CN110927593A - Method for evaluating electrode material of lithium ion battery after circulation by button cell - Google Patents
Method for evaluating electrode material of lithium ion battery after circulation by button cell Download PDFInfo
- Publication number
- CN110927593A CN110927593A CN201911155651.7A CN201911155651A CN110927593A CN 110927593 A CN110927593 A CN 110927593A CN 201911155651 A CN201911155651 A CN 201911155651A CN 110927593 A CN110927593 A CN 110927593A
- Authority
- CN
- China
- Prior art keywords
- button cell
- lithium ion
- battery
- evaluating
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- 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
Abstract
A method for evaluating a lithium ion battery electrode material after circulation by adopting a button cell mainly comprises the following steps: s1, disassembling the lithium ion full battery, and taking out the electrode plate of the battery; s2, wiping off one surface of the pole piece obtained in the step S1, and carrying out vacuum baking; s3, punching the pole piece obtained in the step S2 and assembling the pole piece into a button cell; s4, carrying out electrochemical performance test on the button cell obtained in the step S3; s5, evaluating the capacity exertion condition of the electrode material according to the electrical property test of the step S4. According to the invention, on one hand, the positive and negative electrode plates of the battery after circulation can be assembled into the electricity-buckling battery, and on the other hand, the electrical property test can be carried out on the electrode plate material after the lithium desorption reaction.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a method for evaluating an electrode material of a cycled lithium ion battery by using a button cell.
Background
The lithium ion battery has the advantages of high specific energy, long service life, no memory effect and the like, and is widely applied to the fields of 3C products and new energy automobiles. In the process of charge and discharge test and storage of the lithium ion battery, irreversible lithium source loss is caused by the formation of an SEI film, irreversible lithium intercalation, electrode surface side reaction, lithium deposition and the like, and meanwhile, the loss of active materials on a pole piece is caused by structural change of active materials of the battery, falling of active materials and the like, so that the capacity exertion of the active materials of the pole piece of the battery is reduced.
At present, the electrical performance test means before the electrode material is assembled into the battery is mature, and the electrical performance test problem after the electrode material is assembled into the battery and lithium intercalation and deintercalation reaction needs to be solved urgently. In the research of lithium batteries, a continuous new detection means is needed for comprehensively evaluating the performance of electrode materials in a lithium battery system.
Disclosure of Invention
The invention aims to provide a method for evaluating an electrode material of a lithium ion battery after circulation by adopting a button battery, which aims to solve the technical problem of electrical performance test after the electrode material is assembled into the battery and lithium intercalation and deintercalation reaction is carried out.
In order to achieve the purpose, the specific technical scheme of the method for evaluating the electrode material of the lithium ion battery after circulation by adopting the button cell is as follows:
a method for evaluating a cycled lithium ion battery electrode material by using a button cell comprises the following steps:
s1, disassembling the lithium ion full battery, and taking out the electrode plate of the battery;
s2, wiping off one surface of the pole piece obtained in the step S1, and carrying out vacuum baking;
s3, punching the pole piece obtained in the step S2, assembling the pole piece into a button cell, punching the pole piece into a circular pole piece matched with the model of the button cell, and sequentially assembling the button cell according to the sequence of a positive electrode shell, the pole piece (one surface without active substances is contacted with the positive electrode shell), a diaphragm, a lithium piece, a stainless steel piece, an elastic piece and a negative electrode shell;
s4, carrying out electrochemical performance test on the button cell obtained in the step S3;
s5, evaluating the capacity exertion condition of the electrode material according to the electrical property test of the step S4;
in the present invention, preferably, the positive electrode of the lithium ion battery in step S1 is a ternary material, the negative electrode is one of graphite, silicon carbon or silica material, the lithium ion battery is a battery subjected to a charge-discharge test, and the taken out battery electrode plate encloses the positive electrode plate and the negative electrode plate of trichosanthes kirilowii maxim.
In the present invention, preferably, in step S2, the positive electrode piece is wiped with NMP (N-methylpyrrolidone), the negative electrode is wiped with deionized water on one side of the positive electrode piece, and only the active material on one side of the positive electrode piece is required to exert capacity when the assembly is buckled. Baking at 20-115 deg.C under vacuum degree of 40-1000Pa for 3-36 hr, and baking to remove solvent.
In the invention, preferably, the diameter of the round piece of the punching sheet in the step S3 is phi 5-50mm, and the battery case model is 2450.
In the present invention, the electrochemical performance in step S4 is preferably a charge and discharge test.
