CN114709414A - Sodium battery, and preparation method of positive electrode material and positive electrode plate thereof - Google Patents

Sodium battery, and preparation method of positive electrode material and positive electrode plate thereof Download PDF

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CN114709414A
CN114709414A CN202210416849.1A CN202210416849A CN114709414A CN 114709414 A CN114709414 A CN 114709414A CN 202210416849 A CN202210416849 A CN 202210416849A CN 114709414 A CN114709414 A CN 114709414A
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solution
carbon spheres
positive electrode
electrode material
fef
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马增胜
邱园
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Xiangtan University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a sodium battery and a preparation method of a positive electrode material and a positive plate thereof, wherein the preparation method of the positive electrode material comprises the following steps: preparing hollow carbon spheres; etching the hollow carbon spheres by using HF solution to obtain hollow mesoporous carbon spheres; FeF is mixed2Injecting the mixture into the etched hollow mesoporous carbon spheres to obtain the anode material HMCS @ FeF2(ii) a And the positive plate of the sodium battery and the sodium battery are manufactured by using the positive material. According to the invention, through designing the anode material with a three-dimensional structure, the conductivity of the anode is improved, the dissolution of active substances is avoided, the diffusion path of sodium ions in the electrode is shortened, the utilization rate of the active substances is improved, and the overall electrochemical performance of the battery is improved.

Description

Sodium battery, positive electrode material thereof and preparation method of positive electrode plate
Technical Field
The invention relates to the technical field of battery preparation, in particular to a positive electrode material and a positive plate of a sodium battery and a preparation method of the sodium battery.
Background
The development of electric vehicles, artificial intelligence and the like is very popular, however, high-safety and green pollution-free energy storage devices are required in all the application scenes, and therefore, lithium ion batteries are also unavailable. The large-scale application of lithium ion batteries also further highlights the problem of scarcity of lithium resources. The main application problem of sodium batteries as an energy storage device which has potential to replace lithium batteries is that the ion transmission rate is low and the energy density of the batteries is low because the half valence of sodium ions is greater than that of lithium ions. The development of the positive electrode material with high capacity and high rate performance is the key for improving the energy density of the sodium battery and the successful application of the sodium ion battery in the future.
At present, the sodium battery of the lithium polymer battery company in China uses a Ni/Fe/Mn material as a positive electrode, hard carbon as a negative electrode, and the energy density reaches 100 Wh/kg. However, the conventional anode material in the sodium battery has lower theoretical specific capacity, so the conductivity of the anode is low.
Disclosure of Invention
The invention aims to provide a sodium battery, a positive electrode material thereof and a preparation method of a positive electrode plate.
In order to solve the above problems, a first aspect of the present invention provides a method for preparing a positive electrode material for a sodium battery, comprising the steps of:
preparing carbon spheres;
etching the carbon spheres by using a strong acid solution to obtain hollow mesoporous carbon spheres;
FeF is mixed2And injecting hollow mesoporous carbon spheres to obtain the cathode material.
Preferably, the preparation of the carbon spheres comprises the following steps:
adding the ethyl orthosilicate solution into the first mixed solution, and stirring to obtain a second solution;
adding a dopamine solution or a phenolic resin solution into the second solution, and continuously stirring to obtain a black solid;
and centrifugally separating the black solid, and calcining under an inert gas atmosphere to obtain the hollow carbon spheres.
Preferably, NH in the first mixed solution4OH：H2O: anhydrous ethanol ═ 6: 20: 140.
preferably, the etching the carbon spheres by using a strong acid solution to obtain the hollow mesoporous carbon spheres specifically comprises:
and diluting the HF solution, adding the diluted HF solution into the carbon spheres, fully stirring, cleaning and drying.
Preferably, the FeF is2Injecting hollow mesoporous carbon spheres to obtain the cathode material, wherein the cathode material specifically comprises the following components:
adding an active agent into the aqueous solution mixed with the hollow mesoporous carbon spheres and the ferrous fluosilicate, vacuumizing, and freeze-drying;
calcining in an inert gas atmosphere, and grinding to obtain the cathode material.
