CN111141755A - Method for detecting internal defects of battery cell - Google Patents
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/88—Investigating the presence of flaws or contamination
- G01N21/95—Investigating the presence of flaws or contamination characterised by the material or shape of the object to be examined
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/88—Investigating the presence of flaws or contamination
- G01N21/8851—Scan or image signal processing specially adapted therefor, e.g. for scan signal adjustment, for detecting different kinds of defects, for compensating for structures, markings, edges
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
- G01N23/04—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and forming images of the material
- G01N23/046—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and forming images of the material using tomography, e.g. computed tomography [CT]
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- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/385—Arrangements for measuring battery or accumulator variables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- G01N21/84—Systems specially adapted for particular applications
- G01N21/88—Investigating the presence of flaws or contamination
- G01N21/8851—Scan or image signal processing specially adapted therefor, e.g. for scan signal adjustment, for detecting different kinds of defects, for compensating for structures, markings, edges
- G01N2021/8887—Scan or image signal processing specially adapted therefor, e.g. for scan signal adjustment, for detecting different kinds of defects, for compensating for structures, markings, edges based on image processing techniques
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- G—PHYSICS
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- G01N2223/60—Specific applications or type of materials
- G01N2223/646—Specific applications or type of materials flaws, defects
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a method for detecting internal defects of a battery cell, which comprises the steps of disassembling a battery, analyzing the copper plating uniformity degree and the gray level degree of the corresponding position of a positive pole piece and whether a black area is presented or not, and judging whether the internal defects of the battery cell exist or not. The detection method provided by the invention can effectively detect the state of the internal defects of the finished product battery core, provides an improvement direction for process production, can effectively reduce the reduction of battery performance of the finished product battery caused by diaphragm wrinkles, bubbles between the diaphragm and the pole piece, foreign matters between the diaphragm and the pole piece and unevenness of the pole piece, improves the consistency of the battery and improves the safety of the battery.
Description
Technical Field
The invention relates to the field of battery detection, in particular to a method for detecting internal defects of a battery cell.
Background
Patent CN106248702A discloses a method for detecting internal influence factors of self-discharge of lithium ion batteries. And (3) establishing a three-dimensional tomographic image of the lithium ion battery part by using X-rays, and analyzing the density, the shape and the position of the image. For the electric core with more stacking layers or winding layers, the method is not easy to obtain effective three-dimensional chromatographic images for analysis, and the time consumption is long, and for the materials such as the diaphragm, the cathode material, the air bubble, the foreign matter and the like which are not sensitive to the X-ray, the method can not effectively analyze.
The diaphragm has each item different sex, can take place the uneven circumstances of stress in the course of working, annotate the liquid back, the diaphragm receives organic solvent infiltration and progressively releases the internal stress, two-phase difference is further obvious, the fold appears in the fixed unable timely elimination internal stress of battery interface this moment, serious person influences whole interface flatness, and then influences battery performance, the influence of diaphragm fold is generally through dismantling the affirmation to finished product battery, because the inaccuracy of battery dismantling, can't carry out effectual quantitative measurement to the fold degree.
On the other hand, due to the fact that the surfaces of the pole pieces or the diaphragms are not flat, foreign matters exist between the pole piece layers of the pole pieces, the pole pieces are not in close contact with the diaphragms, lithium ions or electrons are diffused in the charging and discharging process of the battery, local performances of the battery are inconsistent, the performance of the battery is seriously affected, and safety problems are caused, and the problems are not easy to confirm through conventional tests.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a method for detecting the internal defects of a (lithium ion) battery cell.
The invention aims to provide a method for detecting internal defects of a battery cell, which comprises the steps of disassembling a battery, analyzing the copper plating uniformity degree and the gray degree of the corresponding position of a positive pole piece and whether a black area is presented or not, and judging whether the internal defects of the battery cell exist or not.
According to the invention, the detection method can effectively detect whether the diaphragm in the finished product battery cell has wrinkles, whether bubbles exist between the diaphragm and the pole piece, whether foreign matters exist between the diaphragm and the pole piece, and whether the positive pole piece is flat. The detection result reflects the state of the internal defects of the battery core, an improvement direction is provided for process production, the reduction of battery performance caused by diaphragm wrinkles, bubbles between the diaphragm and the pole piece, foreign matters between the diaphragm and the pole piece and unevenness of the pole piece of the finished battery can be effectively reduced, the consistency of the battery is improved, and the safety of the battery is improved.
