CN103390744A - A preparation method for a membrane electrode used for a microbattery, the membrane electrode and the microbattery - Google Patents
A preparation method for a membrane electrode used for a microbattery, the membrane electrode and the microbattery Download PDFInfo
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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.
Description
Technical field
The invention belongs to the micro cell technical field, be specifically related to preparation method and membrane electrode and the micro cell of a kind of micro cell with membrane electrode.
Background technology
Microelectric technique, to the miniaturization development, is integrated into micro-energy of microelectronics instrument (due to the general battery that adopts, therefore also can be described as micro cell) on the microelectronics instrument and becomes main flow trend.If yet by existing micro-energy integration to the components and parts of microelectronics instrument, the volume of micro-energy will account for the 40-80% of whole microelectronics instrument, quality will account for the 50-80% of whole microelectronics instrument, therefore, the core reasons that the miniaturization of the microelectronics instrument of integrated micro-energy is restricted come from the technical development bottleneck of micro-energy.
Micro-energy of prior art mainly comprises the micro-energy of chemical type and the micro-energy of physical, and wherein, the micro-energy of chemical type comprises as miniature lithium ion battery, miniature Zn-silver oxide cell, miniature Ni-MH battery, micro fuel cell etc.; The micro-energy of physical comprises as miniature photovoltaic cell, the micro-energy of bion etc.Because the micro-energy of physical is subject to the reasons such as cost and technology, that uses in the market mostly is the micro-energy of chemical type.
Generally, the microelectronics instrument of integrated micro-energy to the major requirement of micro-energy is: long-life, without electrolytic solution seepage, dependable performance, by contrast, not harsh to the requirement of energy density.This is that application due to existing microelectronics instrument is mainly microelectronic industry, as microsensor, embedded micro medical instrument etc., the operating current of micro-energy gets final product to receiving the amperage magnitude at microampere, when worked as pacemaker batteries, the operating current of micro-energy is for receiving the amperage magnitude, as as embedded glaucoma probe power supply the time, each operating time of micro-energy is the several seconds only, then converts dormant state to.
Yet along with the microelectronics instrument of the integrated micro-energy continuous application development in each technical field, require larger micro-working energy electric current, as as the nerve stimulator power supply time, the operating current that requires micro-energy is the microampere order of magnitude, as as in small-sized non-maintaining signal turn instrument power source or probe power the time, the operating current that requires equally micro-energy is a microampere order of magnitude.When the operating current that requires micro-energy is the microampere order of magnitude, the energy density requirement of micro-energy is wanted to height relatively.And the micro-energy of current chemical type comprises lithium ion micro battery, only can meet and receive the amperage magnitude, but, when to be the microampere order of magnitude for the operating current of micro-energy requiring, also need prior art is carried out to further technological improvement.
Published improved approach mainly contains two kinds at present: a kind of is the three-dimensional micro-energy process technology of exploitation; The second is exactly that the material film of the high Area Ratio capacity of development of new is for the preparation of membrane electrode.Wherein, three-dimensional micro-energy process technology faces the huge challenge of aspects such as comprising reliability, replicability, and by contrast, the high Area Ratio capacity of the exploitation of the second membrane electrode is more reliable and approach production practices, easily promotes.Further, because lithium ion battery has that energy density is large, operating voltage is high, volume is little, quality is light, the excellent properties of pollution-free, fast charging and discharging, the aspect such as have extended cycle life, be that existing market is most widely used general, be also the most popular energy.Yet existing lithium ion micro battery uses the Area Ratio capacity of membrane electrode all at 100nAh/cm
2below, can't reach the requirement of micro cell operating current for the microampere order of magnitude.
Therefore, in the urgent need to developing a kind of high Area Ratio capacity, preparation technology is simple, and the good lithium ion micro battery membrane electrode of controllability, make the operating current of lithium ion micro battery reach a microampere order of magnitude.
Summary of the invention
In view of this, the object of the present invention is to provide preparation method and membrane electrode and the micro cell of a kind of micro cell with membrane electrode, membrane electrode has high Area Ratio capacity, and preparation technology is simple, controllability is good, the service life cycle of micro cell is long, dependable performance, and can meet the requirement of operating current for the microampere order of magnitude.
The Chinese patent that is CN102146564A as publication number is clearly put down in writing in its background technology part: " negative material that current commercial lithium ion battery adopts is nearly all carbon/graphite material; the electrode potential of carbon and lithium metal current potential are very approaching; when battery overcharge; lithium metal may be separated out formation dendrite in carbon electrodes; cause safety issue, simultaneously, lithium ion is in embedding repeatedly and deviating from process; the material with carbon element structure can be damaged, thereby causes the decay of capacity.There are not the problems referred to above in titanium dioxide as lithium ion battery negative material, and the advantage such as structural change is very little in charge and discharge process, degree of polarization is low, thereby has good cycle performance, invertibity and performance fully ".Simultaneously under this background; this patent discloses a kind of prepare on the matrix of the flexible metal method of titanium dioxide array film and the application on lithium ion battery thereof; the method immerses ultrasonic cleaning in sulfuric acid lotion successively by matrix, then immerses ultrasonic cleaning in acetone, finally uses deionized water rinsing; Add in saturated nacl aqueous solution containing titanium salt solution, urea and be made into reactant liquor, be placed in the stainless steel autoclave of Teflon liner; Matrix after cleaning is immersed in reactant liquor, reacts under 150～180 ℃ 2～5 hours; The reacted film obtained rinses with sulfuric acid lotion, deionized water, absolute ethyl alcohol successively together with matrix; Make electrode material 60～100 ℃ of lower vacuumizes after 10～15 hours.According to the embodiment result, can find out, the certain carbon/graphite material than having main employing now of this patent has had raising largely as the lithium ion battery of negative material on service life cycle.Although this patent is open, the titanium dioxide array film prepared is not applied on lithium ion micro battery, the applicant wishes this patent in conjunction with being applied to microbattery applications, yet find through a large amount of repetition tests, although the Area Ratio electric capacity of the titanium dioxide array film of this patent obtains on a large scale, specifically can be up to 45 μ Ah/cm
2, but comparatively mixed and disorderly and uncontrollable owing to obtaining the titanium dioxide array film array, cause the cycle-index of lithium ion battery lower, can't meet actual user demand, in addition, the disclosed preparation method's process of this patent is crossed as complexity, therefore is not suitable as lithium ion micro battery.
Technical problem according to above existence, the arrangement of the titanium dioxide array film that the applicant's discovery obtains by the anodic oxidation preparation method is orderly and facilitate controlled, yet existing have no titanium dioxide array film about adopting anode oxidation method to prepare reporting for work as the membrane electrode of lithium ion battery (comprising micro cell), through overtesting, the Area Ratio capacity of finding titanium dioxide array film prepared by existing disclosed employing anode oxidation method is still lower, general all at 100nAh/cm
2below, can't obtain meeting the lithium ion micro battery of operating current for the microampere order of magnitude, therefore, the applicant is after repetition test and creative work, anodic oxidation preparation method to existing titanium dioxide array film has completed optimization, obtain the application, the application's technical scheme please see below.
To achieve these goals, technical scheme provided by the invention is as follows:
The preparation method of membrane electrode for a kind of micro cell, wherein, its operating procedure comprises:
A), the electrolytic solution that configuration is comprised of the fluoride of the non-aqueous polar alcohol of 90-99wt% and 1-10wt%;
B), be placed in the electrolytic solution that above-mentioned steps a) obtains using the titanium sheet as anode, carry out electrolysis under the periodic voltage effect, obtain having the initial TiO of micro-nano tubular construction on described titanium sheet
2film;
C), by above-mentioned steps b) the initial TiO that obtains
2film heats 1-48 hour at the temperature of 300-600 ℃;
D), obtain having the TiO of micro-nano tubular construction
2film, by described TiO
2film is as the micro cell membrane electrode;
Wherein, described periodic voltage comprises: carry out the voltage effect of 1-300min at the first voltage of 5-100V, then the second voltage at-10-100V carries out the voltage effect of 0-100min, and described cycle times is 1-100 time.
Preferably, described non-aqueous polar alcohol is selected from any one or a few the mixing in glycerine, ethanol, methyl alcohol.
Preferably, described electrolytic solution also comprises the water of 0.5-2wt%.
Preferably, described fluoride is selected from one or more the mixing in sodium fluoride, potassium fluoride, hydrogen fluoride, ammonium fluoride.
Preferably, described periodic voltage comprises: carry out the voltage effect of 1-50min at the first voltage of 10-100V, then the second voltage at-10-30V carries out the voltage effect of 1-10min, and described cycle times is 30-80 time.
Preferably, described non-aqueous polar alcohol is the mixed alcohol that the glycerine by the ethanol of 0-60wt% and 40-100wt% forms.
Preferably, described electrolytic solution is comprised of the water of the non-aqueous polar of 94.5-97.5wt% alcohol, 2-4wt% ammonium fluoride and 0.5-1.5wt%, and described non-aqueous polar alcohol is the mixed alcohol that the glycerine by the ethanol of 0-60wt% and 40-100wt% forms.
Preferably, described periodic voltage comprises: carry out the voltage effect of 1-5min at the first voltage of 10-100V, then the second voltage at-10-10V carries out the voltage effect of 1-5min, and described cycle times is 50-70 time.
Preferably, a kind of micro cell membrane electrode, wherein, adopt micro cell as above to obtain by the preparation method of membrane electrode.
Preferably, a kind of micro cell, using membrane electrode as electrode, lithium metal is as to electrode, and wherein, described membrane electrode adopts membrane electrode as above.
The present invention prepares in the anode oxidation method principle of prior art on the basis of titania nanotube and is optimized, and by after carrying out great many of experiments screening and analytical work, obtained having high Area Ratio capacity, and preparation technology is simple, the titanium dioxide membrane electrode provided that controllability is good, after this membrane electrode is applied to lithium ion micro battery, make the service life cycle of lithium ion micro battery long, dependable performance, and can meet the requirement of operating current for the microampere order of magnitude fully, particularly, the preparation method of titanium dioxide membrane electrode provided of the present invention is: by the electrolyte of the fluoride of the non-aqueous polar alcohol of 90-99wt% and 1-10wt%, carry out electrolysis under the effect of some cycles voltage, periodic voltage is specially the voltage effect of carrying out 1-300min at the first voltage of 5-100V, then the second voltage at-10-100V carries out the voltage effect of 0-100min, described cycle times is 1-100 time, cycle times is 1-100 time, can obtain high Area Ratio capacity, the initial TiO with micro-nano tubular construction that controllability is good
2film, and whole electrolytic process is simple, easy to operate, the initial TiO obtained due to electrolysis
2film is amorphous state mostly, can be higher and has higher crystallization driving force in surface, plays pendulum, and therefore, the present invention further proposes the initial TiO that electrolysis is obtained
2film further carries out the heat treatment of certain hour under the uniform temperature condition, makes TiO
2the abundant crystallization of film, in stable state, further guarantee TiO
2the performance of membrane electrode.
Belong to the present invention further optimally, the mixed alcohol that the present invention proposes to adopt the glycerine by the ethanol of 0-60wt% and 40-100wt% to form, as non-aqueous polar alcohol of the present invention, can further obviously improve TiO
2the Area Ratio capacity of membrane electrode, obviously improved this TiO of application simultaneously
2the service life cycle of the lithium ion micro battery of membrane electrode, further optimally, when the water of this mixed alcohol that adopts 94.5-97.5wt% and 2-4wt% ammonium fluoride and 0.5-1.5wt% forms electrolyte, electrolysis effectiveness the best, can obtain the Area Ratio capacity and be greater than 30 μ Ah/cm
2tiO
2membrane electrode, after being applied to lithium ion micro battery, make lithium ion micro battery circulation up to 5000 times after capacity substantially constant.
In sum, the present invention prepares membrane electrode to the anode oxidation method of above-mentioned optimization and has high Area Ratio capacity, and preparation technology is simple, controllability is good, the service life cycle of micro cell is long, dependable performance, and can meet the requirement of operating current for the microampere order of magnitude fully.
The accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, below will the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described, apparently, the accompanying drawing the following describes is only some embodiment that put down in writing in the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the TiO under different cycle-indexes of the embodiment of the present invention 9
2the variation diagram of the Area Ratio capacity of membrane electrode;
Fig. 2 is the TiO with micro-nano tubular construction that the embodiment of the present invention 9 prepares
2the TEM micrograph of membrane electrode.
Embodiment
The embodiment of the invention discloses the preparation method of a kind of micro cell with membrane electrode, wherein, its operating procedure comprises:
A), the electrolytic solution that configuration is comprised of the fluoride of the non-aqueous polar alcohol of 90-99wt% and 1-10wt%;
B), be placed in the electrolytic solution that above-mentioned steps a) obtains using the titanium sheet as anode, carry out electrolysis under the periodic voltage effect, obtain having the initial TiO of micro-nano tubular construction on described titanium sheet
2film;
C), by above-mentioned steps b) the initial TiO that obtains
2film heats 1-48 hour at the temperature of 300-600 ℃;
D), obtain having the TiO of micro-nano tubular construction
2film, by TiO
2film is as the micro cell membrane electrode;
Wherein, periodic voltage comprises: carry out the voltage effect of 1-300min at the first voltage of 5-100V, then the second voltage at-10-100V carries out the voltage effect of 0-100min, and cycle times is 1-100 time.
Preferably, non-aqueous polar alcohol is selected from any one or a few the mixing in glycerine, ethanol, methyl alcohol.
Preferably, electrolytic solution also comprises the water of 0.5-2wt%.
Preferably, fluoride is selected from one or more the mixing in sodium fluoride, potassium fluoride, hydrogen fluoride, ammonium fluoride.
Preferably, periodic voltage comprises: carry out the voltage effect of 1-50min at the first voltage of 10-100V, then the second voltage at-10-30V carries out the voltage effect of 1-10min, and cycle times is 30-80 time.
Preferably, non-aqueous polar alcohol is the mixed alcohol that the glycerine by the ethanol of 0-60wt% and 40-100wt% forms.
Preferably, electrolytic solution is comprised of the water of the non-aqueous polar of 94.5-97.5wt% alcohol, 2-4wt% ammonium fluoride and 0.5-1.5wt%, and non-aqueous polar alcohol is the mixed alcohol that the glycerine by the ethanol of 0-60wt% and 40-100wt% forms.
Preferably, periodic voltage comprises: carry out the voltage effect of 1-5min at the first voltage of 10-100V, then the second voltage at-10-10V carries out the voltage effect of 1-5min, and cycle times is 50-70 time, and more preferably, cycle times can be 60 times.
The embodiment of the invention also discloses a kind of micro cell membrane electrode, wherein, adopt micro cell as above to obtain by the preparation method of membrane electrode.
The embodiment of the invention also discloses a kind of micro cell, using membrane electrode as electrode, lithium metal is as to electrode, and wherein, membrane electrode adopts membrane electrode as above.
The embodiment of the present invention prepares in the anode oxidation method principle of prior art on the basis of titania nanotube and is optimized, and by after carrying out great many of experiments screening and analytical work, obtained having high Area Ratio capacity, and preparation technology is simple, the titanium dioxide membrane electrode provided that controllability is good, after this membrane electrode is applied to lithium ion micro battery, make the service life cycle of lithium ion micro battery long, dependable performance, and can meet the requirement of operating current for the microampere order of magnitude fully, particularly, the preparation method of the titanium dioxide membrane electrode provided of the embodiment of the present invention is: by the electrolyte of the fluoride of the non-aqueous polar alcohol of 90-99wt% and 1-10wt%, carry out electrolysis under the effect of some cycles voltage, periodic voltage is specially the voltage effect of carrying out 1-300min at the first voltage of 5-100V, then the second voltage at-10-100V carries out the voltage effect of 0-100min, described cycle times is 1-100 time, cycle times is 1-100 time, can obtain high Area Ratio capacity, the initial TiO with micro-nano tubular construction that controllability is good
2film, and whole electrolytic process is simple, easy to operate, the initial TiO obtained due to electrolysis
2film is amorphous state mostly, can be higher and has higher crystallization driving force in surface, plays pendulum, and therefore, the embodiment of the present invention further proposes the initial TiO that electrolysis is obtained
2film further carries out the heat treatment of certain hour under the uniform temperature condition, makes TiO
2the abundant crystallization of film, in stable state, further guarantee TiO
2the performance of membrane electrode.
Belong to the embodiment of the present invention further optimally, the mixed alcohol that the embodiment of the present invention propose to adopt the glycerine by the ethanol of 0-60wt% and 40-100wt% to form, as the non-aqueous polar alcohol of the embodiment of the present invention, can further obviously improve TiO
2the Area Ratio capacity of membrane electrode, obviously improved this TiO of application simultaneously
2the service life cycle of the lithium ion micro battery of membrane electrode, further optimally, when the water of this mixed alcohol that adopts 94.5-97.5wt% and 2-4wt% ammonium fluoride and 0.5-1.5wt% forms electrolyte, electrolysis effectiveness the best, can obtain the Area Ratio capacity and be greater than 30 μ Ah/cm
2tiO
2membrane electrode, after being applied to lithium ion micro battery, make lithium ion micro battery circulation up to 5000 times after capacity substantially constant.
In sum, the embodiment of the present invention prepares membrane electrode to the anode oxidation method of above-mentioned optimization and has high Area Ratio capacity, and preparation technology is simple, controllability is good, the service life cycle of micro cell is long, dependable performance, and can meet the requirement of operating current for the microampere order of magnitude fully.
In order to make those skilled in the art person understand better the technical scheme in the present invention, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making under the creative work prerequisite the every other embodiment obtained, should belong to the scope of protection of the invention.
Embodiment 1:
A), the electrolytic solution that configuration is comprised of the water of sodium fluoride+1wt% of glycerine+3wt% of 96wt%;
B), using the titanium sheet as anode, platinized platinum is as negative electrode, be placed in respectively the electrolytic solution that above-mentioned steps a) obtains, carry out electrolysis under the periodic voltage effect, wherein, periodic voltage is: carry out the voltage effect of 300min at the first voltage of 10V, cycle times is 1 time; Then clean for several times with distilled water, obtain having the initial TiO of micro-nano tubular construction on the titanium sheet
2film;
C), by above-mentioned steps b) the initial TiO that obtains
2film heats 48 hours at the temperature of 300 ℃;
D), obtain having the TiO of micro-nano tubular construction
2film, TiO
2film is as the micro cell membrane electrode.
By the above-mentioned TiO that obtains of the present embodiment
2membrane electrode is as membrane electrode, and lithium metal is as to electrode, and to take the MLiPF6/EC+DEC of 1:1 be electrolyte, and Cergard2400 is barrier film, is assembled into 2032 type lithium ion micro battery, measures TiO
2membrane electrode Area Ratio capacity is 5 μ Ah/cm
2, 500 capacity of lithium ion micro battery circulation are substantially constant.
Embodiment 2:
A), the electrolytic solution that configuration is comprised of the water of sodium fluoride+1wt% of ethanol+3wt% of 96wt%;
B), using the titanium sheet as anode, platinized platinum is as negative electrode, be placed in respectively the electrolytic solution that above-mentioned steps a) obtains, carry out electrolysis under the periodic voltage effect, wherein, periodic voltage is: carry out the voltage effect of 2min at the first voltage of 30V, then carry out the voltage effect of 2min at the second voltage of 10V, cycle times is 60 times; Then clean for several times with distilled water, obtain having the initial TiO of micro-nano tubular construction on the titanium sheet
2film;
C), by above-mentioned steps b) the initial TiO that obtains
2film heats 1 hour at the temperature of 600 ℃;
D), obtain having the TiO of micro-nano tubular construction
2film, TiO
2film is as the micro cell membrane electrode.
By the above-mentioned TiO that obtains of the present embodiment
2membrane electrode is as membrane electrode, and lithium metal is as to electrode, and to take the MLiPF6/EC+DEC of 1:1 be electrolyte, and Cergard2400 is barrier film, is assembled into 2032 type lithium ion micro battery, measures TiO
2membrane electrode Area Ratio capacity is 8 μ Ah/cm
2, 500 capacity of lithium ion micro battery circulation are substantially constant.
Embodiment 3:
A), the electrolytic solution that configuration is comprised of the sodium fluoride of methyl alcohol+2wt% of 98wt%;
B), using the titanium sheet as anode, platinized platinum is as negative electrode, be placed in respectively the electrolytic solution that above-mentioned steps a) obtains, carry out electrolysis under the periodic voltage effect, wherein, periodic voltage is: carry out the voltage effect of 1min at the first voltage of 60V, then carry out the voltage effect of 50min at the second voltage of 2V, cycle times is 30 times; Then clean for several times with distilled water, obtain having the initial TiO of micro-nano tubular construction on the titanium sheet
2film;
C), by above-mentioned steps b) the initial TiO that obtains
2film heats 10 hours at the temperature of 600 ℃;
D), obtain having the TiO of micro-nano tubular construction
2film, TiO
2film is as the micro cell membrane electrode.
By the above-mentioned TiO that obtains of the present embodiment
2membrane electrode is as membrane electrode, and lithium metal is as to electrode, and to take the MLiPF6/EC+DEC of 1:1 be electrolyte, and Cergard2400 is barrier film, is assembled into 2032 type lithium ion micro battery, measures TiO
2membrane electrode Area Ratio capacity is 3 μ Ah/cm
2, 500 capacity of lithium ion micro battery circulation are substantially constant.
Embodiment 4:
A), the electrolytic solution that configuration is comprised of the water of sodium fluoride+1wt% of glycerine+3wt% of 96wt%;
B), using the titanium sheet as anode, platinized platinum is as negative electrode, be placed in respectively the electrolytic solution that above-mentioned steps a) obtains, carry out electrolysis under the periodic voltage effect, wherein, periodic voltage is: carry out the voltage effect of 1min at the first voltage of 100V, then the second voltage at-10V carries out the voltage effect of 1min, and cycle times is 30 times; Then clean for several times with distilled water, obtain having the initial TiO of micro-nano tubular construction on the titanium sheet
2film;
C), by above-mentioned steps b) the initial TiO that obtains
2film heats 2 hours at the temperature of 500 ℃;
D), obtain having the TiO of micro-nano tubular construction
2film, TiO
2film is as the micro cell membrane electrode.
By the above-mentioned TiO that obtains of the present embodiment
2membrane electrode is as membrane electrode, and lithium metal is as to electrode, and to take the MLiPF6/EC+DEC of 1:1 be electrolyte, and Cergard2400 is barrier film, is assembled into 2032 type lithium ion micro battery, measures TiO
2membrane electrode Area Ratio capacity is 10 μ Ah/cm
2, 1000 capacity of lithium ion micro battery circulation are substantially constant.
Embodiment 5:
A), the electrolytic solution that configuration is comprised of the sodium fluoride of methyl alcohol+2wt% of 98wt%;
B), using the titanium sheet as anode, platinized platinum is as negative electrode, be placed in respectively the electrolytic solution that above-mentioned steps a) obtains, carry out electrolysis under the periodic voltage effect, wherein, periodic voltage is: carry out the voltage effect of 1min at the first voltage of 60V, then carry out the voltage effect of 50min at the second voltage of 2V, cycle times is 30 times; Then clean for several times with distilled water, obtain having the initial TiO of micro-nano tubular construction on the titanium sheet
2film;
C), by above-mentioned steps b) the initial TiO that obtains
2film heats 10 hours at the temperature of 600 ℃;
D), obtain having the TiO of micro-nano tubular construction
2film, TiO
2film is as the micro cell membrane electrode.
By the above-mentioned TiO that obtains of the present embodiment
2membrane electrode is as membrane electrode, and lithium metal is as to electrode, and to take the MLiPF6/EC+DEC of 1:1 be electrolyte, and Cergard2400 is barrier film, is assembled into 2032 type lithium ion micro battery, measures TiO
2membrane electrode Area Ratio capacity is 3 μ Ah/cm
2, 500 capacity of lithium ion micro battery circulation are substantially constant.
Embodiment 6:
A), the electrolytic solution that configuration is comprised of the water of ammonium fluoride+1wt% of glycerine+3wt% of 96wt%;
B), using the titanium sheet as anode, platinized platinum is as negative electrode, be placed in respectively the electrolytic solution that above-mentioned steps a) obtains, carry out electrolysis under the periodic voltage effect, wherein, periodic voltage is: carry out the voltage effect of 2min at the first voltage of 45V, then carry out the voltage effect of 2min at the second voltage of 10V, cycle times is 60 times; Then clean for several times with distilled water, obtain having the initial TiO of micro-nano tubular construction on the titanium sheet
2film;
C), by above-mentioned steps b) the initial TiO that obtains
2film heats 24 hours at the temperature of 450 ℃;
D), obtain having the TiO of micro-nano tubular construction
2film, TiO
2film is as the micro cell membrane electrode.
By the above-mentioned TiO that obtains of the present embodiment
2membrane electrode is as membrane electrode, and lithium metal is as to electrode, and to take the MLiPF6/EC+DEC of 1:1 be electrolyte, and Cergard2400 is barrier film, is assembled into 2032 type lithium ion micro battery, measures TiO
2membrane electrode Area Ratio capacity is 15 μ Ah/cm
2, 1000 capacity of lithium ion micro battery circulation are substantially constant.
Embodiment 7:
A), the electrolytic solution that configuration is comprised of the water of potassium fluoride+1wt% of glycerine+3wt% of ethanol+48wt% of 48wt%;
B), using the titanium sheet as anode, platinized platinum is as negative electrode, be placed in respectively the electrolytic solution that above-mentioned steps a) obtains, carry out electrolysis under the periodic voltage effect, wherein, periodic voltage is: carry out the voltage effect of 2min at the first voltage of 45V, then carry out the voltage effect of 2min at the second voltage of 10V, cycle times is 60 times; Then clean for several times with distilled water, obtain having the initial TiO of micro-nano tubular construction on the titanium sheet
2film;
C), by above-mentioned steps b) the initial TiO that obtains
2film heats 24 hours at the temperature of 450 ℃;
D), obtain having the TiO of micro-nano tubular construction
2film, TiO
2film is as the micro cell membrane electrode.
By the above-mentioned TiO that obtains of the present embodiment
2membrane electrode is as membrane electrode, and lithium metal is as to electrode, and to take the MLiPF6/EC+DEC of 1:1 be electrolyte, and Cergard2400 is barrier film, is assembled into 2032 type lithium ion micro battery, measures TiO
2membrane electrode Area Ratio capacity is 7 μ Ah/cm
2, 500 capacity of lithium ion micro battery circulation are substantially constant.
