CN114477101B - Preparation method of self-supporting sodium seleno-titanyl array - Google Patents

Preparation method of self-supporting sodium seleno-titanyl array Download PDF

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CN114477101B
CN114477101B CN202210055085.8A CN202210055085A CN114477101B CN 114477101 B CN114477101 B CN 114477101B CN 202210055085 A CN202210055085 A CN 202210055085A CN 114477101 B CN114477101 B CN 114477101B
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selenium
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CN114477101A (en
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高林
刘洋
陶华超
颜波
张露露
杨学林
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China Three Gorges University CTGU
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01—ELECTRIC ELEMENTS
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract

The invention provides a preparation method of a self-supporting selenium titanium oxygen sodium array. The specific operation is that the titanium foil is sequentially cleaned by deionized water, absolute ethyl alcohol and dilute hydrochloric acid. And then etching the titanium foil through NaOH solution under hydrothermal condition, and in nitrogen atmosphere, taking selenium powder as a selenium source, and carrying out selenization to obtain the self-supporting selenium titanium oxide sodium array. Found that Na is obtained along with the change of the dosage of the selenium powder 2 Ti 3 O 6.2 Se 0.8 The performance of the material is optimal when the material is used as a negative electrode material of a sodium ion battery, and the current density is 1A g within the voltage range of 0.01-3V ‑1 After 1000 circles of lower circulation, the water heater still has 155 mA h g ‑1 Is a specific capacity of (a). Na under large current 2 Ti 3 O 6.2 Se 0.8 Has better electrochemical stability, which is realized by Na 2 Ti 3 O 6.2 Se 0.8 The material has stable performance as a negative electrode material of the sodium ion battery and potential application value in the field of sodium ion batteries.