According to some preferred embodiments of the present invention, the defects include whether the separator in the battery cell has wrinkles, whether foreign matter, air bubbles, wrinkles and unevenness exist between the separator and the positive electrode plate or the negative electrode plate.
According to some preferred embodiments of the invention, the battery is a lithium ion battery or a sodium ion battery with copper foil as negative electrode current collector or other metal ion battery with copper foil as negative electrode current collector.
According to some preferred embodiments of the present invention, the battery is a metal ion secondary battery, preferably a lithium ion secondary battery, and more preferably, the positive active material of the lithium ion secondary battery is one or more of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium manganese phosphate, lithium nickel cobaltate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, and a lithium-rich manganese-based material, and the positive current collector is an aluminum foil; and/or the negative active substance is graphite or a graphite negative material containing silicon, and the negative current collector is copper foil; and/or the electrolyte is an organic electrolyte.
According to some preferred embodiments of the present invention, the positive electrode sheet is a copper-covered positive electrode sheet electrically separated by a negative electrode.
According to some preferred embodiments of the present invention, the method further comprises discharging the freshly assembled and liquid-filled battery, and then removing the battery for disassembly.
According to some preferred embodiments of the present invention, the discharge current is 0.001-1C, the discharge time is 0.1-600 min, and the product of the discharge current and the discharge time is less than or equal to 30 C.min, preferably, the current is 0.1C, and the discharge time is 30 min.
According to some preferred embodiments of the present invention, during the disassembly process, the positive electrode plate, the separator, and the negative electrode plate are numbered in sequence, and the correspondence relationship is determined.
According to some preferred embodiments of the present invention, when foreign matter or bubbles exist between the separator and the positive electrode sheet or the negative electrode sheet, copper is not uniformly plated at the corresponding position of the positive electrode sheet, and a black or light black area is present; and judging the flatness of the foreign matters, the bubbles and the positive and negative electrodes according to the shape and the size of the black or light black area.
According to some preferred embodiments of the present invention, when the diaphragm has wrinkles, the corresponding position of the positive electrode sheet is not plated with copper uniformly, so that the phenomenon of inconsistent gray scale is present, the wrinkle degree of the diaphragm is analyzed through image software, preferably, the electrode sheet is converted into an electronic file through photographing or scanning, the electronic file is converted into a gray scale image through the image software, a one-dimensional and/or two-dimensional total gray scale value of the gray scale image is obtained, and the wrinkle degree is analyzed according to the total gray scale value.
The invention has the beneficial effects that: the method for detecting the internal defects of the metal ion battery cell can effectively detect whether the diaphragm in the finished product battery cell has wrinkles, whether bubbles exist between the diaphragm and the pole piece, whether foreign matters exist between the diaphragm and the pole piece, and whether the positive pole piece is flat. The detection result reflects the state of the internal defects of the battery core, an improvement direction is provided for process production, the reduction of battery performance caused by diaphragm wrinkles, bubbles between the diaphragm and the pole piece, foreign matters between the diaphragm and the pole piece and unevenness of the pole piece of the finished battery can be effectively reduced, the consistency of the battery is improved, and the safety of the battery is improved. Meanwhile, the invention has the characteristics of low cost and simple equipment, is suitable for various types of batteries including wound batteries and laminated batteries, and has great significance for research and production.
Drawings
FIG. 1 is a schematic view of a normal pole piece.
FIG. 2 is a schematic view of the separator not tightly attached to the pole piece.
FIG. 3 is a schematic view of a diaphragm and a pole piece with air bubbles therebetween.
Fig. 4 is a schematic diagram of the unevenness of the edge of the positive electrode plate or the negative electrode plate.
Fig. 5 is a schematic view showing the presence of wrinkles in the separator.
FIG. 6 shows the one-dimensional total gray scale value of the electrode sheet.
