining the spray-dried material to obtain a sodium-ion battery composite positive electrode material;
6. the invention can inhibit Fe by adding ascorbic acid 2+ Is oxidized into Fe 3+ (ii) a The nano graphite added into the precursor is used as a conductive agent, so that the conductivity of the material is improved;
7. according to the invention, the sodium-ion battery composite positive electrode material is synthesized by adopting a method combining spray drying and calcining, and the spray drying method can be used for fully mixing the nano graphite and the precursor, so that the obtained material is in a nano level and has a three-dimensional spherical structure with uniform size, and the precursor is well coated; the iron element can be embedded into the crystal lattice by calcination, so that the electrochemical performance of the battery can be greatly improved, and a good foundation is laid for the next experiment; the nano graphite is added and mixed to form turbid liquid in the process of preparing the precursor, so that carbon elements are provided, the precursor is well coated, and experiments show that the electrochemical performance of the coated material is improved to a certain extent;
8. in the invention, the precursor is fully mixed with the nano-graphite through spray drying and then calcined, and the iron element is embedded into the crystal lattice of the material through the calcination after the spray drying; the invention preferably uses the synthesized nano graphite, the particle size of the nano graphite is small and is about 50-400nm, the precursor is easier to coat after spray drying, and the obtained material has better appearance, so that the battery has better stability compared with the batteries dried by other methods, and the electrochemical performance is also effectively improved; the electrochemical performance detection indexes of the product are mainly the charge and discharge capacity, the coulombic efficiency and the capacity retention rate after circulation of the battery; these electrochemical properties are mainly measured by simple constant current charging and discharging and multiplying power of the battery;
9. the precursor is synthesized by a one-step method, and the precursor is mixed with the nano-graphite and then subjected to spray drying and calcination to obtain the sodium ion battery composite positive electrode material with a novel structure.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a process flow diagram of the present invention;
fig. 2 is an XRD pattern of a sodium ion battery prepared using the sodium ion battery composite positive electrode material of example 1;
fig. 3 is an SEM image of a sodium ion battery prepared using the sodium ion battery composite positive electrode material of example 1;
fig. 4 is a graph of the charge-discharge cycle performance of a sodium ion battery prepared using the positive electrode material of example 1;
fig. 5 is a graph illustrating charge and discharge cycle performance of a sodium ion battery prepared using the cathode material of comparative example 1;
fig. 6 is a graph of rate performance for a sodium ion battery prepared using the positive electrode material of example 1;
fig. 7 is a graph of rate performance for a sodium ion battery prepared using the positive electrode material of comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Synthesis of precursor solution
Dispersing 2g of nano graphite into deionized water, and carrying out ultrasonic treatment for 30min to obtain a nano graphite suspension A; mixing 5g of anhydrous sodium sulfate and 10g of ferrous sulfate heptahydrate, adding 0.17g of ascorbic acid into the mixed solution, dissolving the ascorbic acid into 150mL of deionized water, and stirring at normal temperature for 6 hours to obtain a mixed solution B; mixing the mixed solution A and the nano graphite suspension B, and stirring for 30min to obtain a precursor solution;
synthesis of solid precursor
Spraying and drying the precursor solution by using a spray dryer to obtain a solid precursor, wherein the inlet temperature is set to be 180 ℃, the outlet temperature is set to be 80 ℃, and the feeding speed is set to be 300mL/h;
synthesis of Na 2 Fe(SO 4 ) 2 /C
And placing the powder obtained after spray drying into a porcelain boat, placing the porcelain boat into a tube furnace for calcining, heating to 350 ℃ at a heating rate of 1 ℃/min in a hydrogen-argon atmosphere, and preserving heat for 12 hours at the temperature to obtain the sodium ferrous sulfate/nano graphite composite cathode material.