Description

Preparation method of self-supporting sodium seleno-titanyl array
Technical Field
The invention relates to a preparation method of a self-supporting selenium titanium oxygen sodium array, which is applied to a negative electrode of a sodium ion battery and belongs to the field of sodium ion batteries.
Technical Field
With the continuous deep popularity of low-carbon and environment-friendly life style, the demand for energy storage devices such as lithium ion batteries is increasing. Lithium ion batteries also face their own problems, such as high cost due to low lithium resource reserves and high mining difficulties. Sodium ion batteries have electrochemical properties similar to lithium ion batteries, and sodium salts are abundant in resources, and have received extensive attention from researchers in recent years. The role of the electrode material is particularly important in the overall cell, determining the cycle life of the overall cell. The titanium-based electrode material has abundant raw material resources, high activity, safety and no pollution, so the titanium-based electrode material becomes a more suitable electrode material.In recent years, the use of layered materials with larger interlayer spacing in sodium-based energy storage devices has attracted considerable attention. Na with zigzag layered structure 2 Ti 3 O 7 Has a value of 310 mAh g -1 Has been widely studied and is considered as a promising negative electrode material for sodium ion batteries. We propose an in situ growth of ordered Na on titanium foil 2 Ti 3 O 7 The nano-sheet array is a negative electrode material, and the firm adhesion between the active substance and the current collector enables rapid transmission of electrons and ions. However, low conductivity makes it difficult to reach its theoretical capacity, and furthermore, rapid capacity fade during long cycling greatly limits its practical use in sodium ion batteries. The invention provides a preparation method of a self-supporting selenium titanium sodium oxide array, selenium doping can obviously improve the capacity and the multiplying power performance of a sodium ion battery electrode, and the self-supporting selenium titanium sodium oxide array has more stable cycle performance.
Disclosure of Invention
The invention provides a self-supporting selenium titanium sodium oxide array (Na 2 Ti 3 O 7-x Se x ) A method of preparing an array. The specific operation is to apply titanium foil (thickness 0.1 mm, purity 99.9%, 3×5 cm) 2 ) Sequentially carrying out ultrasonic cleaning by deionized water, absolute ethyl alcohol and dilute hydrochloric acid. Placing the cleaned titanium foil into a container 50 o C oven drying 1h. The dried titanium foil was placed against the inner wall of a 40mL polytetrafluoroethylene lined autoclave filled with 1-5M NaOH and then reacted at 150-200 ℃ for 12-15h. The obtained sample was subjected to a reaction in the range of 50 to 60 o And C, drying in an oven to obtain 10-12 parts h. Transferring the dried material and selenium powder into sintering equipment, wherein the mass ratio of the sodium titanate precursor material to the selenium powder is 1:10-1:80, placing selenium powder on the upstream of tube furnace or uniformly dispersing on the surface of titanium foil, placing the dried titanium foil on the downstream of tube furnace, on the titanium foil a uniform sodium titanate array is grown, under the condition of nitrogen gas, mixing them by 1-5 o Cmin -1 The temperature rise rate of (2) reaches 300-500 o C, preserving heat 2-3 h, cooling to room temperature to obtain self-supporting sodium seleno-titanyl (Na) 2 Ti 3 O 7-x Se x ) A nanoplatelet array.
The invention of the patent is self-supportingSelenium titanium oxygen sodium array (Na) 2 Ti 3 O 7-x Se x ) The preparation method of the catalyst has the following characteristics:
(1) The in-situ growth, no current collector and no binder performance are more excellent.
(2) Selenium doping significantly improves Na 2 Ti 3 O 7 Is a combination of the capacity and rate capability of the battery.
Drawings
Figure 1 is a graph comparing XRD of samples prepared in examples 1, 3 with standard cards.
FIG. 2 is an SEM image at different magnification levels before charge-discharge cycles of the sample prepared in example 1, A is a graph of scale 1. Mu. And B is a graph of scale 0.1. Mu. Respectively.
FIG. 3 is an SEM image at different magnification levels before charge-discharge cycles of the sample prepared in example 2, A is a graph of scale 1. Mu. And B is a graph of scale 0.1. Mu. Respectively.
Fig. 4 is an SEM image of samples prepared in example 3 at different magnifications before charge and discharge cycles, a being the image on scale 1 μ and B being the image on scale 0.1 μ.
Fig. 5 is an SEM image of samples prepared in example 4 at different magnifications before charge and discharge cycles, a being the image on scale 1 μ and B being the image on scale 0.1 μ.
FIG. 6 is a graph showing the comparison of the rate performance of the samples prepared in examples 1, 2, 3 and 4.
FIG. 7 is a graph showing comparison of cycle performance of samples prepared in examples 1, 2, 3 and 4.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
Titanium foil (thickness 0.1. 0.1 mm, purity 99.9%, 3X 5 cm) 2 ) Sequentially carrying out ultrasonic cleaning by deionized water, absolute ethyl alcohol and dilute hydrochloric acid. Placing the cleaned titanium foil into a container 50 o C oven drying 1h. The dried titanium foil was placed against the inner wall of a 40mL polytetrafluoroethylene lined autoclave filled with 1M NaOH, then at 180 o The oven of C was hydrothermal 12h. The obtained sample was subjected to a reaction at 50 o The C oven was dried 12h. The dried titanium foil was treated under nitrogen at 5 o C min -1 The temperature rise rate of (2) reaches 500 o And C, preserving heat for 2h, and cooling to room temperature to obtain the self-supporting sodium titanate array. Drawing of the figure1 is prepared Na 2 Ti 3 O 7 Is compared with standard card and XRD of standard card (Na 2 Ti 3 O 7 PDF # 72-0148) was consistent, showed no significant impurity peaks, and exhibited good crystallinity. FIG. 2 is Na 2 Ti 3 O 7 The microscopic morphology of the material is nano-sheets, the sheets are mutually stacked, and the nano-sheets are uniformly distributed. FIG. 6 is a graph of the prepared Na 2 Ti 3 O 7 Is a graph of the rate performance of (2). Na in FIG. 6 2 Ti 3 O 7 At 2A g -1 138.2 mAh g at current density -1 Is a specific capacity of (a). At 1A g -1 The specific capacity of the current density after 1000 cycles is 113.3 mAh g -1 (FIG. 7).
