CN113113609A - Three-dimensional composite negative electrode material of sodium-ion battery and preparation method and application thereof - Google Patents

Three-dimensional composite negative electrode material of sodium-ion battery and preparation method and application thereof Download PDF

Info

Publication number
CN113113609A
CN113113609A CN202110399454.0A CN202110399454A CN113113609A CN 113113609 A CN113113609 A CN 113113609A CN 202110399454 A CN202110399454 A CN 202110399454A CN 113113609 A CN113113609 A CN 113113609A
Authority
CN
China
Prior art keywords
feps
ion battery
sodium
negative electrode
dimensional composite
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.)
Withdrawn
Application number
CN202110399454.0A
Other languages
Chinese (zh)
Inventor
彭生杰
连欣彤
丁永豪
李林林
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.)
Nanjing University of Aeronautics and Astronautics
Original Assignee
Nanjing University of Aeronautics and Astronautics
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 Nanjing University of Aeronautics and Astronautics filed Critical Nanjing University of Aeronautics and Astronautics
Priority to CN202110399454.0A priority Critical patent/CN113113609A/en
Publication of CN113113609A publication Critical patent/CN113113609A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/5805—Phosphides
    • 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
    • H01M4/36—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/027—Negative 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

Abstract

The invention belongs to the technical field of sodium ion batteries, and particularly discloses a three-dimensional composite negative electrode material of a sodium ion battery, and a preparation method and application thereof. The invention relates to a three-dimensional composite cathode material FePS of a sodium ion battery3the/rGO has a lamellar structure, and tiny FePS is uniformly attached to the surface of the rGO lamellar3Nanosheets. FePS3Is ternary transition metal phosphosulfide and has special two-dimensional layered structure with van der waals force combination between layers, and this structure is favorable to the fast motion and storage of sodium ion between layers. The invention uses FePS3With rGOIs compounded, effectively buffers FePS3The volume expansion of the material in the reaction process promotes the rapid transfer of electrons/ions, and the longer cycle life can be realized on the premise of keeping higher specific capacity. Meanwhile, the rate performance of the material is greatly enhanced by improving the stability of the material system, and the prepared sodium ion battery has high discharge capacity and excellent rate performance.

Description

Three-dimensional composite negative electrode material of sodium-ion battery and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a three-dimensional composite negative electrode material of a sodium ion battery, and a preparation method and application thereof.
Background
Since 1991 lithium ion batteries were first commercialized and have been widely used and developed as efficient energy storage devices in the last 30 years, however, as the demand for electric vehicles and large-scale energy storage increases, lithium resources have limited resources, which leads to an increase in cost, and therefore, sodium ion batteries are expected to be a cheaper energy storage system due to their similar energy storage properties and abundance of sodium resources. However, most carbon materials are not suitable as the negative electrode material of the sodium ion battery according to thermodynamic calculation, and the alloy material and the conversion material have higher specific capacity based on the mechanisms of alloying and conversion reaction, but are in Na+The large volume change occurs when the insertion is released, and the active material is inevitably crushed and pulverized, so that the electrical contact resistance is increased, and the rapid and serious attenuation of the battery capacity is caused. For example, FePS3The ternary transition metal phosphorus sulfide has a special two-dimensional layered structure, the layers are combined by Van der Waals force, the structure is favorable for the rapid movement and storage of sodium ions between the layers, and the conversion reaction mechanism is different from the conventional insertion reaction and alloying reaction. When the material is used as a negative electrode material of a sodium ion battery, the theoretical capacity exceeds 1300 mAh/g, but FePS3The material can cause serious volume expansion due to the intercalation and deintercalation of sodium ions in the charging and discharging processes, so that the capacity is attenuated, the stability of the material is greatly reduced, and the cycle performance of the material is influenced.
To increase FePS3The specific capacity and the cycle life of a negative electrode material, and Chinese patent CN111261857A (southern aviation university) discloses FePS for a sodium ion battery3The preparation method of the/NC composite anode material comprises the following steps: 1) FePS is prepared3Adding dopamine hydrochloride into Tris buffer solution, stirring for 12-48h, carrying out solid-liquid separation,to obtain FePS3@ PDA material; 2) FePS prepared in the step 1)3The @ PDA material is subjected to heat preservation for 1-5 h at 800 ℃ in a reducing atmosphere or an inert atmosphere to obtain the material. FePS prepared by the patent3the/NC composite cathode material is of a lamellar structure, namely FePS3Carbon particles are uniformly attached to the surface of the sheet layer, so that the volume expansion of the material in the reaction process is effectively buffered, and the rapid transfer of electrons/ions is promoted. However, the preparation process of the composite negative electrode material is complex, the yield is low, and the composite negative electrode material is not suitable for large-scale production. Therefore, it is necessary to design a new FePS3The composite negative electrode material is suitable for mass preparation by further optimizing the process, and simultaneously improves the specific capacity and the cycle life of the material.
