CN110687318A - Analysis method of copper dendrite on surface of diaphragm - Google Patents
Analysis method of copper dendrite on surface of diaphragm Download PDFInfo
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- CN110687318A CN110687318A CN201810739668.6A CN201810739668A CN110687318A CN 110687318 A CN110687318 A CN 110687318A CN 201810739668 A CN201810739668 A CN 201810739668A CN 110687318 A CN110687318 A CN 110687318A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
- G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
- G01Q60/24—AFM [Atomic Force Microscopy] or apparatus therefor, e.g. AFM probes
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Abstract
The invention relates to an analysis method of copper dendrite on the surface of a diaphragm. The analysis method comprises the following steps: 1) cleaning a diaphragm obtained by disassembling the lithium ion battery to obtain a sample to be detected; 2) and scanning the sample to be detected by using an atomic force microscope, and analyzing according to the scanning image to obtain the distribution and the growth height of the copper dendrite on the sample to be detected. According to the analysis method of the copper dendrites on the surface of the diaphragm, the diaphragm is cleaned and analyzed by an atomic force microscope, so that the fine characterization analysis of the copper dendrites growing on the diaphragm is realized, the distribution and the growth height of the copper dendrites can be simultaneously characterized, and effective support can be provided for relevant basic theory research or optimization of battery performance.
Description
Technical Field
The invention belongs to the field of evaluation and analysis of lithium ion batteries, and particularly relates to an analysis method of copper dendrites on the surface of a diaphragm.
Background
At present, most lithium ion batteries adopt liquid electrolytes, diaphragms play roles in isolating positive and negative pole pieces and conducting lithium ions in the lithium ion batteries, and the main materials of the diaphragms are PP (polypropylene), PE (polyethylene), PI (polyimide) and the like. The battery voltage is possibly too low due to self-discharge in the long-term storage process of the battery, so that the copper foil of the negative current collector is dissolved, and the dissolved copper element can be separated out again on the surface of the negative plate or the diaphragm in the charging process, so that the diaphragm is pierced, and the positive and negative electrodes are in short circuit.
The fine characterization analysis of the copper dendrites on the surface of the diaphragm can provide important feedback for the optimization of the battery structure or performance and also provide scientific support for relevant basic theory research. Currently, the prior art lacks such an analysis method for copper dendrites on the surface of the diaphragm.
Disclosure of Invention
The invention aims to provide an analysis method of copper dendrites on the surface of a diaphragm, so as to solve the problem that the existing technology can not perform characterization analysis on the copper dendrites growing on the surface of the diaphragm.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for analyzing copper dendrites on the surface of a diaphragm comprises the following steps:
1) cleaning a diaphragm obtained by disassembling the lithium ion battery to obtain a sample to be detected;
2) and scanning the sample to be detected by using an atomic force microscope, and analyzing according to the scanning image to obtain the distribution and the growth height of the copper dendrite on the sample to be detected.
According to the analysis method of the copper dendrites on the surface of the diaphragm, the diaphragm is cleaned and analyzed by an atomic force microscope, so that the fine characterization analysis of the copper dendrites growing on the diaphragm is realized, the distribution and the growth height of the copper dendrites can be simultaneously characterized, and effective support can be provided for relevant basic theory research or optimization of battery performance.
In the step 1), the lithium ion battery can be disassembled by a conventional method to obtain the diaphragm for detection and analysis, and the disassembling process is preferably carried out in a glove box in an inert atmosphere to improve the safety.
The cleaning is to soak the diaphragm in an organic solvent, replace the organic solvent after soaking, carry out ultrasonic treatment, replace the organic solvent after ultrasonic treatment, and then carry out soaking treatment. And then soaking and naturally drying to obtain the sample to be detected. The atomic force microscope images by the tiny acting force between atoms, when the probe is close to the sample surface, because the weak van der Waals acting force exists between the atom at the tip of the probe point and the atom on the sample surface, the micro cantilever fixing the probe is positioned on the equipotential surface corresponding to the acting force between the sample atoms by controlling the constant van der Waals acting force during scanning, the cantilever moves in the direction vertical to the sample surface, the position change corresponding to each scanning point can be measured by an optical detection method, and then the signal is amplified and converted to obtain the scanning image of the sample. The working principle of the atomic microscope is easily obtained, the interaction degree between the probe and the atoms on the surface of the sample can be influenced to a certain degree by processing the sample, and the diaphragm sample obtained by disassembling the battery can directly cause the inaccuracy or the failure of the subsequent analysis and characterization process if the cleaning process is improper. By adopting the optimized cleaning process, the influence of components such as electrolyte on the subsequent analysis and characterization process can be reduced to the greatest extent, the clearer and more accurate surface morphology can be obtained, and the influence of the components on the measurement of the growth height of the copper dendrite can be effectively avoided. More preferably, the soaking time is 5-40 min. The power of the ultrasonic treatment is 60-80Hz, and the time is 5-20 min. The organic solvent is dimethyl carbonate and/or diethyl carbonate.
In the step 2), during scanning, a sample to be detected is bonded on a stainless steel slide. The sample to be measured can be cut into the size of 5mm by 5mm, so that the installation and the measurement of the sample to be measured are facilitated.
The scan was performed using Peak Force mode. The measurement can be carried out by adopting a ScanAsyst inAir mode in a Peak Force mode. The probe used for scanning is RTEAPA-150, and the elastic coefficient k is 6N/m. When scanning, the scanning range is controlled to be (50-120) mu m by (50-120) mu m, and preferably 90 mu m by 90 mu m. The laser is directed at locations 1/3-1/2 on the probe cantilever beam away from the free end face of the cantilever beam.
The threshold of force used during scanning is 5-10 nN. The threshold for the Peak Force tapping amplitude (Peak Force TappinAmplified) is 150-200 nm.
In step 2), the Analysis is performed using NanoScope Analysis software. The height measurement is performed using the Section function in the analysis software.
The analysis method of the copper dendrites on the surface of the diaphragm is suitable for fine characterization of the copper dendrites grown on the diaphragms such as polypropylene PP, polyethylene PE, polyimide PI and the like, can well characterize the height and distribution conditions of the copper dendrites while reproducing the morphology of the copper dendrites, realizes fine evaluation of the diaphragms under different electrochemical conditions, and further can provide effective support for performance optimization of lithium ion batteries.
Drawings
FIG. 1 is a surface topography of a separator without copper dendrites growing on the surface;
FIG. 2 is a surface topography of a diaphragm with small amounts of copper dendrites grown on the surface;
FIG. 3 is a copper dendrite height distribution plot obtained after processing the separator of FIG. 2 using analytical software;
FIG. 4 is a surface topography of a membrane with more copper dendrites grown on the surface.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings.
Example 1
The analysis method of the copper dendrite on the surface of the diaphragm adopts the following steps:
1) the lithium ion battery was disassembled in a glove box, the separator was separated and cut into 5mm by 5mm squares.
2) And (3) soaking the cut diaphragm in 50mL dimethyl carbonate (DMC) for 30min, replacing a soaking solvent with fresh DMC, performing ultrasonic treatment for 10min at 70Hz, replacing an ultrasonic treatment solvent with fresh DMC again after ultrasonic treatment, soaking for 10min, taking out the diaphragm sample, and naturally airing in a fume hood to obtain a sample to be measured.
3) A sample to be tested is adhered to a stainless steel slide piece through double-sided adhesive, scanning is carried out through a ScanAsystin Air mode in a Peak Force mode, the position where laser is emitted is 1/3, far away from the free end face of a cantilever beam, on the cantilever beam of a probe, the scanning range is 90 mu m by 90 mu m, the probe used for scanning is RTEAPA-150 (the elastic coefficient K is 6N/m), the applied Force threshold value is 5-10nN, and the Peak Force Tapping Amplitude (Peak Force Tapping Amplitude) threshold value is 150nm-180 nm.
4) Processing the scanning image obtained in the step 3) by using NanoScope Analysis software, and performing height measurement by using a Section function.
In the embodiment, the diaphragm used by the lithium ion battery is a single-drawn polypropylene diaphragm, the surface appearance of the diaphragm without copper dendrites growing on the surface is shown in fig. 1, the stretching condition and the pore distribution of the surface of the diaphragm can be obviously seen from fig. 1, and the overall roughness of the diaphragm is small.
The morphology of the separator with a small amount of copper dendrites growing on the surface, which is observed by the method of the embodiment, is shown in fig. 2, and the distribution of the copper dendrites in the pores of the separator can be seen. After the scanned image is processed by using analysis software, the specific height and distribution of the copper dendrites are analyzed and shown in fig. 3 and table 1.
TABLE 1 height distribution of copper dendrites over the scan range
As can be seen from the results in Table 1, there were 46 points in the scanning range where copper dendrites were grown and the density was 0.46 pieces/. mu.m2The average height is 86.733nm, the minimum height is 55.694nm, and the maximum height is 174.266 nm; the area with copper dendrites grown in the scanning range is 20466.680nm on average2Minimum area 1525.879nm2Maximum area of 123596.188nm2(ii) a The average equivalent diameter of the copper dendrite area is 136.826nm, the minimum equivalent diameter is 44.077nm, and the maximum equivalent diameter is 396.696 nm.
Another diaphragm sample was analyzed with reference to the method of example 1 and the surface topography of the diaphragm was shown in fig. 4, it can be seen that copper dendrites grow along the voids almost filling the diaphragm voids, and the scanned image can be further processed with analytical software to obtain detailed characterization data similar to table 1. With the characterization results, membrane samples of different processes can be finely compared and evaluated, so that data support can be provided for improvement of battery performance.
In other embodiments of the present invention, the cleaning of the separator may be achieved by replacing dimethyl carbonate with diethyl carbonate or a mixed solvent of dimethyl carbonate and diethyl carbonate according to the method of embodiment 1. In the cleaning process, the time of immersion and the conditions of ultrasonic treatment can be adjusted within the range defined by the present invention, and the effect equivalent to that of example 1 can be obtained.
Claims (8)
1. A method for analyzing copper dendrites on the surface of a diaphragm is characterized by comprising the following steps:
1) cleaning a diaphragm obtained by disassembling the lithium ion battery to obtain a sample to be detected;
2) and scanning the sample to be detected by using an atomic force microscope, and analyzing according to the scanning image to obtain the distribution and the growth height of the copper dendrite on the sample to be detected.
2. The method for analyzing copper dendrites on the surface of a separator according to claim 1 wherein in step 1), the cleaning is performed by soaking the separator in an organic solvent, replacing the organic solvent after soaking, performing ultrasonic treatment, replacing the organic solvent after ultrasonic treatment, and performing soaking treatment.
3. The method for analyzing copper dendrites on the surface of a separator according to claim 2 wherein the soaking time is 5-40 min.
4. The method for analyzing copper dendrites on the surface of a separator according to claim 2 wherein the power of the ultrasonic treatment is 60 to 80Hz and the time is 5 to 20 min.
5. The method of analyzing copper dendrites on the surface of a separator according to claim 2 wherein the organic solvent is dimethyl carbonate and/or diethyl carbonate.
6. The method for analyzing copper dendrites on the surface of a diaphragm of claim 1 wherein in step 2), the scanning is performed using a PeakForce mode, and the threshold of force applied during scanning is 5-10 nN.
7. The method for analyzing copper dendrites on the surface of a diaphragm of claim 1 wherein in step 2), the scanning is performed using a PeakForce mode, and the threshold value of the peak force tapping amplitude during scanning is 150-200 nm.
8. The method for analyzing copper dendrites on the surface of a separator according to claim 1 wherein in step 2), the Analysis is performed using NanoScope Analysis software.
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Address after: 454191 Henan Province, Jiaozuo City Station area coke Rd Applicant after: Duofudo New Material Co.,Ltd. Address before: 454191, Feng County, Henan Province, Jiaozuo Feng Feng Chemical Industry Zone Applicant before: DO-FLUORIDE CHEMICALS Co.,Ltd. |
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Application publication date: 20200114 |