Example 2
Synthesis of precursor solution
Dispersing 2g of nano graphite into deionized water, and carrying out ultrasonic treatment for 30min to obtain a nano graphite suspension A; mixing 5g of anhydrous sodium sulfate and 10g of ferrous sulfate heptahydrate, adding 0.21g of ascorbic acid into the mixed solution, dissolving the ascorbic acid into 150mL of deionized water, and stirring at normal temperature for 6 hours to obtain a mixed solution B; mixing the mixed solution A and the nano graphite suspension B, and stirring for 30min to obtain a precursor solution;
synthesis of solid precursor
Carrying out cold drying on the precursor solution by utilizing a freeze drying method to obtain a solid precursor;
synthesis of Na 2 Fe(SO 4 ) 2 /C
And placing the powder obtained after spray drying into a porcelain boat, placing the porcelain boat into a tube furnace for calcining, heating to 350 ℃ at a heating rate of 1 ℃/min in a hydrogen-argon atmosphere, and preserving heat for 12 hours at the temperature to obtain the sodium ferrous sulfate/nano graphite composite cathode material.
Example 3
Synthesis of precursor solution
Dispersing 0.9g of nano graphite into deionized water, and performing ultrasonic treatment for 30min to obtain a nano graphite suspension A; mixing 5g of anhydrous sodium sulfate and 10g of ferrous sulfate heptahydrate, adding 0.17g of ascorbic acid into the mixed solution, dissolving the ascorbic acid into 150mL of deionized water, and stirring at normal temperature for 6 hours to obtain a mixed solution B; mixing the mixed solution A and the nano graphite suspension B, and stirring for 30min to obtain a precursor solution;
synthesis of solid precursor
Spraying and drying the precursor solution by using a spray dryer to obtain a solid precursor, wherein the inlet temperature is set to be 180 ℃, the outlet temperature is set to be 80 ℃, and the feeding speed is set to be 300mL/h;
synthesis of Na 2 Fe(SO 4 ) 2 /C
And placing the powder obtained after spray drying into a porcelain boat, placing the porcelain boat into a tube furnace for calcination, heating to 350 ℃ at a heating rate of 1 ℃/min in a hydrogen and argon atmosphere, and preserving heat for 12 hours at the temperature to obtain the sodium ferrous sulfate/nano graphite composite cathode material.
Example 4
Synthesis of precursor solution
Dispersing 2g of nano graphite into deionized water, and carrying out ultrasonic treatment for 30min to obtain a nano graphite suspension A; mixing 5g of anhydrous sodium sulfate and 10g of ferrous sulfate heptahydrate, adding 0.35g of ascorbic acid into the mixed solution, dissolving the ascorbic acid into 150mL of deionized water, and stirring for 10 hours at normal temperature to obtain a mixed solution B; mixing the mixed solution A and the nano-graphite suspension B, and stirring for 30min to obtain a precursor solution;
synthesis of solid precursor
Spraying and drying the precursor solution by using a spray dryer to obtain a solid precursor, wherein the inlet temperature is set to be 180 ℃, the outlet temperature is set to be 80 ℃, and the feeding speed is set to be 300mL/h;
synthesis of Na 2 Fe(SO 4 ) 2 /C
And placing the powder obtained after spray drying into a porcelain boat, placing the porcelain boat into a tube furnace for calcination, heating to 350 ℃ at a heating rate of 1 ℃/min in a hydrogen and argon atmosphere, and preserving heat for 12 hours at the temperature to obtain the sodium ferrous sulfate/nano graphite composite cathode material.
Example 5
Synthesis of precursor solution
Dispersing 2g of nano graphite into deionized water, and carrying out ultrasonic treatment for 30min to obtain a nano graphite suspension A; mixing 5g of anhydrous sodium sulfate and 10g of ferrous sulfate heptahydrate, adding 0.17g of ascorbic acid into the mixed solution, dissolving the ascorbic acid into 150mL of deionized water, and stirring at normal temperature for 6 hours to obtain a mixed solution B; mixing the mixed solution A and the nano graphite suspension B, and stirring for 30min to obtain a precursor solution;
synthesis of solid precursor
Spray-drying the precursor solution by using a spray dryer to obtain a solid precursor, wherein the inlet temperature is set to be 170 ℃, the outlet temperature is set to be 70 ℃, and the feeding speed is set to be 200mL/h;
synthesis of Na 2 Fe(SO 4 ) 2 /C
And placing the powder obtained after spray drying into a porcelain boat, placing the porcelain boat into a tube furnace for calcination, heating to 350 ℃ at a heating rate of 1 ℃/min in a hydrogen and argon atmosphere, and preserving heat for 12 hours at the temperature to obtain the sodium ferrous sulfate/nano graphite composite cathode material.
