CN114649508B - Antimony-based integrated electrode and preparation method and application thereof - Google Patents

Antimony-based integrated electrode and preparation method and application thereof Download PDF

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CN114649508B
CN114649508B CN202210360667.7A CN202210360667A CN114649508B CN 114649508 B CN114649508 B CN 114649508B CN 202210360667 A CN202210360667 A CN 202210360667A CN 114649508 B CN114649508 B CN 114649508B
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antimony
titanium foil
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程勇
王照民
尹东明
王春丽
梁飞
吴耀明
王立民
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Changchun Institute of Applied Chemistry of CAS
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
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    • 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
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Abstract

The invention provides an antimony-based integrated electrode and a preparation method and application thereof, belonging to the technical field of electrode preparation methods. The method comprises the steps of sequentially utilizing a hydrothermal reaction process to deposit the stibnite (Sb) in situ on a titanium foil substrate 3+ Sb 5+ O 4 ) And in situ coated titanium hydroxide (Ti (OH) 4 ) And heating the obtained product in an argon gas environment by using a tube furnace to perform a firming treatment. The electrode has a multilayer structure and comprises a titanium foil, wherein Sb is sequentially deposited on the surface of the titanium foil in situ 3+ Sb 5+ O 4 Layer and in-situ coated titanium dioxide (TiO) 2 ) A layer. The antimony-based integrated electrode firmly processes the battery active substance on the current collector of the battery pole piece in the manufacturing process, avoids the use of additives, and can improve the energy density of the battery and inhibit Sb to a certain extent when being applied to lithium and sodium ion batteries 3+ Sb 5+ O 4 Layer and TiO 2 The layer is peeled off.

Description

Antimony-based integrated electrode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrode preparation methods, and particularly relates to an antimony-based integrated electrode and a preparation method and application thereof.
Background
With the development of secondary battery technology, high energy density and flexibility of lithium and sodium ion batteries are desired, and integrated electrodes have been widely researched due to high energy density and flexibilityAnd (5) refining. Among the alloy-based materials, antimony (Sb) is a strong competitor for the negative electrodes of lithium ion batteries and sodium ion batteries because it has a two-dimensional wrinkled layer structure, which is advantageous for improving electrical conductivity. Meanwhile, the Sb-rich interlayer spacing is beneficial to lithium ions with smaller ionic radius
Figure BDA0003585069310000011
Also facilitates the storage of sodium ions with a larger ion radius>
Figure BDA0003585069310000012
And (4) storing. Notably, the potential of sodium is lower, at-2.71V/SHE, than Li/Li + The redox couple has a potential close to (-3.04V) which also has a higher energy density. Compared with the lithium and sodium storage mechanism of graphite, sb reacts with lithium and sodium to form an alloy with a very favorable molar ratio. In addition, it has a superior theoretical specific capacity (Li) 3 Sb、Na 3 Sb：～660mAh g -1 ) Safer discharge potential and a stable discharge plateau, thereby providing a satisfactory operating voltage.
The conventional lithium and sodium ion battery electrode (negative electrode) is composed of a current collector (copper foil), an active material and additives (binder and conductive agent). The preparation of the negative electrode is mainly to combine the active substance to the current collector by a wet-process slurry drawing process, and obviously, the bonding mode of the active substance and the current collector has the objective defect of infirm combination to a certain extent; on the other hand, the additives to be added in the process of preparing the electrode by adopting the technology greatly reduce the energy density of the battery. The energy density of lithium and sodium ion batteries can be improved by reducing additives, so that a new preparation technology of an antimony-based integrated electrode needs to be developed.