Disclosure of Invention
The invention aims to provide a three-dimensional composite cathode material of a sodium-ion battery, which solves the problems of complex preparation process and low yield of the cathode material of the sodium-ion battery in the prior art.
Secondly, the invention provides a preparation method of the three-dimensional composite cathode material of the sodium-ion battery.
The invention further provides an application of the three-dimensional composite negative electrode material of the sodium-ion battery in preparation of the sodium-ion battery.
Finally, the invention provides a sodium ion battery using the three-dimensional composite cathode material of the sodium ion battery.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the three-dimensional composite cathode material for the sodium-ion battery is of a lamellar structure and comprises graphene and FePS attached to the surface of the graphene3。
As a preferred embodiment, the graphene is reduced graphene oxide (rGO). Graphene, the first two-dimensional material widely studied (having a large specific surface area and weak inter-layer van der waals force), is a two-dimensional nanomaterial of a honeycomb-like lattice structure composed of carbon atoms in sp2 hybrid orbitals, has high conductivity, excellent flexibility and stable physicochemical properties, and is widely used as a conductive carrier in energy storage.
According to the invention, high-capacity cathode material FePS is anchored on graphene3The graphene can effectively protect the active material from direct contact with the electrolyte, thereby preventing the formation of an excessive SEI film. Meanwhile, the existence of graphene can enhance the structural stability of the active material and relieve Na as a buffer matrix+The volume changes dramatically after intercalation and deintercalation.
As a preferred embodiment, the FePS is3Is a single-chip or few-chip structure (the number of the few-chip structure is about 2-3), the thickness of the single chip is 1-2nm, and the radial width is 200-500 nm. Preferably, the FePS3Is about 1.5 nm thick.
As a preferred embodiment, the FePS3The preparation method comprises the following steps:
(a) uniformly mixing iron powder, phosphorus powder and sulfur powder, and sintering at 900 ℃ under a vacuum environment for 1-7 days to obtain block FePS3A crystal;
(b) the block FePS prepared in the step (a) is3Calcining the crystal at the temperature of 300-700 ℃ for 2-10h in inert atmosphere to obtain FePS3。
In a preferred embodiment, in the step (a), the molar ratio of the iron powder, the phosphorus powder and the sulfur powder is 1:1: 3-5. Further preferably, the molar ratio of the iron powder to the phosphorus powder to the sulfur powder is 1:1: 3-4.
As a preferred embodiment, in the step (a), the phosphor powder is red phosphor powder.
As a preferred embodiment, in the step (a), the sulfur powder is sublimed sulfur powder.
As a preferred embodiment, in the step (a), the mixed powder of the iron powder, the phosphorus powder and the sulfur powder is heated to 500-900 ℃ at a heating rate of 1-10 ℃/min.
In a preferred embodiment, in the step (a), the vacuum degree of the vacuum environment is 10-7-10-6 mbar。
In a preferred embodiment, in the step (a), the mixed powder of iron powder, phosphorus powder and sulfur powder is sintered at 800 ℃ for 3-6 d in a vacuum environment.
As a preferred embodiment, in step (b), the bulk FePS is3The temperature of the crystal is raised to 300-700 ℃ at a temperature rise rate of 1-10 ℃/min.
As a preferred embodiment, in the step (b), the inert gas atmosphere is a nitrogen gas atmosphere or an argon gas atmosphere.
As a preferred embodiment, the preparation of the three-dimensional composite anode material for the sodium-ion battery comprises the following steps: FePS is prepared3Carrying out wet mixing and ball milling on GO (graphene oxide) and then carrying out solid-liquid separation to obtain FePS3a/GO material; FePS is prepared3Annealing the/GO material in an inert atmosphere to obtain FePS3a/rGO material.
As a preferred embodiment, the wet ball milling is carried out in the presence of a surfactant. The surfactant is CTAB. Further preferably, FePS is added3GO, CTAB and a proper amount of water are added into a planetary ball mill and ball-milled for 5-20 h at the rotating speed of 500-600 rpm (preferably 550 rpm). The FePS3CTAB and GO are in a mass ratio of 3-9:1-2: 1.
In a preferred embodiment, the solid obtained after the solid-liquid separation is washed and vacuum-dried. The washing is carried out by washing with water (preferably deionized water) for more than 3 times, and then washing with absolute ethyl alcohol for more than 3 times. The temperature of the vacuum drying is 50-80 ℃, and the time of the vacuum drying is 12-48 h.
As a preferred embodiment, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
The present invention applies the most widely used method at present-chemical redox method-when generating reduced graphene oxide (rGO): graphite powder is subjected to chemical oxidation stripping to prepare graphene oxide sheets, the transverse size of the graphene oxide sheets can reach tens of microns, and meanwhile, the graphene oxide sheets have good hydrophilicity and are easy to disperse due to more oxygen-containing functional groups on the surfaces of ultrathin single-layer carbon atoms, and the graphene oxide sheets are more active in chemical properties than graphene. And more importantly, Graphene Oxide (GO) can be converted to rGO (reduced graphene oxide) by a thermal annealing process, and its conductivity is greatly improved while removing oxygen-containing functional groups, which is essential for high-power energy storage applications.
