A preparation method for a membrane electrode used for a microbattery, the membrane electrode and the microbattery

A thin-film electrode and micro-battery technology, applied in the field of micro-battery, can solve problems such as inability to achieve micro-battery, and achieve the effects of reliable performance, good controllability and simple preparation process

Inactive Publication Date: 2013-11-13
SUZHOU UNIV
4 Cites 6 Cited by

AI-Extracted Technical Summary

Problems solved by technology

However, the area specific capacity of the existing thin-film electrodes for lithium-ion micro-batteries is 100nAh/cm 2...
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Method used

Belonging to the further optimization of the embodiments of the present invention, the embodiments of the present invention propose to adopt the mixed alcohol composed of the ethanol of 0-60wt% and the glycerol of 40-100wt% as the non-aqueous polar alcohol of the embodiments of the present invention, can further Significantly improve the area specific capacity of the TiO2 thin film electrode, and at the same time significantly improve the cycle life of the lithium ion micro-battery using the TiO2 thin film electrode. Further optimally, when using 94.5-97.5wt% of the mixed alcohol and 2-4wt% fluorine When ammonium chloride and 0.5-1.5wt% water form the electrolyte, the electrolysis effect is the best, and a TiO2 thin film electrode with an area specific capacity greater than 30μAh/cm2 can be obtained. After being applied to a lithium-ion micro-battery, the lithium-ion micro-battery cycle can reach 5000 After that, the capacity remains basically unchanged.
The embodiment of the present invention optimizes on the basis of the anodic oxidation method principle of prior art preparation titanium dioxide nanotube, and after carrying out a large amount of experimental screening and analysis work, has obtained to have high area specific capacity, and preparation process is simple, Titanium dioxide thin-film electrode with good controllability. After the thin-film electrode is applied to lithium-ion micro-battery,...
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Abstract

The invention discloses a preparation method for a membrane electrode used for a microbattery, the membrane electrode and the microbattery. The method comprises operation steps of a) preparing an electrolytic solution comprising 90-99 wt% of a non-water polar alcohol and 1-10 wt% of a fluoride; b) placing a titanium sheet as an anode in the electrolytic solution prepared by the step a), and performing electrolysis under the action of periodic voltages to obtain an initial TiO2 membrane with a micro/nano tube structure on the titanium sheet; c) heating the initial TiO2 membrane, prepared by the step b), at 300-600 DEG C for 1-48 h; and d) obtaining a TiO2 membrane with a micro/nano tube structure and using the TiO2 membrane as the membrane electrode used for the microbattery. The membrane electrode has high area specific capacity, simple preparation technology and good controllability. The microbattery has a long recycling service lifetime and reliable performances, and can meet a requirement that the working current is in a microamp order of magnitude.

Application Domain

Cell electrodesSecondary cells

Technology Topic

TitaniumVoltage +6

Image

  • A preparation method for a membrane electrode used for a microbattery, the membrane electrode and the microbattery
  • A preparation method for a membrane electrode used for a microbattery, the membrane electrode and the microbattery

Examples

  • Experimental program(10)