In the prior art, there are various methods for preparing an integrated electrode, for example, patent publication No. CN 113437247A discloses a molten salt electrodeposition method, which uses a foam metal or a metal plate (foil) as a substrate to form a tin-antimony-based integrated electrode by a molten salt electrochemical deposition method, and the electrode obtained by the method has a strong combination of active materials and current collectors,the use of additives is avoided, but the problem of relatively high energy consumption also exists; patent publication No. CN 110350146A discloses a modified three-dimensional porous antimony electrode, a preparation method and application, mainly using three-dimensional porous copper as a current collector, adopting an electrodeposition method to deposit antimony on the surface thereof, then electrodepositing metallic indium, and further oxidizing to obtain the cathode, when the modified three-dimensional porous antimony electrode is used as a lithium ion battery cathode, the modified three-dimensional porous antimony electrode is prepared by using 500mA g of antimony at the same time -1 After 180 times of circulation, the specific capacity of the alloy still keeps 500mAh g -1 (ii) a Patent publication No. CN 108199003A discloses a three-dimensional large/mesoporous antimony cathode, a preparation method and application thereof, wherein three-dimensional porous copper is also used as a substrate, an electrodeposition method is adopted to deposit Zn-Sb alloy, then the Zn is removed by thermal sublimation, and when the electrode is used as a cathode of a sodium ion battery, the amount of the Zn is 100mA g -1 The first discharge specific capacity under the current density is 710.6mAh g -1 (ii) a Chan et al prepare Sb-NiSb-Ni array structure by AAO template method at 66mA g -1 After the current density is circulated for 300 circles, the specific capacity still remains 391mAh g -1 Corresponding to 59.2% of the theoretical specific capacity (see Nano Energy,2015,5, 2211-2855); sb nanofibers prepared by Zhu et al electrostatic spinning at 100mA g -1 The current density of the alloy still keeps 350mAh g after being cycled for 300 times -1 Specific capacity of (see ACS Nano,2013,5, 6378-6386). The above work avoids the use of additives to a certain extent, but the energy density and the cost of the battery are not obviously optimized, and the steps for preparing the pole piece are complicated; in addition, the pole piece needs to be rolled, so that the mechanical strength of the active substance on the pole piece is reduced to a certain extent, and the falling speed of the active substance is accelerated.
Disclosure of Invention
The invention aims to solve the problems that the existing preparation method of an antimony-based integrated electrode is complicated and the energy density of a battery is low, and provides the antimony-based integrated electrode and the preparation method and application thereof.
The invention provides a preparation method of an antimony-based integrated electrode, which comprises the following steps:
the method comprises the following steps: cleaning the titanium foil to be deposited, and then drying in vacuum;
step two: sbF in a reaction kettle 3 And (2) water solution, vertically placing the titanium foil obtained in the step (I) in a reaction kettle, then placing the screwed reaction kettle in a drying oven, heating the drying oven to 140-200 ℃ and keeping the temperature for 8-16 h to obtain the titanium foil with the surface provided with a deposition layer, and sequentially in-situ deposited Sb 3+ Sb 5+ O 4 Layer and in-situ coated Ti (OH) 4 A layer;
step three: placing the titanium foil with the surface of the deposition layer obtained in the second step in a constant temperature area of a tube furnace, sealing the tube furnace, vacuumizing the tube furnace, introducing argon, vacuumizing again, introducing argon again until the operation is repeated for three times, introducing argon again, adjusting the flow rate of the gas, and setting a temperature control program of the tube furnace, wherein the heating rate is 3-8 ℃ for min -1 The temperature rise is 300-350 ℃, the heat preservation time is 3-8 h, and the temperature reduction rate is 3-8 ℃ for min -1 After the temperature is returned to room temperature, the surface is obtained and Sb is sequentially deposited in situ 3+ Sb 5+ O 4 Layer and coated TiO 2 The antimony-based integrated electrode of the layer.
Preferably, the step one cleaning treatment is as follows: and carrying out ultrasonic cleaning treatment on the surface of the titanium foil to be deposited by using acetone, ethanol and deionized water.
Preferably, the thickness of the titanium foil in the step one is 10-30 μm.
Preferably, the SbF in the second step 3 The mass fraction of the aqueous solution is 0.33-0.50%.
Preferably, the deposition amount of the deposition layer in the second step is 0.6 to 2.1mg cm -2 The deposition method is chemical deposition.
Preferably, the gas flow rate is adjusted to 2-3 bubbles per second in step three.
The invention also provides an antimony-based integrated electrode prepared by the preparation method, which comprises a titanium foil, wherein Sb is sequentially deposited on the surface of the titanium foil in situ 3+ Sb 5+ O 4 Layer and in-situ coated TiO 2 And (3) a layer.
The invention also provides application of the antimony-based integrated electrode as a negative electrode in lithium and sodium ion batteries.
The invention has the advantages of
(1) The antimony-based integrated electrode is prepared on the surface of the titanium foil by adopting a one-step in-situ deposition and coating method, and the process is simple and easy to scale.
(2) By slight adjustment of SbF 3 The mass fraction (concentration) of the aqueous solution can regulate and control the thickness of the deposited layer to a certain extent.