Preferably, the inert gas atmosphere calcination is:
calcining at 250 ℃ and a heating rate of 3 ℃/min for 4 hours under an argon atmosphere.
Preferably, the aqueous solution of the ferrous fluosilicate is FeSiF6·6H2Mixed solution of O powder and deionized water or FeSiF6An aqueous solution of (a).
According to one aspect of the invention, the preparation method of the positive plate of the sodium battery comprises the following steps:
preparing slurry mixed with the positive electrode material, the binder and the conductive agent;
and coating the slurry on an aluminum foil for vacuum drying and cutting to obtain the positive plate.
Preferably, the mass ratio of the positive electrode material, the binder and the conductive agent in the slurry is 8: 1: 1.
according to yet another aspect of the present invention, there is provided a sodium battery comprising a positive electrode sheet made of a positive electrode material.
The technical scheme of the invention has the following beneficial technical effects:
through the design of the anode material with the three-dimensional structure, the conductivity of the anode is improved, the dissolution of active substances is avoided, the diffusion path of sodium ions in the electrode is shortened, the utilization rate of the active substances is improved, and the overall electrochemical performance of the battery is improved.
Drawings
Fig. 1 is a flowchart of a first embodiment of a method for producing a positive electrode material according to the present invention;
FIG. 2 is SiO of the present invention2SEM picture of @ C;
FIG. 3 is a drawing of the present inventionHF treated SiO2SEM picture of @ C;
FIG. 4 is HMCS @ FeF of the present invention2XRD pattern of (a);
FIG. 5 is HMCS @ FeF of the present invention2SEM picture of (1);
FIG. 6 is HMCS @ FeF of the present invention2A TEM image of (B);
FIG. 7a is HMCS @ FeF of the present invention2Mapping graph of the distribution of the medium Fe element;
FIG. 7b is HMCS @ FeF of the present invention2Mapping graph of the distribution of the medium C element;
FIG. 7c is HMCS @ FeF of the present invention2Mapping graph of the distribution of the middle F element;
FIG. 8 is a schematic of the long cycle electrochemical performance of a sodium cell of the present invention;
FIG. 9 is a schematic of the rate electrochemical performance of a sodium cell of the present invention;
fig. 10 is a graph of impedance before and after cycling for a sodium battery of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all 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. In the description of the present invention, it should be noted that the terms "first", "second", and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The first embodiment is as follows:
fig. 1 shows a flow chart of a method for preparing a cathode material of the present invention, comprising the steps of:
s1, preparing carbon spheres;
s2, etching the carbon spheres by using a strong acid solution to obtain hollow mesoporous carbon spheres;
s3, mixing FeF2And injecting the hollow mesoporous carbon spheres to obtain the cathode material.
The invention is realized by adding active substance FeF2Injecting hollow mesoporous carbon spheres HMCS (mesoporous carbon spheres) with three-dimensional structure to obtain positive electrode material HMCS @ FeF2The lithium ion battery has high anode conductivity, can avoid the dissolution of active substances, shortens the diffusion path of sodium ions in an electrode, and improves the utilization rate of the active substances, so that the overall electrochemical performance of the sodium battery is improved.
Wherein, step S1 includes the following steps:
s101, adding an ethyl orthosilicate solution into the first mixed solution, and stirring to obtain a second solution;
s102, adding a dopamine solution or a phenolic resin solution into the second solution, and continuously stirring to obtain a black solid;
s103, centrifugally separating black solids, and calcining in an inert gas atmosphere to obtain black hollow carbon spheres.
In a preferred embodiment of the invention, the preparation is made of SiO2Hollow carbon sphere SiO used as hard template2@ C, in particular:
adding 5.6ml of an ethyl orthosilicate solution with the purity of 99% into a beaker containing 166ml of the first mixed solution and stirring; wherein, NH in the first mixed solution is set4OH：H2O: anhydrous ethanol ═ 6: 20: 140, the synthesized anode material has better appearance.
160mL, 5mg/mL of dopamine solution or phenolic resin solution is added to the second solution, and stirring is continued for 12 hours at 300rmp/min, so that the solution is fully reacted, and further black solid is obtained.