A preparation method of a three-dimensional composite anode material of a sodium-ion battery comprises the following steps:
(1) FePS is prepared3Carrying out solid-liquid separation after wet mixing and ball milling of GO to obtain FePS3a/GO material;
(2) FePS obtained in the step (1)3the/GO material is subjected to heat preservation for 1-3h at the temperature of 200-3the/rGO composite anode material.
As a preferred embodiment, in step (1), the FePS is used3And the mass ratio of GO is 3:1-9: 1.
As a preferred embodiment, in step (1), the wet ball milling is performed in the presence of a surfactant. The surfactant is CTAB. Further preferably, FePS is added3GO, CTAB and a proper amount of water are added into a planetary ball mill and ball-milled for 5-20 h at the rotating speed of 500-600 rpm (preferably 550 rpm). The FePS3CTAB and GO are in a mass ratio of 3-9:1-2: 1.
In a preferred embodiment, in the step (1), the solid obtained after the solid-liquid separation is washed and vacuum-dried. The washing is carried out by washing with water (preferably deionized water) for more than 3 times, and then washing with absolute ethyl alcohol for more than 3 times. The temperature of the vacuum drying is 50-80 ℃, and the time of the vacuum drying is 12-48 h.
As a preferred embodiment, in the step (2), the inert gas atmosphere is a nitrogen gas atmosphere or an argon gas atmosphere.
An application of a three-dimensional composite cathode material of a sodium-ion battery in preparing the sodium-ion battery.
A sodium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode comprises a negative electrode current collector (such as copper foil) and a negative electrode material layer coated on the surface of the negative electrode current collector, and the negative electrode material layer comprises a negative electrode active material and a conductive materialThe negative active material is the three-dimensional composite negative material (FePS) of the sodium ion battery3/rGO）。
The invention has the beneficial effects that:
the invention relates to a three-dimensional composite cathode material FePS of a sodium ion battery3the/rGO has a lamellar structure, and the surface of the lamellar structure of the rGO is uniformly attached with micro FePS3Nanosheets. FePS3Is ternary transition metal phosphosulfide and has special two-dimensional layered structure with van der waals force combination between layers, and this structure is favorable to the fast motion and storage of sodium ion between layers. The invention uses FePS3Is compounded with rGO, effectively buffers FePS3The volume expansion of the material in the reaction process promotes the rapid transfer of electrons/ions, and the longer cycle life can be realized on the premise of keeping higher specific capacity.
The invention relates to a three-dimensional composite cathode material (FePS) of a sodium ion battery3The improvement of the stability of the/rGO) system also greatly enhances the rate capability of the material. Experiments prove that the FePS of the invention is used3The sodium ion battery made of the/rGO composite negative electrode material has high discharge capacity and excellent rate capability, provides 514.3 mAh/g reversible capacity in the first circulation, and still retains 353.8 mAh/g high reversible specific capacity after 600 times of circulation.
Drawings
Fig. 1 is an SEM image of a three-dimensional composite negative electrode material of a sodium ion battery in example 1 of the present invention;
fig. 2 is an XRD spectrum of the three-dimensional composite anode material of the sodium-ion battery in example 1 of the present invention;
FIG. 3 is a charge/discharge cycle chart of a sodium ion battery prepared from the three-dimensional composite anode material of the sodium ion battery in example 1 of the present invention and a sodium ion battery in a comparative example at a current density of 0.1A/g;
FIG. 4 is a charge-discharge cycle chart of a sodium-ion battery made of the three-dimensional composite anode material of the sodium-ion battery in example 1 of the invention and a sodium-ion battery in a comparative example under different current densities;
fig. 5 is a graph comparing impedances of electrodes before and after cyclic voltammetry tests of the three-dimensional composite negative electrode material of the sodium ion battery as the negative electrode active material of the sodium ion battery in example 1 of the present invention.
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the experimental examples are briefly described above. It is to be understood that the above-described drawings illustrate only some experimental examples of the invention and are therefore not to be considered limiting of the scope of the claims. For a person skilled in the art, it is possible to derive other relevant figures from these figures without inventive effort.
Detailed Description
In order to make the technical problems solved by the present invention, the technical solutions adopted and the technical effects achieved easier to understand, the technical solutions of the present invention will be described in detail, completely and clearly below with reference to specific embodiments. Those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or conditions recommended by the product manufacturer. The reagents and instruments used in the examples, comparative examples and experimental examples are not specified by manufacturers, and are all conventional products commercially available. The GO manufacturer is Carbon Solutions (please confirm whether the description is correct, if there is no problem, the draft can be confirmed).