(3) The antimony-based integrated electrode is prepared by in-situ deposition of Sb on the surface of a titanium foil 3+ Sb 5+ O 4 Layer and coated TiO 2 The layer can effectively avoid the use of additives, and obviously improve the energy density of the battery.
(4) In-situ deposition of Sb on the surface of titanium foil 3+ Sb 5+ O 4 Layer and coated TiO 2 The layer can reduce the shedding of the deposition layer, and further effectively inhibit the performance loss caused by the shedding of the deposition layer.
(5) The invention discloses application of an antimony-based integrated electrode as a negative electrode of a lithium-ion battery or a sodium-ion battery, which comprises the following steps: for lithium ion batteries, 1 ag -1 Has a current density of 487.4mAh g after 100 cycles -1 Specific capacity of (a); for sodium ion batteries, at 0.5A g -1 After 50 cycles, 316.1mAh g can be maintained at the current density of (1) -1 The specific capacity of (A).
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an SEM image of an electrode prepared in example 1 of the present invention.
FIG. 2 is an XRD pattern of an electrode prepared in example 2 of the present invention, in which diffraction peaks marked by black triangles represent Sb 3+ Sb 5+ O 4 Diffraction ofPeak(s).
FIG. 3 shows that the current density of the electrode prepared in example 1 of the present invention as the negative electrode of a lithium ion battery is 1 Ag -1 (first three rounds use 0.1A g -1 Current density of (1) to activate the electrode), wherein curve 1 is a discharge cycle performance curve, curve 2 is a charge cycle performance curve, and curve 3 is a charge-discharge efficiency curve.
FIG. 4 shows that the current density of the electrode prepared in example 2 of the present invention as the negative electrode of sodium ion battery is 0.5 ag -1 (first three rounds use 0.1A g -1 Current density of (1) to activate the electrode), wherein curve 1 is a discharge cycle performance curve, curve 2 is a charge cycle performance curve, and curve 3 is a charge-discharge efficiency curve.
FIG. 5 shows that the current density of the electrode prepared in example 3 of the present invention as the negative electrode of a lithium ion battery is 1 Ag -1 (first three rounds use 0.1A g -1 Current density of (1) to activate the electrode), wherein curve 1 is a discharge cycle performance curve, curve 2 is a charge cycle performance curve, and curve 3 is a charge-discharge efficiency curve.
Detailed Description
The invention provides a preparation method of an antimony-based integrated electrode, which comprises the following steps:
the method comprises the following steps: cleaning the titanium foil to be deposited, and then drying in vacuum; the cleaning treatment is preferably ultrasonic cleaning treatment of the titanium foil to be deposited by using acetone, ethanol and deionized water; the temperature of the vacuum drying is preferably 60 ℃, and the time is preferably 20min; the thickness of the titanium foil is preferably 10-30 μm.
Step two: sbF in a reaction kettle 3 And (2) water solution, vertically placing the titanium foil obtained in the step (I) in a reaction kettle, then placing the screwed reaction kettle in an oven, heating the oven to 140-200 ℃ and keeping the temperature for 8-16 h, preferably 180 ℃ and keeping the temperature for 12h, wherein the surface of the obtained titanium foil is provided with a deposition layer, and sequentially in-situ deposited Sb 3+ Sb 5+ O 4 Layer and in-situ coated Ti (OH) 4 A layer; the SbF 3 The mass fraction of the aqueous solution is preferably 0.33 to 0.50%, more preferably 0.33 to 0.50%0.33%, 0.41%, 0.50%; the deposition amount of the deposition layer is preferably 0.6-2.1 mg cm -2 The deposition method is chemical deposition.
Step three: placing the titanium foil with the deposition layer on the surface obtained in the step two in a constant temperature area of a tube furnace, sealing the tube furnace, vacuumizing the tube furnace, introducing argon, vacuumizing again, introducing argon again until the operation is repeated for three times, introducing argon again, adjusting the gas flow rate, preferably 2-3 bubbles per second, and then performing temperature control program setting on the tube furnace, wherein the temperature rise rate is 3-8 ℃ for min -1 The temperature rise is 300-350 ℃, the heat preservation time is 3-8 h, and the temperature reduction rate is 3-8 ℃ for min -1 After the temperature is returned to room temperature, the surface is obtained and Sb is sequentially deposited in situ 3+ Sb 5+ O 4 Layer and coated TiO 2 The antimony-based integrated electrode of the layer.
