CN112213344B - Determination method for lithium separation of pole piece of soft-package lithium ion battery - Google Patents
Determination method for lithium separation of pole piece of soft-package lithium ion battery Download PDFInfo
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- CN112213344B CN112213344B CN201910615631.7A CN201910615631A CN112213344B CN 112213344 B CN112213344 B CN 112213344B CN 201910615631 A CN201910615631 A CN 201910615631A CN 112213344 B CN112213344 B CN 112213344B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 59
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000000926 separation method Methods 0.000 title description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 41
- 238000001125 extrusion Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 11
- 230000007547 defect Effects 0.000 claims abstract description 9
- 238000005259 measurement Methods 0.000 claims abstract description 8
- 238000005481 NMR spectroscopy Methods 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 238000007790 scraping Methods 0.000 claims abstract description 5
- 230000002093 peripheral effect Effects 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 210000000078 claw Anatomy 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000009423 ventilation Methods 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- 239000011366 tin-based material Substances 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- 230000004308 accommodation Effects 0.000 claims 4
- 238000001514 detection method Methods 0.000 abstract description 12
- 230000005311 nuclear magnetism Effects 0.000 abstract description 4
- 238000005429 filling process Methods 0.000 abstract description 2
- 230000000007 visual effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 76
- 230000008569 process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000007600 charging Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000012764 semi-quantitative analysis Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005384 cross polarization magic-angle spinning Methods 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000000449 magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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- Physics & Mathematics (AREA)
- High Energy & Nuclear Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium battery detection, and provides a method for judging lithium precipitation of a pole piece of a soft-package lithium ion battery, which aims at great subjectivity and uncertainty of a method for judging lithium precipitation of a negative pole of the lithium battery, and comprises the following steps: discharging the lithium ion battery to be tested, then disassembling the discharged lithium ion battery in a glove box, taking out a negative pole piece, scraping the negative pole material on the defect position on the negative pole piece to be used as a measurement sample, and finally detecting the measurement sample obtained in the step S2 by adopting a solid nuclear magnetic resonance instrument to judge the lithium precipitation degree of the battery pole piece. According to the invention, the lithium is detected by using the solid nuclear magnetism, visual data can be obtained by detecting the microscopic lithium precipitation which cannot be observed by naked eyes, so that the lithium precipitation degree is judged, and the interference of the detected data is small; the glove box designed for disassembling the battery is more convenient and flexible to operate compared with the glove box by operating the rotating shaft, the extrusion rod and the cap rod with one end exposed outside to finish the filling process of the sample tube.
Description
Technical Field
The invention relates to the technical field of lithium battery detection, in particular to a method for judging lithium precipitation of a pole piece of a soft-package lithium ion battery.
Background
Lithium ion batteries are secondary batteries that rely on lithium ions to move back and forth between a positive electrode sheet and a negative electrode sheet. Lithium ion batteries are widely used because of their environmental friendliness, long life, no memory effect, high specific energy, large specific power, and the like. However, lithium ion batteries may have metal lithium precipitated on the surface of the negative electrode tab during the design and manufacturing process or during an unreasonable charge and discharge process, a phenomenon called lithium precipitation. The lithium separation has great influence on the service life and the safety of the lithium ion battery: on one hand, as part of precipitated lithium metal cannot be oxidized into lithium ions during discharging, the capacity of the battery is attenuated; on the other hand, the precipitated lithium metal may form dendrites, and the continued growth of dendrites may pierce the separator, inducing short circuits in the battery, resulting in dangerous accidents. Therefore, research on the phenomenon of lithium ion battery lithium precipitation is particularly necessary.