Example 2
Titanium foil (thickness 0.1. 0.1 mm, purity 99.9%, 3X 5 cm) 2 ) Sequentially carrying out ultrasonic cleaning by deionized water, absolute ethyl alcohol and dilute hydrochloric acid. Placing the cleaned titanium foil into a container 50 o And C, drying in an oven for 1h. The dried titanium foil was placed against the wall of a 40mL polytetrafluoroethylene-lined autoclave with 1M NaOH, then at 180 o The oven of C was hydrothermal 12h. The obtained sample was subjected to a reaction at 50 o And C, drying in an oven for 12h. The dried sodium titanate material and the selenium powder of 0.1 g are transferred into sintering equipment together, the selenium powder is arranged at the upstream of a tube furnace, the dried sodium titanate material is arranged at the downstream of the tube furnace, and the distance between the dried sodium titanate material and the selenium powder is 15 cm. Under nitrogen at 5 o The heating rate of C/min reaches 500 o C, preserving heat 2h, cooling to room temperature to obtain a self-supporting selenium titanium oxygen sodium array and naming the self-supporting selenium titanium oxygen sodium array as (Na 2 Ti 3 O 6.8 Se 0.2 ). FIG. 3 is Na 2 Ti 3 O 6.8 Se 0.2 In comparison with fig. 2, fig. 3 shows no significant difference, and the shape of the nanosheets is the same, which indicates that the morphology of the doped sodium titanate is not changed when the amount of selenium powder is 0.1. FIG. 6 is a graph of the prepared Na 2 Ti 3 O 6.8 Se 0.2 And (5) multiplying power performance graphs. As can be seen, at 2A g -1 Na at current density 2 Ti 3 O 7-x Se x -1 has 90.7 mAh g -1 Is a specific capacity of (a). At 1A g -1 At current densityThe specific capacity is 124 mAh g after 1000 cycles -1 (FIG. 7).
Example 3
Titanium foil (thickness 0.1. 0.1 mm, purity 99.9%, 3X 5 cm) 2 ) Sequentially carrying out ultrasonic cleaning by deionized water, absolute ethyl alcohol and dilute hydrochloric acid. Placing the cleaned titanium foil into a container 50 o C oven drying 1h. The dried titanium foil was placed against the wall of a 40mL polytetrafluoroethylene lined autoclave with 1M NaOH and then at 180 o The oven of C was hydrothermal 12h. The obtained sample was subjected to a reaction at 50 o The C oven was dried 12h. The dried sodium titanate material and the selenium powder of 0.35g are transferred into sintering equipment together, the selenium powder is arranged at the upstream of a tube furnace, the dried titanium foil is arranged at the downstream of the tube furnace, and the distance between the two is 15 cm. Under nitrogen at 5 o C min -1 The temperature rise rate of (2) reaches 500 o C, keeping the temperature at 2h, wherein 0.35g of selenium powder in FIG. 1 is used as selenium source and doped with Na 2 Ti 3 O 6.2 Se 0.8 With Na and Na 2 Ti 3 O 7 XRD was consistent. FIG. 4 shows Na after selenium doping with 0.35g selenium powder as selenium source 2 Ti 3 O 6.2 Se 0.8 The SEM image of (a) shows that the morphology of the doped sodium titanate is unchanged when the amount of selenium powder is 0.35. 0.35 g. FIG. 6 shows the prepared Na 2 Ti 3 O 6.2 Se 0.8 Is 0.2 Ag -1 The capacity is stable at 215 mAh g under the current density -1 About 2A g -1 Still has 155.7 mAh g at current density -1 Is equal to pure phase Na 2 Ti 3 O 7 And shows better electrochemical performance than the prior art. Na (Na) 2 Ti 3 O 6.2 Se 0.8 At 1A g -1 After 1000 cycles of charge and discharge under current density, the specific capacity is still kept at 150 mAh g -1 Almost no attenuation (FIG. 7), while Na 2 Ti 3 O 7 Only 122 mAh g -1 In comparison with Na 2 Ti 3 O 6.2 Se 0.8 The high-current circulation stability is better.
Example 4
Titanium foil (thickness 0.1. 0.1 mm, purity 99.9%, 3X 5 cm) 2 ) Sequentially useAnd (5) ultrasonic cleaning with deionized water, absolute ethyl alcohol and dilute hydrochloric acid. Placing the cleaned titanium foil into a container 50 o C oven drying 1h. The dried titanium foil was placed against the wall of a 40mL polytetrafluoroethylene lined autoclave with 1M NaOH and then at 180 o The oven of C was hydrothermal 12h. The obtained sample was subjected to a reaction at 50 o The C oven was dried 12h. Transferring the dried sodium titanate material and 0.5 g selenium powder into sintering equipment together, placing selenium powder on the upstream of a tube furnace, placing the dried sodium titanate material on the downstream of the tube furnace, and placing the dried sodium titanate material and the selenium powder under nitrogen at a distance of 5 o C min -1 The temperature rise rate of (2) reaches 500 o C, preserving heat 2h to prepare Na 2 Ti 3 O 6 Se. FIG. 5 is Na 2 Ti 3 O 6 Se morphology, the nano-sheets become blocks after doping, the blocks are gathered together and cross-linked, the original morphology is lost, and the Na is damaged when the selenium powder reaches 0.5 g 2 Ti 3 O 7 Original appearance. Na (Na) 2 Ti 3 O 6 Se has the worst electrochemical properties. FIG. 6 shows the prepared Na 2 Ti 3 O 6 Rate performance of Se at 2A g -1 The specific capacity is only 32.5 mAh g under the current density -1 . At 1A g -1 The specific capacity is only 73.4 mAh g after 1000 circles of current density circulation -1 (FIG. 7).
Example 5
Titanium foil (thickness 0.1. 0.1 mm, purity 99.9%, 3X 5 cm) 2 ) Sequentially carrying out ultrasonic cleaning by deionized water, absolute ethyl alcohol and dilute hydrochloric acid. Placing the cleaned titanium foil into a container 50 o C oven drying 1h. The dried titanium foil was placed against the wall of a 40mL polytetrafluoroethylene lined autoclave with 1M NaOH and then at 180 o The oven of C was hydrothermal 12h. The obtained sample was subjected to a reaction at 50 o The C oven was dried 12h. Transferring the dried sodium titanate material and 0.35g selenium powder into sintering equipment, uniformly dispersing the selenium powder and placing the selenium powder on sodium titanate sheet, and making the powder be uniformly dispersed in the presence of nitrogen gas at a ratio of 5 o C min -1 The temperature rise rate of (2) reaches 500 o C, preserving heat 2h to obtain Na 2 Ti 3 O 6.2 Se 0.8 。Na 2 Ti 3 O 6.2 Se 0.8 At 1A g -1 After 1000 cycles of charge and discharge under current density, the specific capacity is still kept at 132 mAh g -1 。