Example 1
The three-dimensional composite cathode material of the sodium-ion battery is of a lamellar structure and comprises reduced graphene oxide sheets and FePS attached to the reduced graphene oxide sheets3。
The preparation method of the three-dimensional composite anode material of the sodium-ion battery comprises the following steps:
(1) mixing iron powder, red phosphorus powder and sublimed sulfur according to a molar ratio of 1:1:3, grinding thoroughly, and sealing in a quartz ampoule bottle under vacuum (vacuum degree of 10)-6 mbar) in a muffle furnace at a heating rate of 1 ℃/min to 750 ℃ and sintering for 6 d to obtain the block FePS3A crystal;
(2) the obtained block FePS is treated3Putting the crystal into a quartz tube, heating to 500 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, and calcining for 2 h for annealingTreating to obtain FePS3；
(3) The prepared FePS3Adding the mixture, GO and CTAB into a ball milling tank with a volume of 50 mL according to a mass ratio of 3:1:1, adding 20 mL of deionized water, using a planetary ball mill, performing centrifugal separation after ball milling for 10h, sequentially washing for 3 times by using deionized water and absolute ethyl alcohol, and performing vacuum drying for 24 h at 60 ℃ to obtain FePS3a/CTAB/GO material;
(4) the prepared FePS3Placing CTAB/GO in an atmosphere furnace, and keeping the temperature for 1h at 300 ℃ in a nitrogen atmosphere to prepare nanosheet FePS3the/rGO (3:1) composite anode material.
The sodium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, the negative plate comprises a negative current collector copper foil and a negative material layer coated on the surface of the negative current collector, the negative material layer comprises a negative active substance, a conductive agent and a binder, and the negative active substance is the FePS prepared by the method3The composite negative electrode material of/rGO (3:1), the conductive agent is Keqin black, the binder is sodium carboxymethylcellulose and FePS3The mass ratio of the/rGO (3:1) composite negative electrode material to the Ketjen black to the sodium carboxymethyl cellulose is 7:2:1, the diaphragm is a glass fiber membrane (Whatman GF/C), and the electrolyte is dissolved with sodium hexafluorophosphate (NaPF)6) Ethylene carbonate and diethyl carbonate (EC: DEC =1:1, volume ratio 1: 1), concentration of sodium hexafluorophosphate in the electrolyte was 1.0 mol/L.
The preparation method of the sodium-ion battery in the embodiment comprises the following steps: FePS prepared in the above way3Mixing the/rGO (3:1) composite negative electrode material, Ketjen black and sodium carboxymethylcellulose according to the mass ratio of 7:2:1, then adding deionized water, uniformly mixing to obtain slurry, coating the slurry on the surface of a copper foil, carrying out vacuum drying at 80 ℃ overnight, and cutting to obtain a negative electrode sheet; metal sodium sheet as counter electrode, glass fiber membrane (Whatman GF/C) as diaphragm, and dissolved sodium hexafluorophosphate (NaPF)6) Ethylene carbonate and diethyl carbonate (EC: DEC =1:1, volume ratio 1: 1) as electrolyte, sodium hexafluorophosphate concentration in the electrolyte is 1.0 mol/L, and argon is addedThe 2032 coin-type half cell was assembled in a glove box protected and then left to stand for 16 h.
Example 2
The three-dimensional composite cathode material of the sodium-ion battery is of a lamellar structure and comprises reduced graphene oxide sheets and FePS attached to the reduced graphene oxide sheets3。
The preparation method of the three-dimensional composite anode material of the sodium-ion battery comprises the following steps:
(1) mixing iron powder, red phosphorus powder and sublimed sulfur according to a molar ratio of 1:1:3, grinding thoroughly, and sealing in a quartz ampoule bottle under vacuum (vacuum degree of 10)-6 mbar) in a muffle furnace at a heating rate of 1 ℃/min to 750 ℃ and sintering for 6 d to obtain the block FePS3A crystal;
(2) the obtained block FePS is treated3Putting the crystal into a quartz tube, heating to 500 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, calcining for 2 h, and annealing to obtain FePS3；
(3) The prepared FePS3Adding the mixture, GO and CTAB into a ball milling tank with a volume of 50 mL according to a mass ratio of 4:1:1, adding 20 mL of deionized water, using a planetary ball mill, performing centrifugal separation after ball milling for 10h, sequentially washing for 3 times by using the deionized water and absolute ethyl alcohol respectively, and performing vacuum drying for 24 h at 60 ℃ to obtain FePS3a/CTAB/GO material;
(4) the prepared FePS3Placing CTAB/GO in an atmosphere furnace, and keeping the temperature for 1h at 300 ℃ in a nitrogen atmosphere to prepare nanosheet FePS3the/rGO (4:1) composite anode material.
The sodium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, the negative plate comprises a negative current collector copper foil and a negative material layer coated on the surface of the negative current collector, the negative material layer comprises a negative active substance, a conductive agent and a binder, and the negative active substance is the FePS prepared by the method3The composite negative electrode material of/rGO (4:1), the conductive agent is Keqin black, the binder is sodium carboxymethylcellulose and FePS3a/rGO (4:1) composite anode material, Keqin black,The mass ratio of the sodium carboxymethylcellulose is 7:2:1, the diaphragm is a glass fiber membrane (Whatman GF/C), and the electrolyte is dissolved with sodium hexafluorophosphate (NaPF)6) Ethylene carbonate and diethyl carbonate (EC: DEC =1:1, volume ratio 1: 1), concentration of sodium hexafluorophosphate in the electrolyte was 1.0 mol/L.