Example 6
Synthesis of precursor solution
Dispersing 2g of nano graphite into deionized water, and carrying out ultrasonic treatment for 30min to obtain a nano graphite suspension A; mixing 5g of anhydrous sodium sulfate and 10g of ferrous sulfate heptahydrate, adding 0.17g of ascorbic acid into the mixed solution, dissolving the ascorbic acid into 150mL of deionized water, and stirring at normal temperature for 6 hours to obtain a mixed solution B; mixing the mixed solution A and the nano graphite suspension B, and stirring for 30min to obtain a precursor solution;
synthesis of solid precursor
Spraying and drying the precursor solution by using a spray dryer to obtain a solid precursor, wherein the inlet temperature is set to be 180 ℃, the outlet temperature is set to be 80 ℃, and the feeding speed is set to be 300mL/h;
synthesis of Na 2 Fe(SO 4 ) 2 /C
And placing the powder obtained after spray drying into a porcelain boat, placing the porcelain boat into a tube furnace for calcination, heating to 400 ℃ at the heating rate of 3 ℃/min in the hydrogen and argon atmosphere, and preserving heat for 10 hours at the temperature to obtain the sodium ferrous sulfate/nano graphite composite cathode material.
Example 7
Synthesis of precursor solution
Dispersing 1.6g of nano-graphite into deionized water, and carrying out ultrasonic treatment for 30min to obtain a nano-graphite suspension A; mixing 5g of anhydrous sodium sulfate and 10g of ferrous sulfate heptahydrate, adding 0.21g of ascorbic acid into the mixed solution, dissolving the ascorbic acid into 150mL of deionized water, and stirring at normal temperature for 6 hours to obtain a mixed solution B; mixing the mixed solution A and the nano-graphite suspension B, and stirring for 30min to obtain a precursor solution;
synthesis of solid precursor
Carrying out cold drying on the precursor solution by utilizing a freeze drying method to obtain a solid precursor;
synthesis of Na 2 Fe(SO 4 ) 2 /C
And placing the powder obtained after spray drying into a porcelain boat, placing the porcelain boat into a tube furnace for calcination, heating to 350 ℃ at a heating rate of 1 ℃/min in a hydrogen and argon atmosphere, and preserving heat for 12 hours at the temperature to obtain the sodium ferrous sulfate/nano graphite composite cathode material.
Example 8
Synthesis of precursor solution
Dispersing 2g of nano graphite into deionized water, and carrying out ultrasonic treatment for 30min to obtain a nano graphite suspension A; mixing 5g of anhydrous sodium sulfate and 10g of ferrous sulfate heptahydrate, adding 0.48g of ascorbic acid into the mixed solution, dissolving the ascorbic acid into 150mL of deionized water, and stirring at normal temperature for 10 hours to obtain a mixed solution B; mixing the mixed solution A and the nano graphite suspension B, and stirring for 30min to obtain a precursor solution;
synthesis of solid precursor
Carrying out cold drying on the precursor solution by utilizing a freeze drying method to obtain a solid precursor;
synthesis of Na 2 Fe(SO 4 ) 2 /C
And placing the powder obtained after spray drying into a porcelain boat, placing the porcelain boat into a tube furnace for calcination, heating to 350 ℃ at a heating rate of 1 ℃/min in a hydrogen and argon atmosphere, and preserving heat for 12 hours at the temperature to obtain the sodium ferrous sulfate/nano graphite composite cathode material.
Example 9
The inlet temperature of the spray dryer for synthesizing the solid precursor in example 2 was changed to 170 ℃, the outlet temperature was changed to 70 ℃, the feed rate was 200mL/h, and the rest of the procedure was the same as in example 2.
Example 10
Na was synthesized in example 2 2 Fe(SO 4 ) 2 The temperature rise rate of the catalyst/C was changed to 3 ℃/min, the calcination temperature was changed to 400 ℃, the calcination time was changed to 10 hours, and the rest of the steps were the same as in example 2.
Example 11
The amount of nano-graphite used for synthesizing the precursor solution in example 1 was changed to 1.8g, and the procedure was the same as in example 1.
Example 12
The amount of nano-graphite for synthesizing the precursor solution in example 1 was changed to 2.2g, and the procedure was the same as in example 1.
Example 13
The amount of nano graphite for synthesizing the precursor solution in example 2 was changed to 2.4g, and the rest of the procedure was the same as in example 2.
Example 14