Example Embodiment

[0033] The embodiment of the invention discloses a method for preparing a thin film electrode for a micro battery, wherein the operation steps include:
[0034] a). Configure an electrolytic solution composed of 90-99wt% non-aqueous polar alcohol and 1-10wt% fluoride;
[0035] b) Put the titanium sheet as an anode in the electrolytic solution obtained in the above step a), and conduct electrolysis under the action of periodic voltage, and obtain the initial TiO with a micro-nanotube structure on the titanium sheet 2 film;
[0036] c), the initial TiO obtained in the above step b) 2 The film is heated at a temperature of 300-600°C for 1-48 hours;
[0037] d) Get TiO with micro-nanotube structure 2 Thin film, TiO 2 Thin film as thin film electrode for micro battery;
[0038] Among them, the periodic voltage includes: performing a voltage application of 1-300 minutes at a first voltage of 5-100V, and then performing a voltage application of 0-100 minutes at a second voltage of -10-100V, and the number of cycles is 1-100.
[0039] Preferably, the non-aqueous polar alcohol is selected from any one or a mixture of several of glycerol, ethanol and methanol.
[0040] Preferably, the electrolytic solution further includes 0.5-2wt% water.
[0041] Preferably, the fluoride is selected from one or a mixture of sodium fluoride, potassium fluoride, hydrogen fluoride, and ammonium fluoride.
[0042] Preferably, the periodic voltage includes: performing a voltage application at a first voltage of 10-100V for 1-50 minutes, and then performing a voltage application at a second voltage of -10-30V for 1-10 minutes, and the number of cycles is 30-80 times.
[0043] Preferably, the non-aqueous polar alcohol is a mixed alcohol composed of 0-60 wt% ethanol and 40-100 wt% glycerin.
[0044] Preferably, the electrolytic solution is composed of 94.5-97.5wt% non-aqueous polar alcohol, 2-4wt% ammonium fluoride and 0.5-1.5wt% water, and the non-aqueous polar alcohol is composed of 0-60wt% ethanol and 40- Mixed alcohol composed of 100wt% glycerin.
[0045] Preferably, the periodic voltage includes: performing a voltage application of 1-5 minutes at a first voltage of 10-100V, and then performing a voltage application of 1-5 minutes at a second voltage of -10-10V, and the number of cycles is 50-70. Preferably, the number of cycles may be 60 times.
[0046] The embodiment of the present invention also discloses a thin film electrode for a micro battery, which is obtained by the method for preparing a thin film electrode for a micro battery as described above.
[0047] The embodiment of the invention also discloses a micro battery, which uses a thin film electrode as an electrode and metal lithium as a counter electrode, wherein the thin film electrode adopts the above-mentioned thin film electrode.
[0048] The embodiment of the present invention is optimized on the basis of the preparation of titanium dioxide nanotubes based on the principle of anodic oxidation in the prior art, and after a large number of experimental screening and analysis work, a high area specific capacity is obtained, and the preparation process is simple and controllable. A good titanium dioxide thin-film electrode. After the thin-film electrode is applied to a lithium-ion microbattery, the lithium-ion microbattery has a long cycle life and reliable performance, and can fully meet the requirements of a working current of the order of microamperes. Specifically, the present invention is implemented The preparation method of the titanium dioxide thin film electrode of the example is as follows: electrolysis is carried out under the action of a certain periodic voltage with a 90-99wt% non-aqueous polar alcohol and 1-10wt% fluoride electrolyte. The periodic voltage is specifically at 5-100V The first voltage is applied for 1-300min, and then the second voltage is -10-100V for 0-100min. The number of cycles is 1-100, and the number of cycles is 1-100. Obtain the initial TiO with high area specific capacity and good controllability with micro-nanotube structure 2 Thin film, and the whole electrolysis process is simple and easy to operate, because the initial TiO obtained by electrolysis 2 Most of the films are amorphous, with high surface energy and high driving force for crystallization, and are in an unstable state. Therefore, the embodiment of the present invention further proposes to compare the initial TiO obtained by electrolysis. 2 The film is further heat-treated for a certain period of time under certain temperature conditions to make TiO 2 The film is fully crystallized and in a stable state to further ensure the TiO 2 The performance of thin film electrodes.
[0049] The embodiment of the present invention is further optimized. The embodiment of the present invention proposes to use a mixed alcohol composed of 0-60 wt% ethanol and 40-100 wt% glycerin as the non-aqueous polar alcohol in the embodiment of the present invention, which can further significantly improve TiO 2 The area specific capacity of the thin film electrode, and at the same time, the application of the TiO 2 The cycle life of the thin-film electrode lithium-ion microbattery is further optimized. When 94.5-97.5wt% of the mixed alcohol, 2-4wt% of ammonium fluoride and 0.5-1.5wt% of water are used to form the electrolyte, the electrolysis effect Best, the area specific capacity can be greater than 30μAh/cm 2 TiO 2 Thin film electrodes, after being applied to lithium-ion micro-batteries, make the capacity of the lithium-ion micro-batteries basically unchanged after being cycled up to 5000 times.
[0050] In summary, the embodiment of the present invention has a high area specific capacity for the above-mentioned optimized anodic oxidation method to prepare a thin film electrode, and the preparation process is simple, the controllability is good, the cycle life of the microbattery is long, the performance is reliable, and can fully satisfy The working current is in the order of microampere.

Example Embodiment

[0052] Example 1:
[0053] a) Configure an electrolytic solution consisting of 96wt% glycerin + 3wt% sodium fluoride + 1wt% water;
[0054] b). Put the titanium sheet as the anode and the platinum sheet as the cathode, respectively, in the electrolytic solution obtained in the above step a), and conduct electrolysis under the action of a periodic voltage, where the periodic voltage is: a first voltage of 10V for 300 minutes The voltage is applied, and the number of cycles is 1; then it is washed several times with distilled water, and the initial TiO with micro-nanotube structure is obtained on the titanium sheet 2 film;
[0055] c), the initial TiO obtained in the above step b) 2 The film is heated at 300℃ for 48 hours;
[0056] d) Get TiO with micro-nanotube structure 2 Thin film, TiO 2 The thin film is used as a thin film electrode for a micro battery.
[0057] The TiO obtained in the above example 2 The thin-film electrode is used as the thin-film electrode, the metal lithium is used as the counter electrode, and the 1:1 MLiPF6/EC+DEC is used as the electrolyte, Cergard2400 is used as the diaphragm, and assembled into a 2032-type lithium ion micro-battery. The measured TiO 2 The specific capacity of the membrane electrode area is 5μAh/cm 2 , The capacity of lithium-ion micro-battery is basically unchanged after 500 cycles.

Example Embodiment

[0058] Example 2:
[0059] a) Configure an electrolytic solution composed of 96wt% ethanol + 3wt% sodium fluoride + 1wt% water;
[0060] b). Put the titanium sheet as the anode and the platinum sheet as the cathode, respectively, in the electrolytic solution obtained in the above step a), and conduct electrolysis under the action of a periodic voltage, where the periodic voltage is: a first voltage of 30V for 2 minutes The voltage is applied, and then the voltage is applied for 2 minutes at the second voltage of 10V, and the number of cycles is 60; then it is washed several times with distilled water, and the initial TiO with micro-nanotube structure is obtained on the titanium sheet 2 film;
[0061] c), the initial TiO obtained in the above step b) 2 The film is heated at 600°C for 1 hour;
[0062] d) Get TiO with micro-nanotube structure 2 Thin film, TiO 2 The thin film is used as a thin film electrode for a micro battery.
[0063] The TiO obtained in the above example 2 The thin-film electrode is used as the thin-film electrode, the metal lithium is used as the counter electrode, and the 1:1 MLiPF6/EC+DEC is used as the electrolyte, Cergard2400 is used as the diaphragm, and assembled into a 2032-type lithium ion micro-battery. The measured TiO 2 The specific capacity of the membrane electrode area is 8μAh/cm 2 , The capacity of lithium-ion micro-battery is basically unchanged after 500 cycles.

PUM

PropertyMeasurementUnit
Area specific capacity>= 30.0µAh/cm²
Area specific capacity5.0µAh/cm²
Area specific capacity8.0µAh/cm²

Description & Claims & Application Information

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