The preparation method of the sodium-ion battery of the embodiment comprises the following steps: FePS prepared in the above way3Mixing the/rGO (4:1) composite negative electrode material, Ketjen black and sodium carboxymethylcellulose according to the mass ratio of 7:2:1, then adding deionized water, uniformly mixing to obtain slurry, coating the slurry on the surface of a copper foil, drying in vacuum at 80 ℃ overnight, and cutting to obtain a negative electrode sheet; metal sodium sheet as counter electrode, glass fiber membrane (Whatman GF/C) as diaphragm, and dissolved sodium hexafluorophosphate (NaPF)6) Ethylene carbonate and diethyl carbonate (EC: DEC =1:1, volume ratio of 1: 1) is used as electrolyte, concentration of sodium hexafluorophosphate in the electrolyte is 1.0 mol/L, 2032 type coin type half cell is assembled in a glove box with argon protection, and then standing is carried out for 16 h.
Example 3
The three-dimensional composite cathode material of the sodium-ion battery is of a lamellar structure and comprises reduced graphene oxide sheets and FePS attached to the reduced graphene oxide sheets3。
The preparation method of the three-dimensional composite anode material of the sodium-ion battery comprises the following steps:
(1) mixing iron powder, red phosphorus powder and sublimed sulfur according to a molar ratio of 1:1:3, grinding thoroughly, and sealing in a quartz ampoule bottle under vacuum (vacuum degree of 10)-6 mbar) in a muffle furnace at a heating rate of 1 ℃/min to 750 ℃ and sintering for 6 d to obtain the block FePS3A crystal;
(2) the obtained block FePS is treated3Putting the crystal into a quartz tube, heating to 500 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, calcining for 2 h, and annealing to obtain FePS3；
(3) The prepared FePS3Adding the mixture, GO and CTAB into a 50 mL container according to the mass ratio of 5:1:1Adding 20 mL of deionized water into the ball milling tank, ball milling for 10h by using a planetary ball mill, performing centrifugal separation, sequentially washing for 3 times by using the deionized water and absolute ethyl alcohol respectively, and performing vacuum drying for 24 h at 60 ℃ to obtain FePS3a/CTAB/GO material;
(4) the prepared FePS3Placing CTAB/GO in an atmosphere furnace, and keeping the temperature for 1h at 300 ℃ in a nitrogen atmosphere to prepare nanosheet FePS3the/rGO (5:1) composite anode material.
The sodium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, the negative plate comprises a negative current collector copper foil and a negative material layer coated on the surface of the negative current collector, the negative material layer comprises a negative active substance, a conductive agent and a binder, and the negative active substance is the FePS prepared by the method3the/rGO (5:1) composite anode material, the others are the same as in example 2.
The method for preparing the sodium ion battery of this example is the same as that of example 2.
Example 4
The three-dimensional composite cathode material of the sodium-ion battery is of a lamellar structure and comprises reduced graphene oxide sheets and FePS attached to the reduced graphene oxide sheets3。
The preparation method of the three-dimensional composite anode material of the sodium-ion battery comprises the following steps:
(1) mixing iron powder, red phosphorus powder and sublimed sulfur according to a molar ratio of 1:1:3, grinding thoroughly, and sealing in a quartz ampoule bottle under vacuum (vacuum degree of 10)-7 mbar) in a muffle furnace at a heating rate of 1 ℃/min to 750 ℃ and sintering for 6 d to obtain the block FePS3A crystal;
(2) the obtained block FePS is treated3Putting the crystal into a quartz tube, heating to 500 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, calcining for 2 h, and annealing to obtain FePS3；
(3) The prepared FePS3Adding the mixture, GO and CTAB into a ball milling tank with a volume of 50 mL according to the mass ratio of 6:1:1, and then adding 20 mL of deionized waterBall-milling for 10h by using a planetary ball mill, then performing centrifugal separation, sequentially washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and performing vacuum drying for 24 h at 60 ℃ to obtain FePS3a/CTAB/GO material;
(4) the prepared FePS3Placing CTAB/GO in an atmosphere furnace, and keeping the temperature for 1h at 300 ℃ in a nitrogen atmosphere to prepare nanosheet FePS3the/rGO (6:1) composite material.
The sodium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, the negative plate comprises a negative current collector copper foil and a negative material layer coated on the surface of the negative current collector, the negative material layer comprises a negative active substance, a conductive agent and a binder, and the negative active substance is the FePS prepared by the method3the/rGO (6:1) composite anode material, all others are the same as in example 2.
The method for preparing the sodium ion battery of this example is the same as that of example 2.