The amount of nano-graphite used for synthesizing the precursor solution in example 2 was changed to 2.6g, and the procedure was the same as in example 2.
Example 15
The amount of ascorbic acid used in the synthesis of the precursor solution in example 1 was changed to 0.72g, and the procedure was the same as in example 1.
Example 16
The amount of ascorbic acid used in the synthesis of the precursor solution in example 2 was changed to 0.89g, and the procedure was the same as in example 2.
Example 17
The inlet temperature of the spray dryer for synthesizing the solid precursor in example 1 was changed to 190 ℃ and the outlet temperature was changed to 100 ℃, and the rest of the procedure was the same as in example 1.
Example 18
The inlet temperature of the spray dryer for synthesizing the solid precursor in example 2 was changed to 190 ℃ and the outlet temperature was changed to 100 ℃, and the rest of the procedure was the same as in example 2.
Example 19
Na was synthesized in example 1 2 Fe(SO 4 ) 2 The temperature rise rate of the/C is changed to 5 ℃/min, the calcining temperature is changed to 300 ℃, the heat preservation time is changed to 15h, and the rest steps are the same as the example 1.
Example 20
Na was synthesized in example 2 2 Fe(SO 4 ) 2 The temperature rise rate of the/C is changed to 5 ℃/min, the calcining temperature is changed to 300 ℃, the heat preservation time is changed to 15h, and the rest steps are the same as the example 2.
Comparative example 1
Synthesis of precursor solution
Mixing 5g of anhydrous sodium sulfate and 10g of ferrous sulfate heptahydrate, adding 0.17g of ascorbic acid into the mixture, dissolving the mixture into 150mL of deionized water, and stirring the mixture for 6 hours at normal temperature to obtain a precursor solution;
synthesis of solid precursor
Spraying and drying the precursor solution by using a spray dryer to obtain a solid precursor, wherein the inlet temperature is set to be 180 ℃, the outlet temperature is set to be 80 ℃, and the feeding speed is set to be 300mL/h;
synthesis of Na 2 Fe(SO 4 ) 2
And placing the powder obtained after spray drying into a porcelain boat, placing the porcelain boat into a tube furnace for calcination, heating to 350 ℃ at a heating rate of 1 ℃/min in a hydrogen and argon atmosphere, and preserving heat for 12 hours at the temperature to obtain the ferrous sodium sulfate cathode material.
Comparative example 2
Synthesis of precursor solution
Mixing 5g of anhydrous sodium sulfate and 10g of ferrous sulfate heptahydrate, adding 0.21g of ascorbic acid into the mixture, dissolving the mixture into 150mL of deionized water, and stirring the mixture for 6 hours at normal temperature to obtain a precursor solution;
synthesis of solid precursor
Spraying the precursor solution by using a spray dryer to obtain a solid precursor, wherein the inlet temperature is set to be 180 ℃, the outlet temperature is set to be 80 ℃, and the feeding speed is set to be 300mL/h;
synthesis of Na 2 Fe(SO 4 ) 2
And placing the powder obtained after spray drying into a porcelain boat, placing the porcelain boat into a tube furnace for calcination, heating to 350 ℃ at a heating rate of 1 ℃/min in a hydrogen and argon atmosphere, and preserving heat for 12 hours at the temperature to obtain the sodium ferrous sulfate and anode material.
In the invention, effective carbon introduction and building engineering strategies are adopted to improve the conductivity and the power performance, and the iron sodium sulfate material is modified. In order to expand SO of sodium ion battery 4 2- Inserted into the Material database, the present invention is a novel Compound Na 2 Fe(SO 4 ) 2 ·2H 2 O as a highly efficient, rapidly reversible Na + An insert body suitable for use in a rechargeable sodium ion battery. The compound contains economical and rich elements in a Na-S-O-H system, and also has the advantages of preparation at normal temperature, synthesis of a product through one-step dissolution and precipitation, simple operation and easy obtainment of the product. Adopts a monoclinic structure of the Krkate mineral family and has higher Fe 3+ /Fe 2+ Oxidation-reduction potential (ca.3.25V vs Na/Na) + ) The reversible capacity exceeds 70mAh/g. Although its commercial prospect of low capacity would be hindered by its capacity, it is an alternative preparation of the anhydro derivative [ i.e. Na 2 Fe(SO 4 ) 2 ]And other novel SO-based for large-scale sodium ion batteries 4 2- The cathode material paves the road
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the following claims.