At present, the most common method for judging whether the lithium ion battery is used for lithium precipitation is to disassemble the battery, judge the battery with naked eyes or adopt a water dripping method to observe whether bubbles are generated by reaction with water, and subjectively give out the lithium precipitation state and the severity. And the lithium ion battery to be detected is judged to have the lithium precipitation phenomenon by carrying out low-current charge and discharge on the battery core and observing the continuous voltage drop phenomenon at a certain stage. The existing judgment method for lithium ion negative electrode lithium precipitation has great subjectivity and uncertainty. Since the chemical reaction system in the battery is relatively complex, it is difficult to confirm whether the defect existing on the negative electrode sheet is caused by metallic lithium or other side reactions. Even if the reaction with water occurs in the dripping test, it is not possible to accurately determine whether it is a metal lithium or a lithium compound. The lithium precipitation degree can not be intuitively judged through specific data because the small-current charge and discharge is only a qualitative analysis and detection; on the other hand, this method has a certain one-sidedness, and the voltage drop due to the polarization of the battery cannot be excluded. For example, a method for detecting lithium ion battery lithium precipitation disclosed in chinese patent literature, publication No. CN107728078a, includes the following steps: s1: pre-forming the lithium ion battery to be tested, and then placing and sealing; s2: charging the pre-formed lithium ion battery for the first time through the following steps of; placing for one time; carrying out heavy current constant current charging; secondary placing; small-current constant-voltage charging; s3: collecting voltage data in the primary charging process in real time, and judging that the lithium ion battery to be tested has a lithium precipitation phenomenon if the voltage continuously drops at a certain stage in the process of low-current constant-voltage charging; s4: and setting a judgment machine for the voltage change in the S2-4 small current charging process and detecting and screening conditions. Compared with the prior art, the detection method is simple and convenient, has high reliability and can be suitable for batch detection and screening of production. However, this method cannot exclude a voltage drop due to battery polarization, affecting the accuracy of the lithium-ion determination.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the method for judging the lithium precipitation of the pole piece of the soft package lithium ion battery, which effectively judges whether the pole piece of the soft package lithium ion battery is precipitated or not, has small interference, reliable result and convenient detection, provides support for judging suspected lithium precipitation problems in the research, development, design and optimization process and the use process, and increases the safety of the battery.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a method for judging lithium precipitation of a soft package lithium ion battery pole piece comprises the following steps:
s1, discharging a lithium ion battery to be tested;
s2, disassembling the discharged lithium ion battery in a glove box, taking out a negative electrode plate, and scraping the negative electrode material on the defect position on the negative electrode plate to be used as a measurement sample;
and S3, detecting the measurement sample obtained in the step S2 by adopting a solid nuclear magnetic resonance instrument, and further judging the lithium precipitation degree of the battery pole piece.
The invention detects lithium by utilizing the solid nuclear magnetism, has higher detection convenience, can obtain visual data for detecting the microscopic lithium which cannot be observed by naked eyes so as to judge the lithium precipitation degree, has small external interference of the detection data, and has low equipment requirement and low detection cost. In addition, the detection result of the detection method for the circulating microscopic lithium analysis of the lithium ion battery can further perform a relatively clear guiding function on the design of the relevant performance of the lithium ion battery.
Preferably, the lithium ion battery cathode is a carbon material, a silicon-based material, a tin-based material, a nitride, or a transition metal oxide. The lithium ion battery negative electrode is a negative electrode of all possible lithium precipitation, and comprises a carbon material (one or more of graphite, mesophase carbon microspheres and hard carbon), a silicon-based material (Si, silicon oxide, si-C composite material, silicon alloy and a combination thereof), a tin-based material (elemental tin, tin oxide, tin alloy and tin-based composite oxide), a nitride and a transition metal oxide. The method has wide application range and good applicability to batteries of different types.
Preferably, the lithium ion battery is discharged to an SOC of 15% -92%.
The glove box of step S2 is preferably selected, the glove box comprises a peripheral shell, a rest table, a rotating shaft, an extrusion rod and a cap rod, the peripheral shell is formed by closing a front wall, a side wall, a rear wall, a base and a top cover, the side wall is provided with a ventilation branch port, the ventilation branch port is connected with an argon bottle and a vacuum pump through a three-way valve, the front wall is transparent, two operation holes are formed in the front wall, a rubber glove is sleeved on the operation holes, the rest table is used for placing a lithium ion battery, the rest table is horizontally fixed at the position below the operation holes in the front wall, a through hole is formed in the middle of the rest table, a funnel part with a wide upper part and a narrow lower part is connected below the through hole, a positioning ring I is arranged at the opposite position of the lower end of the funnel part, the top cover is detachably arranged above the peripheral shell, the rotating shaft penetrates through the middle of the top cover and then stretches into the peripheral shell, the rotating shaft can rotate and move up and down, the lower end of the rotating shaft is connected with a sample tube accommodating part for placing a sample tube through an iron wire, the sample tube accommodating part falls into the positioning ring I, the opening of the funnel part does not exceed the size of the sample tube opening, the inner side of the base is horizontally fixed at the position of the rotating shaft, the position of the sample tube accommodating part is also provided with a positioning ring II and the positioning ring and the top cover cap, the diameter of the second positioning ring and the top cap rod can be correspondingly positioned in the top cap rod.
Lithium is susceptible to reaction with oxygen, water, etc., and therefore, it is necessary to disassemble the lithium ion battery in a glove box. The common glove box has larger volume, high price and complicated operation steps, and the invention designs a glove box convenient to operate aiming at disassembling the lithium ion battery. Firstly, the glove box is only required to be slightly larger than the lithium ion battery in volume, is small and portable, can be carried out in a fume hood, and is safer. The operation in the glove box is carried out through the glove, the glove can influence the finger flexibility and the operation accuracy, the sample is required to be filled into the sample tube, the solid nuclear magnetic sample tube generally has several specifications of 2.5, 4, 7 and 10 mm, the size is small, and the sample is not easy to be put into the sample tube when the glove is worn. Therefore, a through hole is formed in the middle of the shelving table, a gradually narrowed funnel part is formed below the through hole, a positioning ring I is arranged on the inner side of the base at the position opposite to the lower end of the funnel part, and then the sample tube accommodating part is driven by the rotating shaft to align the sample tube with the lower end of the funnel, so that a sample can conveniently enter the sample tube. The first positioning ring, the second positioning ring and the third positioning ring all play a role in positioning, so that the bottom of the funnel, the extrusion rod and the cap rod are conveniently aligned with the sample tube, and the trouble of repeated adjustment is avoided. The up-and-down movement of the squeeze rod can compact the sample in the sample tube, and the cap rod is used for finally changing the cap of the sample tube on the sample tube. The rotating shaft, the extrusion rod and the cap rod extend out of the top cover, so that the operation of an operator is facilitated.
Preferably, the inner wall of the sample tube receiving portion is provided with a ring of resilient detent formations to secure the sample tube therebetween. In order to fix the sample tube and ensure that the sample tube is positioned in the middle of the sample tube accommodating part, the inner wall of the sample tube accommodating part is provided with a circle of elastic claw structure. The resilient jaw structure also has the advantage of accommodating different sizes of sample tubes without having to replace the sample tube receiving portion.
Preferably, a filter layer is arranged at the upper end of the funnel part, and a plurality of through holes are formed in the filter layer. The sample needs to be ground down and no hard lump fragments can exist. In order to prevent the hard lump fragments from being carelessly dropped, a filter layer of through holes is provided at the upper end of the funnel part.
Preferably, vertical baffles are provided on both sides of the partition. The two sides of the baffle are provided with vertical baffles, so that samples can be prevented from leaking to the base of the glove box, and later cleaning is facilitated.
Preferably, in the step S3, the 90 ° pulse width of the solid state nmr is 2.0 μs.
Therefore, the invention has the following beneficial effects: (1) The lithium separation condition is judged by utilizing the solid nuclear magnetism, so that the method is small in interference, convenient to detect and high in result reliability, and subjective errors caused by artificial observation are avoided; (2) The method has wide application range and good applicability to batteries with different models and sizes. (3) The solid nuclear magnetism is used for detecting the battery cathode material, semi-quantitative analysis can be performed at the same time of qualitative analysis, and pole pieces in different lithium precipitation states can be compared. (4) The glove box designed for disassembling the battery is more convenient and flexible to operate compared with the glove box by operating the rotating shaft, the extrusion rod and the cap rod with one end exposed outside to finish the filling process of the sample tube.
Drawings
Fig. 1 is a schematic diagram of the connection of a glove box.
Fig. 2 is a schematic view of the structure of the glove box interior.
Fig. 3 is a schematic view of the inside of the glove box when the extrusion ram is used.
Fig. 4 is a schematic view of the inside of the glove box when the cap lever is used.
Fig. 5 is an NMR spectrum of a pole piece without lithium precipitation.
FIG. 6 is an NMR spectrum of a pole piece with lithium precipitation.
In the figure: 1. the device comprises a glove box, 2, a front wall, 21, an operation hole, 22, a rest, 221, a funnel part, 222, a filter layer, 3, a top cover, 4, a base, 41, a first positioning ring, 42, a second positioning ring, 43, a third positioning ring, 5, a ventilation branch port, 6, a rotating shaft, 61, a sample tube accommodating part, 611, a sample tube, 612, a claw structure, 7, an extrusion rod, 8, a cap rod, 81, a sample tube cap, 9, a three-way valve, 10, a vacuum pump, 11 and an argon bottle.
Detailed Description
The technical scheme of the invention is further described through specific embodiments.
As shown in fig. 1 and 2, the glove box 1 of the present invention comprises a peripheral casing, a rest 22, a rotating shaft 6, an extrusion rod 7 and a cap rod 8, the peripheral casing is enclosed by a front wall 2, a side wall, a rear wall, a base 4 and a top cover 3 to form a cuboid casing (in order to show the internal structure, the side wall, the rear wall, the base 4 and the top cover 3 of the peripheral casing of the glove box 1 are not shown in fig. 2, only the front wall 2 and the base 4 are reserved, the rotating shaft 6, the extrusion rod 7 and the cap rod 8 are all fixed through the top cover 3 by penetrating through the top cover 3, fig. 3 and 4 are the same), the side wall is provided with a ventilation support opening 5, the ventilation support opening 5 is connected with an argon bottle 11 and a vacuum pump 10 through a three-way valve 9, the front wall 2 adopts a transparent material to conveniently observe the internal condition of the glove box 1, the front wall 2 is provided with two operation holes 21, rubber gloves (not shown) are arranged on the operation holes 21 in a sealing sleeve, the rest 22 is used for placing lithium ion batteries, the rest 22 is horizontally fixed at the position below the operation hole 21 at the inner side of the front wall 2, vertical baffles are arranged at two sides of the rest 22, the width of the rest 22 is not more than half of the width of the glove box 1, enough installation space is provided for the rotating shaft 6, the extruding rod 7 and the cap rod 8, a through hole is arranged in the middle of the rest 22, a funnel part 221 with wide upper part and narrow lower part is connected below the through hole, a filter layer 222 is arranged at the upper end of the funnel part 221, a plurality of small holes are arranged on the filter layer 222, a positioning ring 41 is arranged at the position right opposite to the lower end of the funnel part 221 at the inner side of the base 4, the top cover 3 is detachably and hermetically arranged above the peripheral shell, the rotating shaft 6 penetrates into the peripheral shell from the middle of the top cover 3 after penetrating, the rotating shaft 6 is in sealed fit with the top cover 3 and can rotate and move up and down, a sample tube accommodating part 61 for accommodating a sample tube 611 is connected at the lower end of the rotating shaft 6 through an iron wire, the inner wall of the sample tube accommodating portion 61 is provided with a circle of elastic claw structure 612 for fixing the sample tube 611 in the middle, the claw structure 612 is specifically a plurality of claws uniformly distributed around the circle of the middle part of the inner wall of the sample tube accommodating portion 61, the claws are in a sickle shape, the claws are elastic and can bend in the anticlockwise direction, the sample tube accommodating portion 61 falls into the first positioning ring 41, the opening size of the bottom end of the funnel 221 is not larger than the opening size of the sample tube 611, a second positioning ring 42 and a third positioning ring 43 are further arranged on the moving path of the sample tube accommodating portion 61 when the inner side of the base 4 rotates around the rotating shaft 6, the second positioning ring 42 and the third positioning ring 43 are not covered by the shelving table 22, the pressing rod 7 and the third positioning ring 43 penetrate through the top cover 3 and extend into the peripheral shell respectively, the pressing rod 7 and the third positioning ring 8 are in sealing fit with the top cover 3, the pressing rod 7 and the third cover 8 can move up and down along the top cover 3, when the sample tube accommodating portion 61 is located in the second positioning ring 42, the inner side of the base 4 is located in the positioning ring 6, the second positioning ring 42 is provided with the opening diameter of the sample tube 611, the second positioning ring 42 is located, the positioning ring is located in the top cover 81, and the top cover 81 is located in the top position of the top cover 81, and can be located in the top position, and is located in the top position of the top tube 81.
The specific operation steps are as follows: s1, discharging a lithium cobaltate battery to be tested until the SOC is 50%;
S2, disassembling the discharged battery in a glove box, taking out the negative electrode plate, scraping the negative electrode material on the defect position on the negative electrode plate to serve as a measurement sample, and preventing the defect position on the negative electrode plate from being oxidized by contact with air. The glove box 1 is used in the following steps: the top cover 3 is taken down, the battery to be tested after discharging and the scraper are placed on the placing table 22, the 4mm sample tube 611 is placed in the sample tube accommodating part 61, the sample tube 611 is fixed in the middle by a circle of elastic claw structure on the inner wall of the sample accommodating part, the top of the sample tube cap 81 matched with the sample tube 611 is fixed at the bottom end of the cap rod 8, the top cover 3 is covered and sealed while being observed through the transparent front wall 2, the rotating shaft 6 is rotated to enable the sample tube accommodating part 61 to fall in the positioning ring one 41, the rotating shaft 6 is lifted upwards to enable the opening of the sample tube 611 to be abutted against the lower end of the funnel part 221, and the tightness between the rubber glove and the operation hole 21 is checked. The ventilation branch port 5 is connected with a three-way valve 9 through a rubber tube, and the other two straight tubes of the three-way valve 9 are respectively connected with an argon bottle 11 and a vacuum pump 10. Firstly, the three-way valve 9 is rotated to enable the glove box 1 to be communicated with the vacuum pump 10, the vacuum pump 10 is opened to vacuumize, after a period of time, the three-way valve 9 is rotated to enable the glove box 1 to be communicated with the argon bottle 11, argon is filled into the glove box 1, the three-way valve 9 is closed after repeating the process for at least three times, the construction of a water-free and oxygen-free environment in the glove box 1 is completed, two hands extend into the rubber glove to disassemble a battery in the glove box 1, the defect position on the negative plate is exposed after the disassembly is completed, the funnel 221 is aligned to lightly scrape the negative plate on the defect position by a scraper, two sides of the separator are provided with vertical baffles, so that samples can be prevented from leaking onto the base 4 of the glove box 1, the filter layer 222 is arranged at the upper end of the funnel 221, the negative plate is guaranteed to be ground into a certain particle size to downwards enter the sample tube 611, the opening of the lower end of the funnel 221 is larger than the opening of the sample tube 611, the sample tube 61 can be guaranteed to enter the sample tube 611, the sample tube 611 can be carelessly leaked into the sample tube 61, and cannot fall onto the sample tube 61, and the base 4 of the glove box 1, and the subsequent cleaning is convenient. Scraping can be suspended when the negative electrode material in the sample tube 611 is excessively half, the rotating shaft 6 is rotated to enable the sample tube accommodating part 61 to fall in the second positioning ring 42, the extruding rod 7 is moved up and down to compact the negative electrode material in the sample tube 611, then the negative electrode material is continuously filled, the operation is repeated until the negative electrode material in the sample tube 611 is about 2mm away from the top of the rotor to finish filling, finally the rotating shaft 6 is rotated to enable the sample tube accommodating part 61 to fall in the third positioning ring 43, the cap rod 8 is moved downwards to cover the sample tube cap 81 on the sample tube 611, and the sponge layer at the bottom of the sample tube accommodating part 61 can protect the sample tube 611. After the completion, the three-way valve 9 may be connected to an argon recovery device, and the top cover 3 may be removed after the argon gas in the glove box 1 is discharged, and the sample tube 611 and the sample tube cap 81 may be removed together. For safety, the empty sample tube 611 and the sample tube cap 81 can be weighed in advance, and the weight is weighed again after the sample is loaded, so that the sampling weight is ensured to be more than 160 mg.
And S3, detecting the measurement sample obtained in the step S2 by adopting a solid nuclear magnetic resonance instrument, and further judging the lithium precipitation degree of the battery pole piece. The invention uses AVANCE III MHz wide-cavity solid nuclear magnetic resonance spectrometer (Bruker) of 7 Li MAS NMR spectrum obtained by single pulse, and the specific spectrum acquisition parameters are rotation speed: 10KHz; larmor frequency: 155.5MHz; probe: 4mm temperature-changing CP/MAS;90 ° pulse width: 2.0 μs; each spectrum was sampled 64 times. Fig. 5 is a spectrum of a pole piece without lithium precipitation, and fig. 6 is a spectrum of a pole piece with lithium precipitation. Comparing fig. 5 and fig. 6, it can be seen that a peak of metal lithium appears near 260 ppm in the spectrogram when the pole piece has lithium precipitation, it can obviously determine whether the pole piece has lithium precipitation, and by fitting and integrating the peak, it can perform semi-quantitative analysis on the content of lithium precipitation, give preliminary determination on the degree of lithium precipitation, and the detection result of lithium precipitation has great guiding significance for the design of improvement of the relevant performance of lithium batteries.