Wherein the tetraethoxysilane is used for leading the shell of the carbon sphere to contain SiO2A dopamine solution or a phenolic resin is used to make the outer shell of the carbon sphere contain carbon.
The black solid was separated by centrifugation and used deionized water and anhydrousWashed three times with ethanol to remove NH4 from the black solid+(ii) a Then calcining for 5 hours under the conditions that the nitrogen atmosphere is 800 ℃ and the heating rate is 2 ℃/min to obtain black powder, namely the hollow carbon sphere SiO with the three-dimensional structure shown in figure 2 is obtained2@C。
See SiO in FIG. 22@ C, the resulting hollow carbon spheres have a diameter of about 200nm-400nm, and the hollow carbon spheres are intact in shape.
The anode material disclosed by the invention utilizes the three-dimensional structure of the hollow carbon spheres, so that the circulation stability of the sodium battery can be improved, and the electrochemical performance and the circulation life of the sodium battery are finally improved.
In step S2, etching the hollow carbon spheres with the strong acid solution to form hollow mesoporous carbon spheres HMCS with a pore structure, so as to facilitate the subsequent active substance to enter the cavity of the hollow mesoporous carbon spheres HMCS, specifically comprising the following operations:
and 4ml of HF solution is added into 50ml of polytetrafluoroethylene Dimura as a substrate and 12ml of deionized water for dilution, so that the diluted acidity and corrosiveness can etch only a small part of the hollow carbon spheres, and the control of the appearance of the etched hollow carbon spheres is facilitated.
By preparing the appropriate acidity and corrosivity of the HF solution, the corrosion degree of the hollow carbon spheres can be well controlled, the carbon spheres are prevented from being broken due to too strong acidity and corrosivity or the hole structure is incomplete due to weak acidity and corrosivity, and the FeSiF is further facilitated6Into the subsequent reaction to form FeF2。
Stirring the diluted HF solution at the rotating speed of 100rmp/min for 10 minutes to dilute the solution evenly, adding 0.4g of hollow carbon spheres, stirring for 1 hour, cleaning and drying the solution in a water suction filtration system by using deionized water and absolute ethyl alcohol, and drying the solution in a 60 ℃ oven for 12 hours to obtain HF-etched hollow mesoporous carbon spheres HMCS shown in figure 3.
In the embodiment, deionized water is firstly used for cleaning, and meanwhile, absolute ethyl alcohol is added, so that the drying time is shortened by utilizing the property of easy volatilization of the absolute ethyl alcohol, and meanwhile, the absolute ethyl alcohol is placed into a circulating water suction filtration system, namely a vacuum pump for suction filtration, so that solid-liquid separation is realized as soon as possible, and water filtration and drying are accelerated;
in the embodiment, the etching degree of the hollow carbon spheres can be controlled by controlling the rotating speed, so that insufficient or excessive corrosion to the hollow carbon spheres is avoided.
In this embodiment, using HF as a strong acid can shorten the time to etch the hollow carbon spheres.
In another embodiment of the present invention, the HF solution may also be replaced with a NaOH solution.
In step S3, FeF is mixed2Injecting the mixture into the etched hollow mesoporous carbon spheres to obtain a positive electrode material, namely HMCS @ FeF2The method specifically comprises the following steps:
adding an active agent into the aqueous solution mixed with the prepared hollow mesoporous carbon spheres HMCS and the ferrous fluosilicate, vacuumizing, and freeze-drying; wherein the aqueous solution of the ferrous fluosilicate is FeSiF6·6H2Mixed solution of O powder and deionized water or FeSiF6An aqueous solution of (a).