Example 5
The three-dimensional composite cathode material of the sodium-ion battery is of a lamellar structure and comprises reduced graphene oxide sheets and FePS attached to the reduced graphene oxide sheets3。
The preparation method of the three-dimensional composite anode material of the sodium-ion battery comprises the following steps:
(1) mixing iron powder, red phosphorus powder and sublimed sulfur according to a molar ratio of 1:1:3, grinding thoroughly, and sealing in a quartz ampoule bottle under vacuum (vacuum degree of 10)-6 mbar) in a muffle furnace at a heating rate of 1 ℃/min to 750 ℃ and sintering for 6 d to obtain the block FePS3A crystal;
(2) the obtained block FePS is treated3Putting the crystal into a quartz tube, heating to 500 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, calcining for 2 h, and annealing to obtain FePS3；
(3) The prepared FePS3Adding the mixture, GO and CTAB into a ball milling tank with a volume of 50 mL according to a mass ratio of 7:1:1, adding 20 mL of deionized water, using a planetary ball mill, performing centrifugal separation after ball milling for 10hSeparating, sequentially washing with deionized water and anhydrous ethanol for 3 times, vacuum drying at 60 deg.C for 24 hr to obtain FePS3a/CTAB/GO material;
(4) the prepared FePS3Placing CTAB/GO in an atmosphere furnace, and keeping the temperature for 1h at 300 ℃ in a nitrogen atmosphere to prepare nanosheet FePS3the/rGO (7:1) composite material.
The sodium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, the negative plate comprises a negative current collector copper foil and a negative material layer coated on the surface of the negative current collector, the negative material layer comprises a negative active substance, a conductive agent and a binder, and the negative active substance is the FePS prepared by the method3the/rGO (7:1) composite anode material, the others are the same as in example 2.
The method for preparing the sodium ion battery of this example is the same as that of example 2.
Example 6
The three-dimensional composite cathode material of the sodium-ion battery is of a lamellar structure and comprises reduced graphene oxide sheets and FePS attached to the reduced graphene oxide sheets3。
The preparation method of the three-dimensional composite anode material of the sodium-ion battery comprises the following steps:
(1) mixing iron powder, red phosphorus powder and sublimed sulfur according to a molar ratio of 1:1:3, grinding thoroughly, and sealing in a quartz ampoule bottle under vacuum (vacuum degree of 10)-6 mbar) in a muffle furnace at a heating rate of 1 ℃/min to 750 ℃ and sintering for 6 d to obtain the block FePS3A crystal;
(2) the obtained block FePS is treated3Putting the crystal into a quartz tube, heating to 500 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, calcining for 2 h, and annealing to obtain FePS3；
(3) The prepared FePS3Adding the mixture, GO and CTAB into a ball milling tank with a volume of 50 mL according to a mass ratio of 9:1:1, adding 20 mL of deionized water, using a planetary ball mill, performing centrifugal separation after ball milling for 10h, and sequentially washing with deionized water and absolute ethyl alcohol respectivelyVacuum drying at 60 deg.C for 24 hr for 3 times to obtain FePS3a/CTAB/GO material;
(4) the prepared FePS3Placing CTAB/GO in an atmosphere furnace, and keeping the temperature for 1h at 300 ℃ in a nitrogen atmosphere to prepare nanosheet FePS3a/rGO (9:1) composite.
The sodium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, the negative plate comprises a negative current collector copper foil and a negative material layer coated on the surface of the negative current collector, the negative material layer comprises a negative active substance, a conductive agent and a binder, and the negative active substance is the FePS prepared by the method3the/rGO (9:1) composite anode material, all others are the same as in example 2.
The method for preparing the sodium ion battery of this example is the same as that of example 2.
Comparative example
The negative electrode material of the sodium-ion battery of the comparative example is FePS3The preparation method is the same as that of example 1.
The sodium ion battery of the comparative example comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, the negative plate comprises a negative current collector copper foil and a negative material layer coated on the surface of the negative current collector, the negative material layer comprises a negative active substance, a conductive agent and a binder, and the negative active substance is the FePS prepared by the above method3The negative electrode material was otherwise the same as in example 1.
The method of making the sodium ion battery of this comparative example was the same as example 1.
Examples of the experiments
(1) Topography testing
FePS for sodium ion Battery in example 1 was used3SEM test is carried out on the/rGO (3:1) composite anode material, and the test result is shown in figure 1.
As can be seen from FIG. 1, FePS for sodium ion battery in example 13the/rGO (3:1) composite anode material is of a lamellar structure, and tiny FePS are uniformly attached to the surface of the GO lamellar structure3Nanosheets.
FePS for sodium ion Battery in example 1 was used3Composite negative electrode of/rGO (3:1)XRD testing was performed on the material, and the results are shown in FIG. 2.
As can be seen from FIG. 2, FePS for sodium ion battery in example 13FePS on XRD (X-ray diffraction) spectrum of/rGO (3:1) composite anode material3The diffraction peak of (A) is sharp and obvious, which shows that the crystal property is excellent.
(2) Electrochemical performance test
a. Respectively taking FePS in example 13Composite negative electrode material/rGO (3:1) and FePS in comparative example3The sodium ion battery prepared from the negative electrode material is subjected to charge-discharge cycle test at a constant temperature of 28 ℃ and a current density of 1A/g, and the test result is shown in figure 3.