Claims (9)

1.Na 2 Fe(SO 4 ) 2 The preparation method of the composite positive electrode material of the sodium-ion battery with the/C is characterized by comprising the following steps:
the method comprises the following steps: dispersing nano graphite into deionized water, and performing ultrasonic treatment to obtain a nano graphite suspension;
step two: mixing anhydrous sodium sulfate and ferrous sulfate heptahydrate in a certain proportion, adding a certain amount of ascorbic acid into the mixed solution, dissolving the ascorbic acid into deionized water, and stirring at normal temperature to obtain a mixed solution;
step three: adding the nano graphite turbid liquid into the mixed solution of the anhydrous sodium sulfate and the ferrous sulfate heptahydrate, stirring, and fully and uniformly mixing to obtain a precursor solution;
step four: spraying and drying the precursor solution by using a spray dryer to obtain a solid precursor;
step five: and calcining the solid precursor to obtain the composite positive electrode material of the sodium-ion battery.
2. Na according to claim 1 2 Fe(SO 4 ) 2 The preparation method of the/C composite positive electrode material of the sodium-ion battery is characterized in that the amount of the nano graphite in the step one is 5-15wt%.
3. Na according to claim 1 2 Fe(SO 4 ) 2 The preparation method of the composite positive electrode material of the sodium-ion battery with the/C is characterized in that the ultrasonic time in the step one is 30-40min.
4. Na according to claim 1 2 Fe(SO 4 ) 2 The preparation method of the/C composite positive electrode material of the sodium-ion battery is characterized in that the molar ratio of the anhydrous sodium sulfate to the ferrous sulfate heptahydrate in the step two is 1:1.
5. na according to claim 1 2 Fe(SO 4 ) 2 The preparation method of the/C composite positive electrode material for the sodium-ion battery is characterized in that the amount of the ascorbic acid in the step two is 1-5 wt%.
6. Na according to claim 1 2 Fe(SO 4 ) 2 The preparation method of the sodium-ion battery composite positive electrode material is characterized in that the stirring time in the step two is 6-10h.
7. Na according to claim 1 2 Fe(SO 4 ) 2 The preparation method of the sodium-ion battery composite positive electrode material is characterized in that the stirring time in the third step is 20-30min.
8. Na according to claim 1 2 Fe(SO 4 ) 2 The preparation method of the sodium-ion battery composite positive electrode material/C is characterized in that the inlet temperature of the spray drying device in the fourth step is 150-190 ℃, the outlet temperature is 70-100 ℃, and the feeding speed is 200-600mL/h.
9. Na according to claim 1 2 Fe(SO 4 ) 2 The preparation method of the composite positive electrode material of the sodium-ion battery is characterized in that the calcination in the fifth step is to place the sprayed and dried precursor in a porcelain boat, place the porcelain boat in a tubular furnace for calcination, wherein the calcination atmosphere is inert gas atmosphere, the temperature rise rate of the calcination is 1-5 ℃/min, the calcination temperature is 300-400 ℃, and the calcination time is 10-15h.
CN202210916572.9A 2022-08-01 2022-08-01 Na 2 Fe(SO 4 ) 2 Preparation method of/C as composite positive electrode material of sodium-ion battery Pending CN115159581A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210916572.9A CN115159581A (en) 2022-08-01 2022-08-01 Na 2 Fe(SO 4 ) 2 Preparation method of/C as composite positive electrode material of sodium-ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210916572.9A CN115159581A (en) 2022-08-01 2022-08-01 Na 2 Fe(SO 4 ) 2 Preparation method of/C as composite positive electrode material of sodium-ion battery