Embodiment 8:
A), the electrolytic solution that configuration is comprised of the water of potassium fluoride+1wt% of glycerine+3wt% of ethanol+48wt% of 48wt%;
B), using the titanium sheet as anode, platinized platinum is as negative electrode, be placed in respectively the electrolytic solution that above-mentioned steps a) obtains, carry out electrolysis under the periodic voltage effect, wherein, periodic voltage is: carry out the voltage effect of 2min at the first voltage of 45V, then at the second voltage of 10V, carry out the voltage effect of 2min, then at the first voltage of 60V, carry out the voltage effect of 2min, then the second voltage at-10V carries out the voltage effect of 1min, and cycle times is 30 times; Then clean for several times with distilled water, obtain having the initial TiO of micro-nano tubular construction on the titanium sheet
2film;
C), by above-mentioned steps b) the initial TiO that obtains
2film heats 24 hours at the temperature of 450 ℃;
D), obtain having the TiO of micro-nano tubular construction
2film, TiO
2film is as the micro cell membrane electrode.
By the above-mentioned TiO that obtains of the present embodiment
2membrane electrode is as membrane electrode, and lithium metal is as to electrode, and to take the MLiPF6/EC+DEC of 1:1 be electrolyte, and Cergard2400 is barrier film, is assembled into 2032 type lithium ion micro battery, measures TiO
2membrane electrode Area Ratio capacity is 17 μ Ah/cm
2, 500 capacity of lithium ion micro battery circulation are substantially constant.
Embodiment 9:
A), the electrolytic solution that configuration is comprised of the water of ammonium fluoride+1wt% of glycerine+3wt% of ethanol+48wt% of 48wt%;
B), using the titanium sheet as anode, platinized platinum is as negative electrode, be placed in respectively the electrolytic solution that above-mentioned steps a) obtains, carry out electrolysis under the periodic voltage effect, wherein, periodic voltage is: carry out the voltage effect of 2min at the first voltage of 45V, then carry out the voltage effect of 2min at the second voltage of 10V, cycle times is 60 times; Then clean for several times with distilled water, obtain having the initial TiO of micro-nano tubular construction on the titanium sheet
2film;
C), by above-mentioned steps b) the initial TiO that obtains
2film heats 2 hours at the temperature of 450 ℃;
D), obtain having the TiO of micro-nano tubular construction
2film, TiO
2film is as the micro cell membrane electrode, and the TiO with micro-nano tubular construction for preparing of the present embodiment 9 shown in Figure 2
2the TEM micrograph of membrane electrode.
By the above-mentioned TiO that obtains of the present embodiment
2membrane electrode is as membrane electrode, and lithium metal is as to electrode, and to take the MLiPF6/EC+DEC of 1:1 be electrolyte, and Cergard2400 is barrier film, is assembled into 2032 type lithium ion micro battery, measures TiO
2membrane electrode Area Ratio capacity is 35 μ Ah/cm
2, the TiO under different cycle-index N of the present embodiment 9 shown in Figure 1
2the variation diagram of the Area Ratio capacity M of membrane electrode, and can clearly learning from Fig. 1, after lithium ion micro battery circulation 5000 times, capacity is substantially constant.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, and in the situation that do not deviate from spirit of the present invention or essential characteristic, can realize the present invention with other concrete form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, therefore is intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in scope.Any Reference numeral in claim should be considered as limit related claim.
In addition, be to be understood that, although this specification is described according to execution mode, but not each execution mode only comprises an independently technical scheme, this narrating mode of specification is only for clarity sake, those skilled in the art should make specification as a whole, and the technical scheme in each embodiment also can, through appropriate combination, form other execution modes that it will be appreciated by those skilled in the art that.
Claims (10)
1. the preparation method of a micro cell use membrane electrode, is characterized in that, its operating procedure comprises:
A), the electrolytic solution that configuration is comprised of the fluoride of the non-aqueous polar alcohol of 90-99wt% and 1-10wt%;
B), be placed in the electrolytic solution that above-mentioned steps a) obtains using the titanium sheet as anode, carry out electrolysis under the periodic voltage effect, obtain having the initial TiO of micro-nano tubular construction on described titanium sheet
2film;
C), by above-mentioned steps b) the initial TiO that obtains
2film heats 1-48 hour at the temperature of 300-600 ℃;
D), obtain having the TiO of micro-nano tubular construction
2film, by described TiO
2film is as the micro cell membrane electrode;
Wherein, described periodic voltage comprises: carry out the voltage effect of 1-300min at the first voltage of 5-100V, then the second voltage at-10-100V carries out the voltage effect of 0-100min, and described cycle times is 1-100 time.