As can be seen from FIG. 3, FePS3the/rGO provides a reversible capacity of 514.3 mAh/g in the first circulation, the coulombic efficiency of the first circle is about 49.8%, and after 600 cycles, a high reversible specific capacity of 353.8 mAh/g is still kept. However, FePS3After 600 cycles of circulation, the capacity of the negative electrode material is attenuated to 47.2 mAh/g, obvious capacity attenuation is shown, and the FePS is effectively improved by the load of the graphene3Cycling performance of the active.
b. Respectively taking FePS in example 13Composite negative electrode material/rGO (3:1) and FePS in comparative example3The sodium ion battery prepared from the negative electrode material is subjected to charge-discharge cycles at constant temperature of 28 ℃ and current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g and 5A/g, and the test result is shown in figure 4.
As is clear from FIG. 4, FePS in example 13the/rGO (3:1) composite negative electrode material has better rate discharge performance when being used for a sodium ion battery, the discharge capacity is about 400 mAh/g at 0.1A/g, about 400 mAh/g at 1A/g and about 340 mAh/g at 5A/g. In contrast, FePS in comparative example3The discharge capacity of the negative electrode material is approximately 301.6 mAh/g at 0.1A/g, approximately 120.9 mAh/g at 1A/g, and approximately 43.1 mAh/g at 5A/g. FePS3The negative electrode material exhibits poor rate performance.
c. Taking FePS in example 13Preparation of/rGO (3:1) composite anode materialThe obtained negative electrode of the sodium ion battery was subjected to an electrochemical impedance test, and the test results are shown in fig. 5.
As can be seen from FIG. 5, FePS3the/rGO shows smaller electrochemical transfer resistance and simultaneously shows excellent ion diffusion performance. The reduced graphene oxide is used as a conductive matrix, so that the conductivity of the electrode material is improved, and the diffusion efficiency of ions is improved due to the large specific surface area of the electrode material.
The experiment results show that the three-dimensional composite cathode material of the sodium-ion battery is FePS3Is compounded with rGO, and can effectively buffer FePS3The volume of the material expands in the reaction process, the rapid transfer of electrons/ions is promoted, and the longer cycle life is realized on the premise of keeping higher specific capacity. The sodium ion battery prepared from the composite anode material FePS3/rGO has high specific capacity, excellent cycling stability and rate capability.
The above description is only a preferred embodiment and experimental examples of the present invention, and is not intended to limit the scope of the present invention. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A three-dimensional composite negative electrode material of a sodium ion battery is characterized in that: the material is of a lamellar structure and comprises graphene and FePS attached to the surface of the graphene3。
2. The three-dimensional composite anode material of the sodium-ion battery as claimed in claim 1, wherein: the graphene is reduced graphene oxide.
3. The three-dimensional composite anode material of the sodium-ion battery as claimed in claim 1, wherein: the FePS3The structure is a single-chip or a few-chip structure, the thickness of the single chip is 1-2nm, and the radial width is 200-500 nm.
4. The three-dimensional composite anode material for the sodium-ion battery according to any one of claims 1 to 3, wherein: the FePS3The preparation method comprises the following steps:
(a) uniformly mixing iron powder, phosphorus powder and sulfur powder, and sintering at 900 ℃ under a vacuum environment for 1-7 days to obtain block FePS3A crystal;
(b) the block FePS prepared in the step (a) is3Calcining the crystal at the temperature of 300-700 ℃ for 2-10h in inert atmosphere to obtain FePS3。
5. The three-dimensional composite anode material of the sodium-ion battery as claimed in claim 4, wherein: in the step (a), the molar ratio of the iron powder to the phosphorus powder to the sulfur powder is 1:1: 3-5; preferably, the phosphorus powder is red phosphorus powder, and the sulfur powder is sublimed sulfur powder; preferably, the mixed powder of the iron powder, the phosphorus powder and the sulfur powder is heated to 500-900 ℃ at a heating rate of 1-10 ℃/min; preferably, the vacuum degree of the vacuum environment is 10-7-10-6mbar; in step (b), the bulk FePS3The temperature of the crystal is raised to 300-700 ℃ at the temperature raising rate of 1-10 ℃/min; the inert atmosphere is nitrogen atmosphere or argon atmosphere.
6. A method for preparing the three-dimensional composite anode material of the sodium-ion battery as claimed in any one of claims 1 to 5, wherein the method comprises the following steps: the method comprises the following steps:
(1) FePS is prepared3Carrying out solid-liquid separation after wet mixing and ball milling of GO to obtain FePS3a/GO material;
(2) FePS obtained in the step (1)3the/GO material is subjected to heat preservation for 1-3h at the temperature of 200-3the/rGO composite anode material.
7. The preparation method of the three-dimensional composite anode material of the sodium-ion battery as claimed in claim 6, wherein the preparation method comprises the following steps: in the step (1), the FePS3And the mass ratio of GO is 3:1-9: 1.