Publications (1)

Publication Number Publication Date
CN115159581A true CN115159581A (en) 2022-10-11

Family

ID=83477379

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210916572.9A Pending CN115159581A (en) 2022-08-01 2022-08-01 Na 2 Fe(SO 4 ) 2 Preparation method of/C as composite positive electrode material of sodium-ion battery

Country Status (1)

Country Link
CN (1) CN115159581A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115849454A (en) * 2022-11-22 2023-03-28 湖北万润新能源科技股份有限公司 Preparation method of sodium ferrous sulfate cathode material
CN116354405A (en) * 2023-04-06 2023-06-30 北京理工大学 In-situ carbon-coated sodium ferrous sulfate composite positive electrode material, preparation and sodium ion battery
CN116404144A (en) * 2023-06-09 2023-07-07 华大钠电(北京)科技有限公司 Sodium ion battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848236A (en) * 2017-02-20 2017-06-13 中南大学 A kind of ferrous sulfate sodium/grapheme composite positive electrode material for sodium-ion battery and preparation method thereof
CN110336021A (en) * 2019-07-24 2019-10-15 郑州大学 Graphene and/or compound Na2Fe (SO4) 2/C electrode material, preparation method and the battery of preparation of acetylene black
CN114050246A (en) * 2021-11-16 2022-02-15 郑州大学 Micron-sized porous sodium ferrous sulfate/carbon composite cathode material and sodium ion battery or sodium battery prepared from same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848236A (en) * 2017-02-20 2017-06-13 中南大学 A kind of ferrous sulfate sodium/grapheme composite positive electrode material for sodium-ion battery and preparation method thereof
CN110336021A (en) * 2019-07-24 2019-10-15 郑州大学 Graphene and/or compound Na2Fe (SO4) 2/C electrode material, preparation method and the battery of preparation of acetylene black
CN114050246A (en) * 2021-11-16 2022-02-15 郑州大学 Micron-sized porous sodium ferrous sulfate/carbon composite cathode material and sodium ion battery or sodium battery prepared from same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
黄惠宁等: "《陶瓷干法制粉工艺与设备》", 华南理工大学出版社, pages: 120 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115849454A (en) * 2022-11-22 2023-03-28 湖北万润新能源科技股份有限公司 Preparation method of sodium ferrous sulfate cathode material
CN115849454B (en) * 2022-11-22 2023-07-11 湖北万润新能源科技股份有限公司 Preparation method of ferrous sodium sulfate positive electrode material
CN116354405A (en) * 2023-04-06 2023-06-30 北京理工大学 In-situ carbon-coated sodium ferrous sulfate composite positive electrode material, preparation and sodium ion battery
CN116404144A (en) * 2023-06-09 2023-07-07 华大钠电(北京)科技有限公司 Sodium ion battery
CN116404144B (en) * 2023-06-09 2023-08-15 华大钠电(北京)科技有限公司 Sodium ion battery

Similar Documents

Publication Publication Date Title
CN115159581A (en) Na 2 Fe(SO 4 ) 2 Preparation method of/C as composite positive electrode material of sodium-ion battery
CN101330141B (en) Method for preparing lithium ionic battery anode material spherical LiFePO4 /C
CN108511714B (en) Transition metal phosphide-carbon composite material and preparation method and application thereof
CN101327922B (en) Preparation of LiFePO4
CN101964411B (en) LiFePO4 composite type positive pole material preparation method
CN106784815B (en) A kind of iron-based sulfide electrode material, preparation method and the application in solid state battery
CN105470455A (en) Modified lithium ion battery positive electrode material and preparation method therefor
CN111430687B (en) Carbon-coated lithium iron phosphate composite material, preparation method thereof and lithium ion battery
CN102088074A (en) Anode material of composite silicate and preparation method thereof
CN102208637A (en) ZnFe2O4/C composite cathode material with hollow sphere structure and one-step preparation method thereof
CN102104143A (en) Hydrothermal synthesis method of composite material for high-performance power battery
CN102790216A (en) Supercritical solvent thermal preparation method of cathode material lithium iron phosphate of lithium ion battery
CN102244244B (en) Method for improving tap density of composite anode material xLiFePO4.yLi3V2(PO4)3 of lithium ion battery
CN103066255A (en) A nano-metal coated sulfur composite material and applications thereof
CN111816874B (en) Preparation method of positive active material of lithium slurry battery
CN102820465A (en) Application of polyacrylic acid in preparation of lithium ion battery anode material nano-sized iron oxide/carbon composite material
CN107123794A (en) A kind of preparation method of carbon coating manganese monoxide/N doping redox graphene lithium ion battery negative material
CN105826524A (en) Synthesis method of lithium iron phosphate of graphene in-situ nucleation
CN103413918B (en) A kind of synthetic method of anode material for lithium ion battery cobalt phosphate lithium
CN102259933A (en) Preparation method and application of rice-grain alpha-iron trioxide
CN104681814B (en) A kind of anode material for lithium-ion batteries LiFePO with porous star pattern4And preparation method thereof
CN103050697B (en) Method for preparing micron-sized LiFePO4/C serving as high-rate lithium ion battery anode material
CN110444741A (en) Graphene modified LiFePO4 quantum dot composite material and its preparation method and application
CN117049604A (en) Ferrous polyanion type sodium ion battery positive electrode material and preparation method thereof
CN108305996A (en) A method of improving lithium-rich manganese-based anode material clad uniformity

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination