CN109900657A - A kind of method of testing film electrode material structure change - Google Patents
A kind of method of testing film electrode material structure change Download PDFInfo
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- CN109900657A CN109900657A CN201910145744.5A CN201910145744A CN109900657A CN 109900657 A CN109900657 A CN 109900657A CN 201910145744 A CN201910145744 A CN 201910145744A CN 109900657 A CN109900657 A CN 109900657A
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Abstract
The present invention relates to battery material technical fields, and in particular to a kind of method of testing film electrode material structure change.Specific steps are as follows: circulation rear film electrode material, non-circulation film electrode material and polymer nanofiber thin-film electrode material are rinsed and are dried in vacuo, 3 kinds of test thin-film electrode materials are obtained；3 kinds of tests are detected with thin-film electrode material using terahertz time-domain spectroscopy instrument, obtain the sample time domain pulse signal of 3 kinds of thin-film electrode materials respectively, and obtain reference signal under the conditions of same spectra；The absorptivity for obtaining the thin-film electrode material is calculated according to scheduled calculation method according to the sample time domain pulse signal and reference signal.Non-intrusion type of the present invention, lossless detection method, and it is simple to operate, a kind of new method and thinking can be provided for membrane electrode detection by material structure and polar change in the simple and quick judgement membrane electrode cyclic process of absorptivity.
Description
Technical field
The present invention relates to battery material technical fields, and in particular to a kind of side of testing film electrode material structure change
Method.
Background technique
Flexible foldable or flexible portable electronic products, such as laptop, tablet computer and mobile phone will very
It is fast to become next-generation electronic product mainstream.How fastly flexible electronic product is used cooperatively using battery that must be flexible,
Speed, simply to the structure change situation before and after flexible use carry out detection be a very meaningfully research work.
Often mainly have with spectrum measurement method to the measuring method of electrode material structure and composition at present: Raman spectrum, X are penetrated
Line diffraction (XRD), infrared spectroscopy etc..
Raman spectrum is a kind of scattering spectrum, is analyzed the scattering spectrum different from incident light frequency to obtain molecule
Vibration, rotation aspect information, and it is applied to a kind of analysis method of molecular structure research.Raman spectrum can once cover simultaneously
The section of 50-4000 wave number can analyze organic matter and inorganic matter, and spectral peak is clearly sharp, be more suitable for quantitative study, data
Library searching and utilization variance analysis carry out qualitative research.
A kind of electromagnetic wave of wavelength of X-ray diffraction very short (about 20-0.06 angstroms), can penetrate certain thickness substance, lead to
It crosses and X-ray diffraction is carried out to material, analyze its diffracting spectrum, obtain the ingredient of material, the structure of material internal atom or molecule
Or the research means of the information such as form.Only with the atomic arrangement period by closing, intensity then depends on for the position of diffracted ray on diffracting spectrum
In properties such as atomic species, quantity and relative positions.The sample fineness of usual quantitative analysis should be in 45 microns, i.e., should mistake
325 meshes.
The method of above-mentioned testing film electrode material structure change requires height to electrode material, and influences in test process
Factor is more, and operating process is cumbersome, can not fast qualitative analysis utilizing thin-film electrode material structure change situation.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of sides of testing film electrode material structure change
Method, comprising the following steps:
It will circulation rear film electrode material, non-circulation film electrode material and polymer nanofiber thin-film electrode material point
It is not rinsed and is dried in vacuo, obtain the first, second, third thin-film electrode material of test；
The test is examined with the first, second, third thin-film electrode material using terahertz time-domain spectroscopy instrument respectively
It surveys, after obtaining the circulation, does not recycle and the first, second, and third sample time domain of polymer nanofiber thin-film electrode material
Pulse signal, and background time domain pulse signal is obtained as reference signal under the conditions of same spectra；
By the first, second, third sample time domain pulse signal respectively with reference signal according to scheduled calculation method
Calculate the suction for obtaining circulation the rear film electrode material, non-circulation film electrode material and polymer nanofiber thin-film material
Yield.
The utility model has the advantages that
Non-intrusion type of the present invention, lossless detection method, and it is simple to operate, convenient for observation, work efficiency is high, Neng Goutong
Cross in the simple and quick judgement membrane electrode cyclic process of absorptivity leads to material structure and polar changes because material changes
Become, provides a kind of new method and thinking for lithium ion cell film electrode detection.
Detailed description of the invention
Fig. 1 is LiMn2O4@nano-cellulose membrane electrode after recycling 100 times, does not recycle LiMn2O4@nano-cellulose film
The absorptivity of electrode and nano-cellulose membrane electrode compares spectrogram；
Fig. 2 is nickle cobalt lithium manganate@nano-cellulose membrane electrode after recycling 100 times, does not recycle nickle cobalt lithium manganate@Nanowire
The absorptivity for tieing up plain membrane electrode and nano-cellulose membrane electrode compares spectrogram；
Specific embodiment
In order to more fairly set out technology contents of the invention, it is described in detail in conjunction with specific embodiments herein, it is clear that
Cited embodiment is the preferred embodiment of the technical program, and those skilled in the art can be according to disclosed skill
The other technologies scheme that art content is apparent from still falls within protection scope of the present invention.
Embodiment 1
LiMn2O4@nano-cellulose membrane electrode is cut to the disk of diameter 12mm through size, with lithium piece be to electrode,
Concentration is the LiPF of 1mol/L6EC/DEC=1/1 (mass ratio) mixed liquor be electrolyte, Celgard2400 polypropylene film
For diaphragm, complete button cell assembling in the glove box full of argon gas, button half-cell the filling of 3-4.35V voltage range,
Discharge cycles 100 times.
By recycle 100 times after battery dismantled in glove box, and will circulation after LiMn2O4@nano-cellulose membrane electrode
It rinses and is moved back within 2-3 minutes to drying in vacuum oven in dimethyl carbonate (DMC), drying temperature is 45 DEG C, drying time
For 4 hours, test the first film electrode material is then taken out；LiMn2O4@nano-cellulose membrane electrode, pure will not be recycled
Nano-cellulose membrane electrode is cleaned and dried in the same manner respectively, is obtained and is tested second, third membrane electrode
Material.
The preheating of Terahertz instrument is opened, sample room is dried to sample room humidity less than 3%, spectral conditions parameter is set
Are as follows: pulse width are as follows: 1 picosecond, maximum impulse energy are as follows: 10 receive joule, repetition rate are as follows: 6Hz, angular frequency are as follows: 0.5~
2Thz saves peak position, measures background single channel, the reference signal of background when collecting no sample, by mangaic acid after the circulation prepared
Lithium@nano-cellulose membrane electrode, uncirculated LiMn2O4@nano-cellulose membrane electrode and nano-cellulose film are successively put
Set and tested on specimen holder, after obtaining the circulation respectively, do not recycle and polymer nanofiber thin-film electrode material first,
Second and third sample time domain pulse signal.
By the first, second, third sample time domain pulse signal EsamWith reference signal ErefFourier transformation is carried out, and
Respectively by the first, second, third sample time domain pulse signal EsamWith reference signal ErefIt is calculated by formula (1) and obtains institute
State the absorptivity of circulation rear film electrode material, non-circulation film electrode material and polymer nanofiber thin-film material.
Wherein, Absorbance is absorptivity, EsamFor sample time domain signal, ErefFor with reference to time-domain signal, FFT is quick
Fourier changes operator.
Retest obtains multiple groups testing film electrode absorption spectra data, draws figure by analyzing software after being averaged,
Compare the absorptivity waveform diagram peak shape change and absorption value of three, comparison spectrogram is as shown in Fig. 1, according to three's absorptivity peak
It is found that material structure is better, material granule scatters terahertz signal for the variation of shape, and the terahertz signal tested absorbs
Rate is small, it is possible thereby to qualitatively judge the variation of circulation front and back membrane electrode.
Embodiment 2
Nickle cobalt lithium manganate@nano-cellulose membrane electrode is cut to the disk of diameter 12mm through size, is pair with lithium piece
Electrode, the LiPF that concentration is 1mol/L6EC/DEC=1/1 (mass ratio) mixed liquor be electrolyte, Celgard2400 polypropylene
Film is diaphragm, button cell assembling is completed in the glove box full of argon gas, button half-cell is in 3-4.35V voltage range
Charge and discharge cycle 100 times.
By recycle 100 times after battery dismantled in glove box, and will circulation after nickle cobalt lithium manganate@nano-cellulose film
Electrode rinses in dimethyl carbonate (DMC) to be moved back to drying in vacuum oven for 2-3 minutes, and drying temperature is 45 DEG C, dry
Time is 4 hours, then takes out test the first film electrode material；It is thin that nickle cobalt lithium manganate@nano-cellulose will not be recycled
Membrane electrode, pure nano-cellulose membrane electrode are cleaned and dried in the same manner respectively, are obtained test and are used second, third
Thin-film electrode material.
The preheating of Terahertz instrument is opened, sample room is dried to sample room humidity less than 3%, spectral conditions parameter is set
Are as follows: pulse width are as follows: 1.2 picoseconds, maximum impulse energy are as follows: 12 receive joule, repetition rate are as follows: 8Hz, angular frequency are as follows: 0.5-
2Thz saves peak position, measures background single channel, the reference signal of background when collecting no sample, by nickel cobalt after the circulation prepared
LiMn2O4@nano-cellulose membrane electrode, uncirculated nickle cobalt lithium manganate@nano-cellulose membrane electrode and nano-cellulose are thin
Film is placed sequentially on specimen holder and tests, and after obtaining the circulation respectively, does not recycle and polymer nanofiber membrane electrode material
First, second, and third sample time domain pulse signal of material.