According to the invention, the SbF in step two 3 The method has double functions on the titanium foil, and firstly, the fluoride ions have the pitting corrosion effect on the surface of the titanium foil; secondly, under the action, the antimony ions more easily replace the titanium on the surface of the titanium foil, and the replaced titanium ions are hydrolyzed to form Ti (OH) 4 Further in-situ depositing Sb on the titanium foil substrate 3+ Sb 5+ O 4 Layer and in-situ coating Ti (OH) 4 Removing crystal water by adopting a heating mode to prepare an antimony-based integrated electrode; the active material on the electrode has very strong binding force with the current collector, so that Sb is enabled to be 3+ Sb 5+ O 4 Layer and TiO 2 The layers are not easy to fall off.
The invention also provides an antimony-based integrated electrode prepared by the preparation method, which comprises a titanium foil, wherein Sb is sequentially deposited on the surface of the titanium foil in situ 3+ Sb 5+ O 4 Layer and in-situ coated titanium dioxide (TiO) 2 ) A layer.
The invention also provides application of the antimony-based integrated electrode as a negative electrode in lithium and sodium ion batteries.
According to the invention, the prepared antimony-based integrated electrode is used as a lithium ion battery cathode material, and the specific application method comprises the following steps:
cutting the above antimony-based integrated electrode into an area of 1.13cm 2 The electrode plate of (1) is used as a negative electrode material of a lithium ion battery, a lithium foil is used as a counter electrode, and the electrolyte adopts 1M lithium hexafluorophosphate (LiPF) 6 ) Solution: specifically, ethylene Carbonate (EC) is prepared firstly: diethyl carbonate (DEC): dimethyl carbonate (DMC) solvent at volume ratio 1 6 Dissolving in the solvent;
the assembly of the button-type half cells (CR 2025) was carried out in an argon-filled glove box, in which both the oxygen and the moisture contents were less than 0.1ppm, and the button-type half cells were tested at room temperature using a LAND CT2001A multichannel tester, the voltage test interval being 0.01-3V.
According to the invention, the assembly of the half-cell of the sodium ion button type is carried out in the same manner as above, except that the counter electrode is replaced by a sodium foil and the electrolyte is 1M sodium perchlorate (NaClO) 4 ) Preparing a solution, specifically preparing Propylene Carbonate (PC): ethylene Carbonate (EC) solvent at 1 vol.% plus 3vol.% FEC, after which NaClO was added 4 Dissolving in the above solvent, and testing voltage interval of 0.01-2.5V.
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 preferred 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.
Example 1
The method comprises the following steps: carrying out ultrasonic cleaning treatment on the surface of a titanium foil (30 mm multiplied by 45 mm) to be deposited by using acetone, ethanol and deionized water, and drying for 20min in a vacuum drying oven;
step two: preparing 0.33 mass percent of SbF in a 50mL reaction kettle 3 The titanium foil obtained in the step one is vertically placed in a reaction kettle, then the screwed reaction kettle is placed in an oven, the oven is heated to 180 ℃, andkeeping for 12h, and obtaining titanium foil with a deposition layer on the surface, which is sequentially Sb deposited in situ 3+ Sb 5+ O 4 Layer and in-situ coated Ti (OH) 4 A layer, the deposition method of which is chemical deposition;
step three: and C, performing firming treatment on the titanium foil obtained in the step II, which specifically comprises the following steps: placing the titanium foil in a constant-temperature area of a tube furnace, and sealing the tube furnace; then, vacuumizing the tube furnace, introducing argon, vacuumizing again, introducing argon again until the operation is repeated for three times, introducing argon again, and adjusting the gas flow rate to be two bubbles per second; then, the temperature control program setting is carried out on the tube furnace, and the temperature rise rate is 3 ℃ for min -1 The temperature rise is 350 ℃ (titanium foil is easy to break when the temperature is too high), the heat preservation time is 3h, and the temperature reduction rate is 3 ℃ for min -1 After the temperature is returned to room temperature, the surface is obtained and Sb is sequentially deposited in situ 3+ Sb 5+ O 4 Layer and coated TiO 2 An antimony-based integrated electrode of the layer;
SEM and XRD analysis are carried out on the antimony-based integrated electrode obtained in example 1, and as shown in figure 1, SEM analysis results show that the surface of the obtained sample shows array growth, and the good morphology of the sample is favorable for stability of electrochemical cycle performance.