8.The preparation method of the three-dimensional composite anode material of the sodium-ion battery as claimed in claim 6, wherein the preparation method comprises the following steps: in the step (1), the wet mixing ball milling is carried out in the presence of a surfactant, wherein the surfactant is CTAB; preferably, FePS is used3Wet mixing and ball milling GO, CTAB and water, and FePS3CTAB and GO are in a mass ratio of 3-9:1-2: 1; washing and vacuum drying the solid obtained after the solid-liquid separation; preferably, the washing is carried out for more than 3 times by using water, and then, the washing is carried out for more than 3 times by using absolute ethyl alcohol; the temperature of the vacuum drying is 50-80 ℃, and the time of the vacuum drying is 12-48 h; in the step (2), the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
9. Use of the three-dimensional composite anode material of the sodium-ion battery as defined in any one of claims 1 to 5 in the preparation of the sodium-ion battery.
10. A sodium ion battery, characterized by: the sodium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode comprises a negative electrode current collector and a negative electrode material layer coated on the surface of the negative electrode current collector, the negative electrode material layer comprises a negative electrode active substance, a conductive agent and a binder, and the negative electrode active substance adopts the three-dimensional composite negative electrode material of the sodium ion battery as defined in any one of claims 1-5.
CN202110399454.0A 2021-04-14 2021-04-14 Three-dimensional composite negative electrode material of sodium-ion battery and preparation method and application thereof Withdrawn CN113113609A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110399454.0A CN113113609A (en) 2021-04-14 2021-04-14 Three-dimensional composite negative electrode material of sodium-ion battery and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110399454.0A CN113113609A (en) 2021-04-14 2021-04-14 Three-dimensional composite negative electrode material of sodium-ion battery and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN113113609A true CN113113609A (en) 2021-07-13

Family

ID=76716869

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110399454.0A Withdrawn CN113113609A (en) 2021-04-14 2021-04-14 Three-dimensional composite negative electrode material of sodium-ion battery and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113113609A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113903886A (en) * 2021-11-15 2022-01-07 珠海冠宇电池股份有限公司 Negative plate and lithium ion battery comprising same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113903886A (en) * 2021-11-15 2022-01-07 珠海冠宇电池股份有限公司 Negative plate and lithium ion battery comprising same
CN113903886B (en) * 2021-11-15 2023-02-28 珠海冠宇电池股份有限公司 Negative plate and lithium ion battery comprising same

Similar Documents

Publication Publication Date Title
WO2021004150A1 (en) Preparation method for negative electrode material sns/nd-cn of lithium-ion battery
Han et al. Graphene oxide-decorated Fe 2 (MoO 4) 3 microflowers as a promising anode for lithium and sodium storage
CN112038614B (en) Negative electrode material for sodium ion battery and preparation method thereof
CN109167048B (en) Titanium and nitrogen co-doped carbon-coated silicon monoxide material and preparation method and application thereof
CN113675402A (en) Metal-nitrogen doped porous carbon material and preparation method and application thereof
CN113823781A (en) Composite negative electrode material and preparation method thereof
CN109546099B (en) Graphite composite negative electrode material, preparation method thereof and lithium ion battery
CN113871605A (en) Pre-lithiated silicon-based negative electrode material and preparation method and application thereof
CN110752361B (en) Preparation method of modified silicon-based negative electrode material of lithium battery
CN112421049A (en) Method for preparing lithium battery silicon-carbon negative electrode material through ball milling and silicon-carbon negative electrode material
CN113113609A (en) Three-dimensional composite negative electrode material of sodium-ion battery and preparation method and application thereof
CN111747449A (en) Superfine MoO uniformly bridged inside flaky carbon matrix2Electrode material of nano particles and preparation method and application thereof
CN114039051B (en) MXene/SnO with three-dimensional structure 2 Negative electrode composite material and preparation method thereof
CN112421002B (en) High-capacity silicon-carbon material and preparation method thereof
CN115275166A (en) Long-life graphite composite material and preparation method thereof
CN114792788A (en) Sodium ion full cell and preparation method thereof
CN114695881A (en) Bismuth sulfide negative electrode material and preparation method and application thereof
CN114122371A (en) Preparation method of porous silicon-carbon negative electrode material of lithium ion battery
CN109935821B (en) SiO (silicon dioxide)xPreparation method of-G/PAA-PANI/graphene composite material
CN112520787A (en) Preparation method of solution of beta-phase sodium metavanadate and application of solution in lithium ion battery
CN112018356A (en) Flaky potassium ion negative electrode material
CN114079044A (en) Three-dimensional porous silicon/graphene composite negative electrode material, preparation method thereof and lithium ion battery
CN112652744A (en) Preparation method of high-capacity high-cycle lithium battery negative electrode material and lithium battery
CN111261857B (en) FePS for sodium ion battery3/NC composite negative electrode material, preparation method thereof and sodium ion battery
CN111293297A (en) Carbon-coated MoSe2Black phosphorus composite material and preparation method thereof

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
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20210713