Claims (8)
1. The method for judging the lithium precipitation of the pole piece of the soft-package lithium ion battery is characterized by comprising the following steps of:
s1, discharging a lithium ion battery to be tested;
S2, disassembling the discharged lithium ion battery in a glove box, taking out a negative electrode plate, and scraping the negative electrode material on the defect position on the negative electrode plate to be used as a measurement sample; the glove box comprises a peripheral shell, a rest table, a rotating shaft, an extrusion rod and a cap rod, wherein a through hole is formed in the middle of the rest table, a gradually narrowed funnel part is formed below the through hole, a first positioning ring is arranged on the inner side of the glove box at the position opposite to the lower end of the funnel part, a top cover is detachably and hermetically arranged above the peripheral shell, the rotating shaft penetrates through the middle of the top cover and then stretches into the peripheral shell, the rotating shaft can rotate and move up and down, the lower end of the rotating shaft is connected with a sample tube accommodating part through an iron wire, and the sample tube accommodating part falls into the first positioning ring; the inner side of the base is also provided with a second positioning ring and a third positioning ring on the movement path of the sample tube accommodating part when the rotating shaft rotates, the extrusion rod and the cap rod respectively correspond to the second positioning ring and the third positioning ring and extend into the peripheral shell after penetrating through the top cover, and the extrusion rod and the cap rod can move up and down along the top cover;
and S3, detecting the measurement sample obtained in the step S2 by adopting a solid nuclear magnetic resonance instrument, and further judging the lithium precipitation degree of the battery pole piece.
2. The method for determining lithium precipitation of a pole piece of a soft-packaged lithium ion battery according to claim 1, wherein in the step S1, the negative electrode of the lithium ion battery is a carbon material, a silicon-based material, a tin-based material, a nitride or a transition metal oxide.
3. The method for determining lithium precipitation of a pole piece of a soft package lithium ion battery according to claim 1, wherein in the step S1, the lithium ion battery is discharged until the SOC is 15% -92%.
4. The method for judging the lithium precipitation of the pole piece of the soft-packaged lithium ion battery according to claim 1, wherein the glove box (1) in the step S2 comprises a peripheral shell, a rest table (22), a rotating shaft (6), a squeezing rod (7) and a cap rod (8), the peripheral shell is formed by closing a front wall (2), side walls, a rear wall, a base (4) and a top cover (3), the side walls are provided with ventilation branch openings (5), the ventilation branch openings (5) are connected with an argon bottle (11) and a vacuum pump (10) through three-way valves (9), the front wall (2) is transparent, the front wall (2) is provided with two operation holes (21), a rubber glove is sleeved on the operation holes (21), the rest table (22) is used for placing the lithium ion battery, the rest table (22) is horizontally fixed at a position below the operation holes (21) at the inner side of the front wall (2), a through hole is arranged in the middle of the rest table (22), a funnel part (221) with a wide upper part and a narrow lower part is connected, the inner side of the base (4) is provided with a positioning ring (41) at the right position of the lower end of the funnel part (221), the top cover (3) can be detachably arranged above the shell and can be rotatably arranged in the peripheral shell (6) in a rotary manner, and can be rotatably arranged in the peripheral shell (6) from the middle of the rotating shaft (6), the lower extreme of pivot (6) is connected with sample tube accommodation portion (61) that are used for placing sample tube (611) through the iron wire, sample tube accommodation portion (61) falls into retainer plate one (41), funnel portion (221) bottom opening size is not more than sample tube (611) opening size, still be equipped with retainer plate two (42) and retainer plate three (43) on the motion path of sample tube accommodation portion (61) when pivot (6) rotate in base (4) inboard, extrusion rod (7) and lid pole (8) correspond retainer plate two (42) and retainer plate three (43) respectively, stretch into peripheral casing after passing top cap (3), extrusion rod (7) and lid pole (8) can follow top cap (3) and reciprocate, the cross-sectional diameter of extrusion rod (7) is less than the opening diameter of sample tube (611), when sample tube accommodation portion (61) are arranged in retainer plate two (42), extrusion rod (7) can stretch into in sample tube (611), lid pole (8) bottom is fixed with sample tube (81) that is fit for sample tube (611), but in lid pole (81) are arranged in sample tube (81) at the position cap (81).
5. The method for determining lithium precipitation of a pole piece of a soft-pack lithium ion battery according to claim 4, wherein a ring of elastic claw structures (612) are arranged on the inner wall of the sample tube accommodating portion (61) to fix the sample tube (611) in the middle.
6. The method for judging lithium precipitation of the pole piece of the soft-package lithium ion battery according to claim 4, wherein a filter layer (222) is arranged at the upper end of the funnel part (221), and a plurality of through holes are formed in the filter layer (222).
7. The method for judging lithium precipitation of a pole piece of a soft package lithium ion battery according to claim 4, wherein vertical baffles are arranged on two sides of the rest (22).
8. The method for determining lithium precipitation of a soft-pack lithium ion battery electrode according to claim 1,2 or 3, wherein in the step S3, the 90 ° pulse width of the solid state nuclear magnetic resonance apparatus is 2.0 μs.
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