CN111128568A - Monodisperse Ti3C2Preparation method of nanowire transparent electrode - Google Patents
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- 239000002070 nanowire Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 20
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 69
- 239000002135 nanosheet Substances 0.000 claims abstract description 39
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000004528 spin coating Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 11
- 238000002834 transmittance Methods 0.000 abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 2
- 238000005530 etching Methods 0.000 abstract 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention discloses a monodisperse Ti3C2The preparation method of the nanowire transparent electrode comprises the steps of etching Ti by hydrochloric acid and lithium fluoride3AlC2Obtaining accordion-shaped Ti3C2Mixing the block with KOH solution, and stirring at room temperature to obtain monodisperse Ti3C2Nanowires of monodisperse Ti by spin coating3C2And transferring the nanowires onto a transparent substrate to assemble the transparent electrode. The preparation method is simple, the reaction condition is mild, and the preparation can be completed under hydrothermal and normal pressure conditions; the invention obtains uniform and monodisperse one-dimensional Ti for the first time3C2Nanowire, and two-dimensional Ti3C2Compared with a nano sheet, the nano sheet has higher specific surface area and more active sites; monodisperse Ti prepared by the method disclosed by the invention3C2The nanowires are assembled into the transparent electrode, so that two-dimensional Ti can be effectively avoided3C2Stacking occurs during the charge/discharge process of the nanosheets; the transparent electrode hasExcellent light transmittance, conductivity and energy storage performance.
Description
Technical Field
The invention relates to a transparentThe technical field of super capacitor preparation, in particular to monodisperse Ti3C2A method for preparing a nanowire transparent electrode.
Background
With the continuous and deep research work, transparent portable intelligent electronic products will become more intelligent, comfortable and fashionable in the near future, and the rapid development trend thereof puts higher demands on the performance of energy storage devices. For example, a smart phone, a display screen, a transparent touch sensing screen and the like need to be matched with a transparent energy storage device, and the transparent super capacitor as an excellent energy storage device has important guiding significance for the development of future transparent energy storage equipment.
In recent years, MXene has become one of popular materials in the energy storage field due to its excellent electrical conductivity and electrochemical energy storage performance. MXene is a generic term for two-dimensional layered metal carbides, nitrides or carbonitrides having the general chemical formula Mn+1XnTx(N = 1-3), wherein M represents a transition metal (e.g., Ti, V, Nb, Mo, etc.), X represents a C or N element, and T represents a chemical functional group including-OH, -O, and-F. MXene has high electronic conductivity (9880S cm)-1) And excellent capacitance energy storage characteristics, and becomes one of ideal electrode materials for constructing transparent supercapacitors. Chuanfang (John) Zhang group applied 2D Ti by a simple spin coating method3C2The nano-sheets are transferred to a transparent substrate to be assembled into a transparent energy storage electrode, the light transmittance of the film is 29%, and the conductivity of the film is 9880S cm-1. The area capacitance of the conductive electrode with the light transmittance of 91 percent is 0.48 mF cm-2These transparent electrodes all exhibit high capacitance and long lifetime. In general, Ti3C2The transparent electrode can be used as a latest technology of a future transparent and conductive capacitive electrode to supply energy for next-generation wearable electronic products. However, 2D Ti3C2The nanosheets inevitably cause stacking during charge/discharge, which is detrimental to ion/electron transport and thus to electrochemical performance.
Mixing 2D Ti3C2The nano-sheet is one-dimensionally monodisperse Ti3C2Nanowire replacement is effective in avoiding two-dimensional Ti3C2Method of nanosheet stacking, and one-dimensional monodisperse Ti3C2Nanowire and two-dimensional Ti3C2Compared with the nano-sheet, the nano-sheet has more reactive active sites and higher specific surface area, and one-dimensional monodisperse Ti3C2The nanowire can effectively avoid two-dimensional Ti3C2The stacking of the nano sheets is beneficial to the transmission of ionic electrons, so that the electrochemical performance is improved.
Therefore, it is necessary to design a simple and easy one-dimensional monodisperse Ti3C2Nanowire fabrication methods to improve 2DTi3C2The nanosheets have deficiencies in performance.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the monodisperse Ti with low cost, low energy consumption and simple process3C2The preparation method of the nanowire transparent electrode avoids two-dimensional Ti3C2The stacking of the nanosheet transparent electrodes improves light transmittance.
The technical scheme of the invention is as follows: monodisperse Ti3C2The preparation method of the nanowire transparent electrode comprises the following specific operation steps:
(1) mixing Ti in accordion shape3C2Mixing the block with KOH, and continuously stirring at room temperature under Ar atmosphere;
(2) centrifuging the reacted product with deionized water for 5 times, centrifuging to neutrality, ultrasonically homogenizing, and centrifuging to transfer the upper solution, wherein the upper solution is monodisperse Ti3C2A nanowire;
(3) adopting a spin coating method to obtain monodisperse Ti3C2The nano wires are transferred to the transparent substrate ITO glass;
(4) and (4) transferring the transparent electrode obtained in the step (3) to a tube furnace for vacuum annealing to obtain the transparent electrode.