FIG. 7 is a diagram illustrating CT test results.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. The technical solution of the present invention is not limited to the following specific embodiments, and includes any combination of the specific embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
In the present invention, the specific techniques or conditions not specified in the examples are performed according to the techniques or conditions described in the literature in the art or according to the product specification. The instruments and the like are conventional products which are purchased by normal distributors and are not indicated by manufacturers. The chemical raw materials used in the invention can be conveniently bought in domestic chemical product markets. The positive electrode active material of the lithium ion secondary battery used in the following examples is one or a mixture of more of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium manganese phosphate, lithium nickel cobaltate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, and a lithium-rich manganese-based material, and the positive electrode current collector is an aluminum foil; the negative active substance is graphite or a graphite negative material containing silicon, and the negative current collector is copper foil; the electrolyte is an organic electrolyte. In the embodiment, the battery cell is selected as the INP115104309, and the manufacturer is the Limited liability company of the research institute of automobile power batteries in the Union of China.
Example 1
And (2) connecting the freshly assembled lithium ion secondary battery after liquid injection into a charging and discharging instrument, discharging at a current of 0.1C for 30min, taking down the battery, disassembling, sequentially numbering a positive pole piece, a diaphragm and a negative pole piece in the disassembling process, determining a corresponding relation, and observing the positive state (the positive pole piece is covered by copper analyzed by the negative pole).
When the positive pole piece, the negative pole piece and the diaphragm are tightly attached, the copper is uniformly distributed at the corresponding positions of the positive pole piece and the negative pole piece. The positive pole piece presents copper red orange or red orange to black colors, as shown in figure 1.
When the diaphragm is not tightly attached to the positive pole piece or the negative pole piece, if foreign matters or bubbles exist between the positive pole piece and the diaphragm and between the diaphragm and the negative pole piece, copper is not uniformly plated at the corresponding position of the positive pole piece, and a black or light black area is presented. The black or light black areas are shaped and sized to conform to foreign matter or bubbles, as shown in fig. 2.
When air bubbles exist between the diaphragm and the positive pole piece or the negative pole piece, copper is not uniformly plated at the corresponding position of the positive pole piece, and a black or light black area is presented. The black or light black areas are shaped and sized to conform to the bubbles, as shown in fig. 3.
When the edge of the positive pole piece or the negative pole piece is uneven, the corresponding position of the positive pole piece is not plated with copper uniformly, and a black area is presented. The shape and size of the black area are consistent with those of the uneven area, and the unevenness of the positive electrode plate or the negative electrode plate can be confirmed according to the flatness of the positive electrode and the negative electrode, as shown in fig. 4.
When the diaphragm has wrinkles, copper is not uniformly plated at the corresponding position of the positive pole piece, and the phenomenon of inconsistent gray scale is presented. The shape and size of the region are consistent with those of the uneven region, and a semi-quantitative result of the fold degree of the diaphragm can be obtained through image software analysis, as shown in figure 5.
The image software analysis means that the disassembled anode is converted into an electronic file by a photographing or scanning method, the electronic file is converted into a gray image by the image software, and then the total gray value is positively correlated with the copper thickness by measuring the one-dimensional or two-dimensional total gray value of the image, and further positively correlated with the flatness of the diaphragm and the pole piece, so that the semi-quantitative diaphragm wrinkle degree is obtained, as shown in fig. 6.
Comparative example 1
Carrying out CT test on a fresh finished lithium ion secondary battery, wherein the test equipment is Phoenix v | tome | x CT, GE, and the scanning voltage is as follows: 250kv, current: 90 μ a, number of pictures: 1200 sheets, test duration: 90min, resolution 35 μm.
The obtained CT data is shown in FIG. 7, and the CT is used for testing, so that professional CT equipment is needed, and negative materials, diaphragms, foreign matters, bubbles and the like which are insensitive to X-rays are needed, and the CT cannot perform effective imaging; on the other hand, the surface condition of the pole piece cannot be effectively focused in the CT due to the bending of the battery cell pole piece; in addition, because the intensity of the X-ray is low, the X-ray can not penetrate through a large battery cell, the resolution of the center position of the battery cell is poor, and effective judgment can not be carried out.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A method for detecting internal defects of a battery cell is characterized by comprising the steps of disassembling the battery, analyzing the copper plating uniformity degree and the gray level degree of the corresponding position of a positive pole piece and whether a black area is presented or not, and judging whether the internal defects of the battery cell exist or not.
2. The method of claim 1, wherein the defects comprise whether the separator in the cell has wrinkles, whether foreign matter, bubbles, wrinkles and unevenness exist between the separator and the positive electrode plate or the negative electrode plate.
3. The method of claim 1, wherein the battery is a lithium ion battery or a sodium ion battery with copper foil as negative current collector or other metal ion battery with copper foil as negative current collector.