Claims (3)

1. A preparation method of a self-supporting selenium titanium oxygen sodium array is characterized by comprising the following steps of:
(1) Cleaning and drying the titanium foil, leaning against the inner wall of a polytetrafluoroethylene lining autoclave filled with NaOH, and drying after hydrothermal reaction to obtain a sodium titanate precursor material;
(2) Transferring the sodium titanate precursor material and selenium powder into a tube furnace together for sintering to obtain a self-supporting sodium seleno-titanyl array;
(3) Selenium powder is placed at the upstream of a tube furnace, and sodium titanate material is placed at the downstream of the tube furnace for selenizing; or the selenium powder is directly and evenly dispersed and coated on the sodium titanate material for selenizing, and the dosage ratio of the sodium titanate active material to the selenium powder is 1:10-1:80; the sintering condition is that under inert atmosphere, the temperature is 1-5 ℃ for min -1 And (3) after the temperature rising rate reaches 300-500 ℃, preserving the heat for 2-3 hours to obtain the self-supporting selenium titanium sodium oxide array.
2. The method for preparing the self-supporting sodium seleno-titanyl array according to claim 1, wherein the method comprises the following steps: the concentration of NaOH in the step (1) is 1-5M.
3. The method for preparing the self-supporting sodium seleno-titanyl array according to claim 1, wherein the method comprises the following steps: the hydrothermal reaction condition is that the reaction is carried out for 12-15h at 150-200 ℃.
CN202210055085.8A 2022-01-18 2022-01-18 Preparation method of self-supporting sodium seleno-titanyl array Active CN114477101B (en)

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WO2016137401A1 (en) * 2015-02-25 2016-09-01 National University Of Singapore Sodium-ion battery anode
CN107369560B (en) * 2017-08-04 2019-02-19 哈尔滨工业大学 A kind of flexibility sodium ion capacitor and preparation method thereof
CN109167054B (en) * 2018-07-17 2021-03-30 广东工业大学 Phosphorus-doped sodium titanate nanowire and preparation method and application thereof
CN109950526A (en) * 2019-03-04 2019-06-28 三峡大学 Sodium base Dual-ion cell of sodium titanate nano-chip arrays cathode and preparation method thereof
CN112467081B (en) * 2020-12-02 2021-10-15 四川大学 High-load self-supporting lithium titanate electrode with multilayer hierarchical nanostructure and preparation method thereof
CN113104824B (en) * 2021-03-01 2022-09-16 三峡大学 Se doped Fe 2 Preparation method of P self-supporting sodium ion battery cathode material

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