2. the preparation method of membrane electrode for micro cell as claimed in claim 1, is characterized in that, described non-aqueous polar alcohol is selected from any one or a few the mixing in glycerine, ethanol, methyl alcohol.
3. the preparation method of membrane electrode for micro cell as claimed in claim 1, is characterized in that, described electrolytic solution also comprises the water of 0.5-2wt%.
4. the preparation method of membrane electrode for micro cell as claimed in claim 1, is characterized in that, described fluoride is selected from one or more the mixing in sodium fluoride, potassium fluoride, hydrogen fluoride, ammonium fluoride.
5. the preparation method of membrane electrode for micro cell as claimed in claim 1, it is characterized in that, described periodic voltage comprises: carry out the voltage effect of 1-50min at the first voltage of 10-100V, then the second voltage at-10-30V carries out the voltage effect of 1-10min, and described cycle times is 30-80 time.
6. the preparation method of membrane electrode for micro cell as claimed in claim 2, is characterized in that, described non-aqueous polar alcohol is the mixed alcohol that the glycerine by the ethanol of 0-60wt% and 40-100wt% forms.
7. the preparation method of membrane electrode for micro cell as claimed in claim 1, it is characterized in that, described electrolytic solution is comprised of the water of the non-aqueous polar of 94.5-97.5wt% alcohol, 2-4wt% ammonium fluoride and 0.5-1.5wt%, and described non-aqueous polar alcohol is the mixed alcohol that the glycerine by the ethanol of 0-60wt% and 40-100wt% forms.
8. the preparation method of membrane electrode for micro cell as claimed in claim 7, it is characterized in that, described periodic voltage comprises: carry out the voltage effect of 1-5min at the first voltage of 10-100V, then the second voltage at-10-10V carries out the voltage effect of 1-5min, and described cycle times is 50-70 time.
9. a micro cell membrane electrode, is characterized in that, employing obtains by the preparation method of membrane electrode as the described micro cell of claim 1-8 any one.
10. a micro cell, using membrane electrode as electrode, lithium metal, as to electrode, is characterized in that, described membrane electrode adopts membrane electrode as claimed in claim 9.
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Cited By (3)
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| CN104377381A (en) * | 2014-11-06 | 2015-02-25 | 湖州创亚动力电池材料有限公司 | Ultra-low-temperature onboard micro energy resource system and manufacturing method of ultra-low-temperature onboard micro energy resource system, manufacturing method of positive electrode |
| CN105070943A (en) * | 2015-08-27 | 2015-11-18 | 深圳市燕峰科技有限公司 | Quick charging lithium battery |
| CN109216681A (en) * | 2018-09-21 | 2019-01-15 | 合肥工业大学 | One kind being based on TiO2Nano-tube array/titanium foam lithium an- ode material and preparation method thereof |
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| CN102354747A (en) * | 2011-08-29 | 2012-02-15 | 复旦大学 | Lithium ion battery thin film anode Cu6Sn5@TiO2 nanotube array and preparation method thereof |
| CN102534727A (en) * | 2012-01-13 | 2012-07-04 | 天津大学 | Titanium dioxide nanocomposite and one-step preparation method by utilizing anodic oxidation device |
| CN102776543A (en) * | 2012-05-07 | 2012-11-14 | 中国科学院合肥物质科学研究院 | Preparation method of large-area smooth-surface uncracked anodic oxidation titanium dioxide nanometer tube arrays |
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| CN102354747A (en) * | 2011-08-29 | 2012-02-15 | 复旦大学 | Lithium ion battery thin film anode Cu6Sn5@TiO2 nanotube array and preparation method thereof |
| CN102534727A (en) * | 2012-01-13 | 2012-07-04 | 天津大学 | Titanium dioxide nanocomposite and one-step preparation method by utilizing anodic oxidation device |
| CN102776543A (en) * | 2012-05-07 | 2012-11-14 | 中国科学院合肥物质科学研究院 | Preparation method of large-area smooth-surface uncracked anodic oxidation titanium dioxide nanometer tube arrays |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104377381A (en) * | 2014-11-06 | 2015-02-25 | 湖州创亚动力电池材料有限公司 | Ultra-low-temperature onboard micro energy resource system and manufacturing method of ultra-low-temperature onboard micro energy resource system, manufacturing method of positive electrode |
| CN105070943A (en) * | 2015-08-27 | 2015-11-18 | 深圳市燕峰科技有限公司 | Quick charging lithium battery |
| CN109216681A (en) * | 2018-09-21 | 2019-01-15 | 合肥工业大学 | One kind being based on TiO2Nano-tube array/titanium foam lithium an- ode material and preparation method thereof |
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