The antimony-based integrated electrode obtained in example 1 was used as a negative electrode material of a lithium ion battery, a lithium foil was used as a counter electrode, and 1M LiPF was used as an electrolyte 6 EC: and (4) DEC: DMC (volume ratio 1; assembling the button-type half cell (CR 2025) in an argon-filled glove box, wherein the oxygen and moisture content in the glove box is less than 0.1ppm; the button-type half cell was tested at room temperature using a LAND CT2001A multichannel tester, with a voltage test interval of 0.01-3V. The results are shown in FIG. 3 at 1 ag -1 The current density of the current still can release 470.6mAh g after circulating for 100 circles -1 The first coulombic efficiency of the specific capacity of (1) is 63.9%;
the antimony-based integrated electrode obtained in example 1 was used as a negative electrode material of a sodium ion battery, a sodium foil was used as a counter electrode, and 1M NaClO was used as an electrolyte 4 (ii)/PC: EC (volume to volume 1, fec 3vol.%); also in glove boxesAssembling into a button-type half cell; the button type half cell was tested at room temperature using a LAND CT2001A multichannel tester with a voltage test interval of 0.01-2.5V.
Example 2
This example is the same as example 1 except that SbF 3 The mass fraction of the aqueous solution is 0.41 percent; as shown in fig. 2, XRD analysis confirmed the presence of Sb in the resulting sample 3+ Sb 5+ O 4 And (4) phase(s).
As shown in FIG. 4, at 0.5 ag -1 Can still release 316.1mAh g after circulating for 50 circles under the current density -1 The first coulombic efficiency of the specific capacity of (a) was 66.5%.
Example 3
This example is the same as example 1 except that SbF 3 The mass fraction of the aqueous solution was 0.50%.
As shown in FIG. 5, at 1 ag -1 449.8mAh g can still be released after circulating for 100 circles under the current density -1 The first coulombic efficiency was 71%.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.

Claims (7)

1. A method for preparing an antimony-based integrated electrode, comprising:
the method comprises the following steps: cleaning the titanium foil to be deposited, and then drying in vacuum;
step two: sbF in a reaction kettle 3 And (2) water solution, vertically placing the titanium foil obtained in the step (I) in a reaction kettle, then placing the screwed reaction kettle in a drying oven, heating the drying oven to 140-200 ℃ and keeping the temperature for 8-16 h to obtain the titanium foil with the surface provided with a deposition layer, and sequentially in-situ deposited Sb 3+ Sb 5+ O 4 Layer and in-situ coated Ti (OH) 4 A layer;
step three: the obtained in the second stepThe titanium foil with the settled layer on the surface is placed in a constant-temperature area of the tube furnace, then the tube furnace is sealed, the tube furnace is vacuumized firstly, argon is introduced again, then the argon is introduced again, the argon is introduced again until the operation is repeated for three times, then the argon is introduced again and the flow rate of the gas is adjusted, then the temperature control program setting is carried out on the tube furnace, and the heating rate is 3-8 ℃ for min -1 The temperature rise is 300-350 ℃, the heat preservation time is 3-8 h, and the temperature reduction rate is 3-8 ℃ for min -1 After the temperature is returned to the room temperature, the Sb sequentially deposited in situ on the surface is obtained 3+ Sb 5+ O 4 Layer and coated TiO 2 An antimony-based integrated electrode of the layer;
in the second step, sbF 3 The mass fraction of the aqueous solution is 0.33-0.50%.
2. The method for preparing an antimony-based integrated electrode according to claim 1, wherein the step of cleaning comprises: and carrying out ultrasonic cleaning treatment on the surface of the titanium foil to be deposited by using acetone, ethanol and deionized water.
3. The method as claimed in claim 1, wherein the thickness of the titanium foil in the first step is 10 to 30 μm.
4. The method of claim 1, wherein the deposition amount of the deposition layer in the second step is 0.6-2.1 mgcm -2 The deposition method is chemical deposition.
5. The method of claim 1, wherein the gas flow rate is adjusted to 2 to 3 bubbles per second in the third step.
6. The antimony-based integrated electrode obtained by the preparation method of claim 1, comprising a titanium foil, wherein Sb is sequentially deposited in situ on the surface of the titanium foil 3+ Sb 5+ O 4 Layer and in-situ coated TiO 2 And (3) a layer.
7. Use of the antimony-based integrated electrode of claim 6 as a negative electrode in a lithium, sodium ion battery.
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