Further, in the step (1), Ti is accordion-shaped3C2The mass of the block is 70-120 mg, the molar concentration of KOH is 6-12M, the volume is 12 mL, and the stirring time is 24-72 h.
Further, in step 2, the centrifugation conditions were 3500 rpm, 5 min.
Further, in step 4, the vacuum annealing process is carried out at 200 ℃ for 2 h.
Further, the accordion-like Ti3C2The preparation method of the block body comprises the following steps:
1) mixing LiF and 9M HCl and stirring until LiF is completely dissolved, and slowly adding Ti with the same mass as LiF3AlC2Placing the mixture in a reaction kettle to react for 72 hours at the temperature of 50-70 ℃;
2) centrifuging the product at 3500 rpm for 5 min, washing the product with deionized water to pH>6, drying in vacuum to obtain the product, namely the accordion-shaped Ti3C2And (3) a block body.
Utilizing accordion-shaped Ti prepared based on the above method3C2Preparing Ti from block3C2The specific operation steps of the nanosheet transparent electrode are as follows:
1) mixing Ti in accordion shape3C2Drying the block, dispersing the dried block in deionized water according to the concentration of 10 mg/mL, and performing ultrasonic treatment for 4 hours at the frequency of 600W;
2) centrifuging the solution after ultrasonic treatment at 3500 rpm for 1 h to obtain upper suspension as Ti3C2Nanosheets;
3) taking 50 mu L of Ti3C2Dropping the nanosheet solution on ITO glass of 1 cm multiplied by 2 cm, and spin-coating at 3000 rpm for 30 s;
4) subjecting the obtained Ti to3C2Transferring the nano-sheet transparent electrode into a tube furnace, and carrying out vacuum annealing at 200 ℃ for 2 h to obtain Ti3C2A nanosheet transparent electrode.
The invention has the beneficial effects that:
(1) the preparation method disclosed by the invention is simple, easy to operate, mild in reaction condition and capable of being completed under a hydrothermal condition;
(2) ti prepared by the method disclosed by the invention3C2The nano-wire is a monodisperse nano-wire, has a one-dimensional structure and higher conductivity, and is two-dimensional with Ti3C2Compared with a nano sheet, the nano sheet has higher specific surface area and more active sites;
(3) monodisperse Ti prepared by the method disclosed by the invention3C2The transparent electrode assembled by the nano-wires can effectively avoid two-dimensional Ti3C2Stacking occurs during the charge/discharge process of the nanosheets;
(4) monodisperse Ti prepared by the method disclosed by the invention3C2The nanowire transparent electrode has excellent light transmittance and energy storage performance.
Drawings
FIG. 1 shows monodisperse Ti obtained in example 33C2SEM images of nanowires;
FIG. 2 shows monodisperse Ti obtained in example 33C2XRD spectrogram of the nanowire;
FIG. 3 shows monodisperse Ti obtained in example 63C2Nanowire transparent electrode, Ti3C2A light transmittance spectrogram of the nanosheet transparent electrode;
FIG. 4 shows monodisperse Ti obtained in example 73C2Nanowire transparent electrode, Ti3C2Comparing the cyclic voltammetry curves of the nanosheet transparent electrode;
FIG. 5 shows monodisperse Ti obtained in example 73C2A cyclic voltammetry curve of the nanowire transparent electrode;
FIG. 6 shows monodisperse Ti obtained in example 83C2Constant current charge and discharge curve of the nanowire transparent electrode.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1 accordion-shaped Ti3C2Of blocksPreparation of
(1) Mixing 0.5 g LiF with 10 mL 9M HCl, and stirring until LiF is completely dissolved;
(2) to prevent local overheating, 0.5 g Ti was slowly added3AlC2；
(3) Reacting the mixture in a reaction kettle at 60 ℃ for 72 hours;
(4) after the product is cooled to room temperature, the product is centrifuged for 5 times by deionized water and ethanol under 3500 rpm and 5 min, and the product is obtained by vacuum drying after 1 time of ethanol centrifugation3C2And (3) a block body.
Example 2 one-dimensional monodisperse Ti3C2Preparation of nanowires
(1) Weigh 100 mg of accordion-like Ti3C2The block was transferred to a 30 mL plastic bottle and 12 mL of 9M KOH solution was added;
(2) discharging Ar for 20 min, and continuously stirring at room temperature for 72 h under Ar atmosphere;
(3) after the reaction is finished, centrifuging the product for 5 times by using deionized water under the conditions of 3500 rpm and 5 min;
(4) centrifuging to neutrality, homogenizing with ultrasound, centrifuging at 3500 rpm for 30 min, transferring the upper solution which is uniform one-dimensional monodisperse Ti3C2A nanowire.