In a preferred embodiment of the present invention, HMCS and FeF are used for precise control of the hollow mesoporous carbon spheres2The proportion of (1) avoids agglomeration of ferrous fluosilicate particles when the hollow mesoporous carbon spheres are compounded, and 50mg of etched hollow mesoporous carbon spheres and 40mg of light green powdery FeSiF are mixed6·6H2Adding O into a beaker containing 40ml of deionized water, adding 4 drops of an active agent, preferably triton X-100, vacuumizing in a transition bin of a glove box for 2 times, 5min each time, stirring for 24 hours, and freeze-drying;
in this embodiment, air inside the hollow mesoporous carbon spheres and water in the ferrous fluorosilicate solution can be pumped out by vacuumizing the transition chamber of the glove box, so that the precursor solution (ferrous fluorosilicate solution) can conveniently enter the hollow mesoporous carbon spheres.
Calcining the mixture of the ferrous fluosilicate solution and the hollow mesoporous carbon spheres for 4 hours at the temperature rise rate of 3 ℃/min at 250 ℃ under the argon atmosphere to react and generate FeF2Grinding to obtain the positive electrode for manufacturing the sodium batteryMaterial HMCS @ FeF2。
In the embodiment, the freeze drying is adopted to avoid the sedimentation phenomenon of the ferrous fluorosilicate generated by drying, and the freeze drying can keep the original solution state, reduce the sedimentation of the ferrous fluorosilicate and keep the ferrous fluorosilicate in the hollow mesoporous carbon spheres.
In this embodiment, the ferrous fluorosilicate may be fully reacted to form FeF in any inert gas atmosphere by controlling parameters such as temperature, heating rate, and calcination time2。
FIGS. 4-6 are respectively HMCS @ FeF of the present invention2XRD, SEM and TEM images of FeF, as can be seen from FIG. 52Successfully injecting into the carbon spheres;
HMCS @ FeF from FIG. 42And SiO2The XRD comparison of @ C deal with HF shows that the main peak is basically unchanged, but FeF is not detected2From which it can be concluded that the carbon spheres are completely coated with FeF2；
In the high-resolution TEM image shown in FIG. 6, white is FeF2The shaded part is a hollow mesoporous carbon sphere, and the FeF is successfully coated on the carbon sphere2。
Further, from the high resolution mapping distribution of Fe/C/F elements in FIG. 7 a-FIG. 7C, the Fe/F elements are substantially overlapped.
Example two:
preparation of HMCS @ FeF2The positive plate specifically comprises the following steps:
mixing substances for manufacturing an electrode to prepare slurry, wherein the substances in the electrode comprise a positive electrode material HMCS @ FeF2A binder and a conductive agent, wherein the positive electrode material HMCS @ FeF in the slurry2And the mass ratio of the binder to the conductive agent is 8: 1: 1.
in a preferred embodiment of the invention, 0.08mg of HMCS @ FeF is selected2Adding 0.01mg of adhesive PVDF and 0.01mg of conductive agent Super P into a mortar, uniformly mixing, grinding for 1 hour, adding a proper MNP solution, continuously grinding for 30min, coating the ground slurry on an aluminum foil, and drying in vacuum at 100 ℃ for 24 hours; dryingCutting the positive plate into a square pole piece with the size of 8mm multiplied by 8mm after the positive plate is finished, and weighing to obtain the active substance HMCS @ FeF in the positive plate2Has a mass of about 0.5 mg.
Example three:
preparing a sodium battery comprising the steps of:
in a preferred embodiment of the invention, a coin cell of the type CR2032 is selected, the material is 304 stainless steel, the separator is made of glass fiber (Waterman), the negative electrode is made of a sodium sheet with the diameter of 14mm, and 1M NaClO4in EC/PC (1: 1V%) + 5% FEC electrolyte. Wherein the sodium tablet is obtained by cutting purchased block sodium in a glove box, rolling into thin slices and punching.
And assembling the half-cell in a glove box according to the sequence of the metal sodium sheet, the diaphragm, the positive plate, the gasket and the spring sheet, and then pressing the half-cell into the sodium cell by using a press (Kejing).
The following performance test experiments were performed on the sodium battery of the present invention:
as shown in FIG. 8, 1M NaClO is used as the electrolyte4Long cycle electrochemical performance plot of cells at in EC/PC (1: 1V%) + 5% FEC, it can be seen that: under room temperature, the loading capacity of about 0.5mg is long circulated for 90 times under the condition of 100mA/g, the specific capacity of about 200mAh/g still exists, and compared with pure ferrous fluoride, the electrochemical performance is obviously excellent.