By the first, second, third sample time domain pulse signal EsamWith reference signal ErefFourier transformation is carried out, and
Respectively by the first, second, third sample time domain pulse signal EsamWith reference signal ErefIt is calculated by formula (1) and obtains institute
State the absorptivity of circulation rear film electrode material, non-circulation film electrode material and polymer nanofiber thin-film material.
Wherein, Absorbance is absorptivity, and Esam is sample time domain signal, and Eref is with reference to time-domain signal, and FFT is fast
Fast Fourier changes operator.
Retest obtains multiple groups testing film electrode absorption spectra data, draws figure by analyzing software after being averaged,
Compare the absorptivity waveform diagram peak shape change and absorption value of three, comparison spectrogram is as shown in Fig. 2, according to three's absorptivity peak
It is found that material structure is better, material granule scatters terahertz signal for the variation of shape, and the terahertz signal tested absorbs
Rate is small, it is possible thereby to qualitatively judge the variation of circulation front and back membrane electrode.
Relative to measuring technologies such as existing Raman spectrum, infrared spectroscopies, Terahertz measuring technology is non-intrusion type, lossless
Detection method, and it is simple to operate, material structure in the simple and quick judgement membrane electrode cyclic process of absorptivity can be passed through
With polar change.
Embodiment described above is merely preferred embodiments of the present invention, but protection scope of the present invention not office
Be limited to this, anyone skilled in the art within the technical scope of the present invention, according to the technique and scheme of the present invention
And its design is subject to equivalent substitution or change, should be covered by the scope of protection of the present invention.
Claims (9)
1. a kind of method of testing film electrode material structure change, which is characterized in that
Will circulation rear film electrode material, non-circulation film electrode material and polymer nanofiber thin-film electrode material respectively into
Row is rinsed and is dried in vacuo, and obtains the first, second, third thin-film electrode material of test；
The test is detected with the first, second, third thin-film electrode material using terahertz time-domain spectroscopy instrument respectively, is obtained
After the circulation, do not recycle and the first, second, and third sample time domain pulse of polymer nanofiber thin-film electrode material
Signal, and background time domain pulse signal is obtained as reference signal under the conditions of same spectra；
The first, second, third sample time domain pulse signal is calculated with reference signal according to scheduled calculation method respectively
Obtain the absorption of circulation the rear film electrode material, non-circulation film electrode material and polymer nanofiber thin-film material
Rate.
2. the method for testing film electrode material structure change according to claim 1, which is characterized in that the film
Electrode material includes electrode active material and polymeric nanofiber web.
3. the method for testing film electrode material structure change according to claim 2, which is characterized in that the electrode
Active material be LiMn2O4, nickel ion doped, cobalt acid lithium, nickle cobalt lithium manganate, titanium dioxide, black phosphorus, natural graphite, artificial graphite,
One of graphene, graphene oxide, carbonaceous mesophase spherules, carbon fiber, carbon nanotube and lithium titanate are a variety of.
4. the method for testing film electrode material structure change according to claim 1, which is characterized in that the film
Electrode material is with a thickness of 50um-500um.
5. the method for testing film electrode material structure change according to claim 1, which is characterized in that the thin-film electro
The wash reagent used in the material flushing process of pole is dimethyl carbonate.
6. the method for testing film electrode material structure change according to claim 1, which is characterized in that the thin-film electro
Vacuum drying condition in the material drying process of pole specifically includes:
Drying temperature is 30-60 DEG C, drying time 2-8h.
7. the method for testing film electrode material structure change according to claim 1, which is characterized in that described by institute
It states test and is carried out in detection process with thin-film electrode material using terahertz time-domain spectroscopy instrument, spectral conditions are as follows:
Pulse width are as follows: 0.8-1.5 picoseconds；
Maximum impulse energy are as follows: 8-20 receives joule；
Repetition rate are as follows: 5-10Hz；
Angular frequency are as follows: 0.5-2Thz.
8. the method for testing film electrode material structure change according to claim 1, which is characterized in that the Terahertz
Time-domain spectroscopy instrument in sample test sample room humidity less than 3%.
9. the method for testing film electrode material structure change according to claim 1, which is characterized in that it is described will be described
First, second, third sample time domain pulse signal calculates according to scheduled calculation method with reference signal follow described in acquisition respectively
It is predetermined during the absorptivity of ring rear film electrode material, non-circulation film electrode material and polymer nanofiber thin-film material
Calculation method specifically include:
By the first, second, third sample time domain pulse signal EsamWith reference signal ErefFourier transformation is carried out, and respectively
By the first, second, third sample time domain pulse signal EsamWith reference signal ErefPass through formulaIt calculates and obtains the circulation rear film electrode material, non-circulation film electrode
The absorptivity of material and polymer nanofiber thin-film material.
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Application publication date: 20190618 |