Example 3 monodisperse Ti3C2Characterization of nanowires
FIG. 1 is a drawing showing monodispersed Ti3C2SEM characterization of nanowires, as can be seen from the SEM images, Ti3C2The nano wires are single and dispersed nano wires, and the length of the nano wires is more than 1-3 mu m. FIG. 2 shows monodisperse Ti3C2The nanowire is characterized by XRD, and the XRD result shows that the nanowire is 6.9oCorresponds to Ti3C2(002) crystal face of (a).
Example 4 monodisperse Ti3C2Preparation of nanowire transparent electrode
(1) 50. mu.L of one-dimensional monodisperse Ti obtained in example 2 was taken3C2Dropping the nanowires on 1 cm × 2 cm ITO glass, and spinning at 3000 rpm for 30 sCoating;
(2) subjecting the obtained monodisperse Ti3C2And transferring the nanowire transparent electrode into a tube furnace, and carrying out vacuum annealing at 200 ℃ for 2 h to obtain the transparent electrode.
Example 5 Ti3C2Preparation of nanosheet transparent electrode
(1) Accordion-like Ti prepared in example 13C2Dispersing the block in deionized water according to the concentration of 10 mg/mL, and carrying out ultrasonic treatment for 4 h at the frequency of 600W;
(2) centrifuging the solution after ultrasonic treatment at 3500 rpm for 1 h to obtain upper suspension as Ti3C2Nanosheets;
(3) taking 50 mu L of Ti3C2Dropping the nanosheet solution on ITO glass of 1 cm multiplied by 2 cm, and spin-coating at 3000 rpm for 30 s;
(4) subjecting the obtained Ti to3C2Transferring the nano-sheet transparent electrode into a tube furnace, and carrying out vacuum annealing at 200 ℃ for 2 h to obtain Ti3C2A nanosheet transparent electrode.
Example 6 monodisperse Ti3C2Nanowire transparent electrode, Ti3C2Light transmittance test of nanosheet transparent electrode
FIG. 3 is a spectrum of light transmittance, from which a blank ITO glass, monodisperse Ti3C2Nanowire transparent electrode and Ti3C2The light transmittance of the nano-sheet transparent electrode is 86.1%, 77.8% and 74.7% in sequence, and Ti is controlled3C2The transparent electrode with similar light transmittance can be obtained by the spin coating quality of the nano wire and the nano sheet.
Example 7 one-dimensional monodisperse Ti3C2Nanowire transparent electrode, Ti3C2Cyclic voltammetry testing of nanosheet transparent electrodes
A working electrode: monodisperse Ti obtained in examples 4 and 53C2Nanowire transparent electrode, Ti3C2A nanosheet transparent electrode (1 cm × 2 cm); electrolyte: 3M H2SO4(ii) a Reference electrode: Ag/AgCl; counter electrode: pt plate, voltageWindow: -0.2-0.5V.
The test results are shown in FIG. 4 at 100 mV s-1At sweeping speed of Ti3C2The area capacitance value of the nanowire transparent electrode is 4.6 mF cm-2Higher than Ti3C2The area capacitance value of the nano sheet is 1.3 mF cm-2The area capacitance value is far higher than that of blank substrate ITO glass by 0.02 mF cm-2Indicating a close light transmittance, Ti3C2The nano-wire has better performance than Ti3C2Area capacitance value of the nanosheet.
FIG. 5 shows monodisperse Ti3C2The sweep rate of the cyclic voltammetry curve of the nanowire transparent electrode at different sweep rates is 10 mV s-1、20 mV·s-1、50 mV·s-1And 100 mV. s-1The corresponding area capacitance values are 5.2 mF cm in sequence-2、5.0 mFcm-2、4.8 mF cm-2And 4.6 mF cm-2Sweeping speed from 10 mV s-1Increase to 100 mV s-1The capacity retention was 88.5%, and it was found that monodisperse Ti3C2The nanowire transparent electrode has excellent energy storage property and rate capability.
Example 8 one-dimensional monodisperse Ti3C2Constant current charge-discharge test of nanowire transparent electrode
A working electrode: monodisperse Ti3C2Nanowire transparent electrodes (1 cm × 2 cm); electrolyte: 3M H2SO4(ii) a Reference electrode: Ag/AgCl; counter electrode: pt plate, voltage window: -0.2-0.5V.