4. The method according to claim 3, wherein the battery is a metal ion secondary battery, preferably a lithium ion secondary battery, more preferably, the positive active material of the lithium ion secondary battery is one or more of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium manganese phosphate, lithium nickel cobaltate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium rich manganese based material, and the positive current collector is aluminum foil; and/or the negative active substance is graphite or a graphite negative material containing silicon, and the negative current collector is copper foil; and/or the electrolyte is an organic electrolyte.
5. The method according to claim 3 or 4, wherein the positive electrode sheet is a copper-covered positive electrode sheet galvanically separated by a negative electrode.
6. The method of any one of claims 1 to 5, further comprising discharging the freshly assembled, liquid-filled battery, and removing the battery for disassembly.
7. The method according to claim 6, wherein the discharge current is 0.001-1C, the discharge time is 0.1-600 min, and the product of the discharge current and the discharge time is less than or equal to 30C-min, preferably, the current is 0.1C, and the discharge time is 30 min.
8. The method according to any one of claims 1 to 7, wherein during the disassembly, the positive electrode sheet, the separator and the negative electrode sheet are numbered in sequence to determine the correspondence.
9. The method according to any one of claims 1 to 8, wherein when foreign matter or air bubbles exist between the separator and the positive electrode plate or the negative electrode plate, copper is not uniformly plated at the corresponding position of the positive electrode plate, and a black or light black area is presented; and judging the flatness of the foreign matters, the bubbles and the positive and negative electrodes according to the shape and the size of the black or light black area.
10. The method according to any one of claims 1 to 9, wherein when the diaphragm has wrinkles, the corresponding position of the positive electrode plate is not plated with copper uniformly, so that a phenomenon of inconsistent gray scale is presented, the wrinkle degree of the diaphragm is analyzed through image software, preferably, the electrode plate is converted into an electronic file through photographing or scanning, the electronic file is converted into a gray scale image through the image software, a one-dimensional and/or two-dimensional total gray scale value of the gray scale image is obtained, and the wrinkle degree is analyzed according to the total gray scale value.
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| CN112881922A (en) * | 2020-12-30 | 2021-06-01 | 天津国安盟固利新材料科技股份有限公司 | Button lithium battery and method for detecting assembling quality of button lithium battery |
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| CN113777516A (en) * | 2021-07-27 | 2021-12-10 | 蜂巢能源科技有限公司 | Method and device for judging abnormal battery cell |
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| CN115829907B (en) * | 2022-04-18 | 2024-02-23 | 宁德时代新能源科技股份有限公司 | Method, device and system for detecting defects of composite material belt diaphragm |
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|---|---|---|---|---|
| CN111579568A (en) * | 2020-05-13 | 2020-08-25 | 苏州龙眼科技有限公司 | Method for rapidly detecting cavity defects of new energy automobile control panel |
| CN112881922A (en) * | 2020-12-30 | 2021-06-01 | 天津国安盟固利新材料科技股份有限公司 | Button lithium battery and method for detecting assembling quality of button lithium battery |
| CN113129260A (en) * | 2021-03-11 | 2021-07-16 | 广东工业大学 | Automatic detection method and device for internal defects of lithium battery cell |
| WO2022257991A1 (en) * | 2021-06-08 | 2022-12-15 | 蜂巢能源科技股份有限公司 | Method for determining short-circuit point position in battery cell |
| CN113777516A (en) * | 2021-07-27 | 2021-12-10 | 蜂巢能源科技有限公司 | Method and device for judging abnormal battery cell |
| CN113777516B (en) * | 2021-07-27 | 2023-07-21 | 蜂巢能源科技有限公司 | Method and device for judging abnormal battery cells |
| WO2023071763A1 (en) * | 2021-10-26 | 2023-05-04 | 江苏时代新能源科技有限公司 | Electrode sheet wrinkling detection apparatus and battery cell production equipment |
| CN115829907B (en) * | 2022-04-18 | 2024-02-23 | 宁德时代新能源科技股份有限公司 | Method, device and system for detecting defects of composite material belt diaphragm |
| CN114993232A (en) * | 2022-07-18 | 2022-09-02 | 苏州宇量电池有限公司 | Method for detecting morphology of electrode material |
| CN114993232B (en) * | 2022-07-18 | 2022-10-18 | 苏州宇量电池有限公司 | Method for detecting morphology of electrode material |
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