Fig. 9 is a graph of the rate electrochemical performance of the sodium battery, and it can be seen that the sodium battery manufactured by using the cathode material of the present invention has better rate performance.
Fig. 10 is a graph of impedance before and after cycling of the sodium cell, and it can be seen that the sodium cell has reduced impedance before and after cycling, indicating that the interface transfer impedance is reduced, forming a better collected electrolyte interface CEI during cycling.
The sodium battery adopts a core-shell ferrous fluoride material coated by carbon spheres as a positive electrode, utilizes hollow mesoporous carbon spheres HMCS as a coating shell, and then utilizes HF to corrode the shell, thereby injecting an active substance into the shell.
According to the invention, through designing the anode with a three-dimensional structure, the conductivity of the anode is improved, the dissolution of active substances is avoided, the diffusion path of sodium ions in the electrode is shortened, and the utilization rate of the active substances is improvedThe overall electrochemical performance of the battery is improved. Compared with the prior art, the FeF is improved2Improving the dispersibility of FeF2Utilization rate, avoiding FeF2Dissolved in the electrolyte.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.

Claims (10)

1. A preparation method of a positive electrode material of a sodium battery is characterized by comprising the following steps:
preparing carbon spheres;
etching the carbon spheres by using a strong acid solution to obtain hollow mesoporous carbon spheres;
FeF is mixed2And injecting hollow mesoporous carbon spheres to obtain the cathode material.
2. The method for preparing a positive electrode material according to claim 1, wherein the preparing of the carbon spheres comprises the steps of:
adding the ethyl orthosilicate solution into the first mixed solution, and stirring to obtain a second solution;
adding a dopamine solution or a phenolic resin solution into the second solution, and continuously stirring to obtain a black solid;
and centrifugally separating the black solid, and calcining under an inert gas atmosphere to obtain the hollow carbon spheres.
3. The method for producing a positive electrode material according to claim 2, wherein NH is contained in the first mixed solution4OH：H2O: anhydrous ethanol ═ 6: 20: 140.
4. the method for preparing the cathode material according to claim 1, wherein the etching of the carbon spheres with a strong acid solution to obtain the hollow mesoporous carbon spheres comprises:
and diluting the HF solution, adding the diluted HF solution into the carbon spheres, fully stirring, cleaning and drying.
5. The method for producing a positive electrode material according to claim 1, wherein the FeF is mixed2Injecting hollow mesoporous carbon spheres to obtain the cathode material, wherein the cathode material specifically comprises the following components:
adding an active agent into the aqueous solution mixed with the hollow mesoporous carbon spheres and the ferrous fluosilicate, vacuumizing, and freeze-drying;
calcining in an inert gas atmosphere, and grinding to obtain the cathode material.
6. The method for producing a positive electrode material according to claim 5, wherein the inert gas atmosphere calcination is:
calcining at 250 ℃ and a heating rate of 3 ℃/min for 4 hours under an argon atmosphere.
7. The method for producing a positive electrode material according to claim 5, wherein the aqueous solution of ferrous fluorosilicate is FeSiF6·6H2Mixed solution of O powder and deionized water or FeSiF6An aqueous solution of (a).
8. The preparation method of the positive plate of the sodium battery is characterized by comprising the following steps of:
preparing a slurry in which a positive electrode material according to any one of claims 1 to 7, a binder and a conductive agent are mixed;
and coating the slurry on an aluminum foil for vacuum drying and cutting to obtain the positive plate.
9. The method for preparing the positive plate according to claim 8, wherein the mass ratio of the positive electrode material, the binder and the conductive agent in the slurry is 8: 1: 1.
10. a sodium battery comprising a positive electrode sheet produced from the positive electrode material according to any one of claims 1 to 7.
CN202210416849.1A 2022-04-20 2022-04-20 Sodium battery, and preparation method of positive electrode material and positive electrode plate thereof Pending CN114709414A (en)

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