FIG. 6 shows a one-dimensional monodisperse Ti3C2GCD (GCD direct current) diagram of the nanowire transparent electrode under different current densities, and the current density is 24 mu A cm-2、48 μA cm-2、96 μA cm-2、192 μA cm-2And 384. mu.A cm-2The capacitance value of the time is 5.8 mF cm-2、4.6 mF cm-2、3.8 mF cm-2、2.9 mF cm-2And 1.9 mF cm-2Further, it was confirmed that the Ti was monodisperse3C2The nanowire transparent electrode has excellent energy storage performance.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (6)
1. Monodisperse Ti3C2The preparation method of the nanowire transparent electrode is characterized by comprising the following specific operation steps:
(1) mixing Ti in accordion shape3C2Mixing the block with KOH, and continuously stirring at room temperature under Ar atmosphere;
(2) centrifuging the reacted product with deionized water for 5 times, centrifuging to neutrality, ultrasonically homogenizing, and centrifuging to transfer the upper solution, wherein the upper solution is monodisperse Ti3C2A nanowire;
(3) adopting a spin coating method to obtain monodisperse Ti3C2The nano wires are transferred to the transparent substrate ITO glass;
(4) and (4) transferring the transparent electrode obtained in the step (3) to a tube furnace for vacuum annealing to obtain the transparent electrode.
2. A monodisperse Ti as claimed in claim 13C2The preparation method of the nanowire transparent electrode is characterized in that in the step 1, accordion-shaped Ti3C2The mass of the block is 70-120 mg, the molar concentration of KOH is 6-12M, the volume is 12 mL, and the stirring time is 24-72 h.
3. A monodisperse Ti as claimed in claim 13C2The preparation method of the nanowire transparent electrode is characterized in that in the step 2, the centrifugation condition is 3500 rpm and 5 min.
4. A monodisperse Ti as claimed in claim 13C2The preparation method of the nanowire transparent electrode is characterized in thatIn step 4, the vacuum annealing process is carried out at 200 ℃ for 2 h.
5. A monodisperse Ti as claimed in claim 13C2The preparation method of the nanowire transparent electrode is characterized in that the accordion-shaped Ti3C2The preparation method of the block body comprises the following steps:
1) mixing LiF and 9M HCl and stirring until LiF is completely dissolved, and slowly adding Ti with the same mass as LiF3AlC2Placing the mixture in a reaction kettle to react for 72 hours at the temperature of 50-70 ℃;
2) centrifuging the product at 3500 rpm for 5 min, washing the product with deionized water to pH>6, drying in vacuum to obtain the product, namely the accordion-shaped Ti3C2And (3) a block body.
6. Ti3C2The preparation method of the nanosheet transparent electrode is characterized by comprising the following specific operation steps:
1) mixing Ti in accordion shape3C2Drying the block, dispersing the dried block in deionized water according to the concentration of 10 mg/mL, and performing ultrasonic treatment for 4 hours at the frequency of 600W;
2) centrifuging the solution after ultrasonic treatment at 3500 rpm for 1 h to obtain upper suspension as Ti3C2Nanosheets;
3) taking 50 mu L of Ti3C2Dropping the nanosheet solution on ITO glass of 1 cm multiplied by 2 cm, and spin-coating at 3000 rpm for 30 s;
4) subjecting the obtained Ti to3C2Transferring the nano-sheet transparent electrode into a tube furnace, and carrying out vacuum annealing at 200 ℃ for 2 h to obtain Ti3C2A nanosheet transparent electrode.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113808859A (en) * | 2021-09-08 | 2021-12-17 | 青岛科技大学 | Preparation method of two-dimensional layered MXene composite TiN electrode material |
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| CN1603238A (en) * | 2004-09-27 | 2005-04-06 | 南京大学 | Preparation method of titanium carbide and titanium nitride one dimension nanometer construction material |
| CN108298540A (en) * | 2018-01-22 | 2018-07-20 | 浙江理工大学 | A kind of preparation method of titanium carbide nano-wires |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603238A (en) * | 2004-09-27 | 2005-04-06 | 南京大学 | Preparation method of titanium carbide and titanium nitride one dimension nanometer construction material |
| CN108298540A (en) * | 2018-01-22 | 2018-07-20 | 浙江理工大学 | A kind of preparation method of titanium carbide nano-wires |
Non-Patent Citations (1)
| Title |
|---|
| PEICHAO LIAN 等: "Alkalized Ti3C2 MXene nanoribbons with expanded interlayer spacing for high-capacity sodium and potassium ion batteries", 《NANO ENERGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113808859A (en) * | 2021-09-08 | 2021-12-17 | 青岛科技大学 | Preparation method of two-dimensional layered MXene composite TiN electrode material |
| CN113808859B (en) * | 2021-09-08 | 2022-11-11 | 青岛科技大学 | Preparation method of two-dimensional layered MXene composite TiN electrode material |
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