In the invention, preferably, in the electrical property test, the charge-discharge multiplying power of the button cell assembled by the positive pole piece is 0.1-1C, the charge-discharge cut-off voltage is 2.75V and 4.3V respectively, the charge-discharge multiplying power of the button cell assembled by the negative pole piece is 0.03C, and the charge-discharge cut-off voltage is 1.5V and 0.05V respectively.
The method for evaluating the electrode material of the lithium ion battery after the circulation by adopting the button cell has the following advantages: the method for manufacturing the button cell by the electrode pole piece after circulation can be used for evaluating the electrical property of the electrode material in a lithium battery system and accurately testing the electrochemical properties of different electrode materials after charge-discharge reaction.
Drawings
FIG. 1 is a flow chart of the operation of a method of evaluating a cycled lithium ion battery electrode material using a button cell battery in accordance with the present invention;
FIG. 2 is test data from example 1 of a method of evaluating a cycled lithium ion battery electrode material using a button cell battery in accordance with the present invention;
fig. 3 is test data from example 2 of a method of evaluating lithium ion battery electrode material after cycling using a button cell battery in accordance with the present invention.
Detailed Description
For better understanding of the objects, structure and functions of the present invention, a method for evaluating an electrode material of a lithium ion battery after cycling by using a button cell battery will be described in further detail with reference to the accompanying drawings.
As shown in fig. 1-3, the present invention is directed to evaluating the electrical properties of lithium battery electrode materials after a lithium deintercalation reaction using button cells.
Example 1:
the button cell type is 2450, the anode is high nickel ternary material, the cathode is lithium cell electrode to test:
a method for evaluating a cycled lithium ion battery electrode material by using a button cell comprises the following steps:
s1, disassembling the lithium ion full battery as the lithium ion battery after the charge and discharge test, taking out the electrode plate of the battery, and wrapping the positive and negative electrode plates of the trichosanthes kirilowii with the taken-out electrode plate of the battery;
and S2, wiping the positive pole piece in the step S1 with NMP (N-methyl pyrrolidone), wiping one surface of the pole piece with deionized water, wherein the surface of the wiped pole piece is only required to be used as an active substance on one surface of the pole piece to exert capacity during assembling and fastening electricity. Baking at 20-115 deg.C under vacuum degree of 40-1000Pa for 3-36 hr, and baking to remove solvent;
s3, punching the pole piece obtained in the step S2, assembling the punched piece into a button cell, punching the pole piece into a circular pole piece matched with the model of the button cell, and sequentially assembling the pole piece into the button cell according to the sequence of a positive pole shell, the pole piece (one surface without active substances is contacted with the positive pole shell), a diaphragm, a lithium piece, a stainless steel piece, an elastic piece and a negative pole shell;
s4, carrying out charge and discharge tests on the button cell obtained in the step S3, wherein the charge and discharge multiplying power of the button cell assembled by the positive pole piece in the tests is 0.1-1C, the charge and discharge cutoff voltage is 2.75V and 4.3V respectively, the charge and discharge multiplying power of the button cell assembled by the negative pole piece is 0.03C, and the charge and discharge cutoff voltage is 1.5V and 0.05V respectively;
s5, evaluating the capacity exertion condition of the electrode material according to the electrical property test of the step S4;
the electrochemical test data for example 1 is shown in figure 2:
FIGS. 2 a-f show the discharge curves of nickel-cobalt-manganese (NCM) ternary materials with different nickel contents before and after 100 cycles in a full battery (NCM/silicon-oxygen system):
a) after NCM811 cycles; b) after NCM622 cycling; c) after cycle of NCM 523; d) before cycle of NCM 523; e) before cycle NCM 622; f) discharge plot before NCM811 cycle.
As can be seen from fig. 2, the gram capacities of the NCM523, NCM622, and NCM811 materials before circulation are respectively 175mAh/g, 182mAh/g, and 185mAh/g, and after 1C charge and discharge for 100 cycles in the full cell, the gram capacities of the NCM523, NCM622, and NCM811 materials are respectively reduced by 10mAh/g, 27mAh/g, and 35mAh/g, and from the test results, the gram capacity of the NCM811 material after circulation for 100 cycles is the lowest and 150mAh/g, the gram capacity of the NCM622 material is the next highest and is 155mAh/g, and the gram capacity of the NCM523 material is the highest and is 165 mAh/g.
After long-term circulation, the CEI film on the surface of the high-nickel ternary material is thickened, particles are crushed, polarization is increased, internal resistance is increased, and further gram capacity of the material is reduced, so that the gram capacity of the circulated high-nickel NCM811 material is the lowest, the gram capacity of the NCM622 is the next highest, and the gram capacity of the NCM523 is the highest, which is consistent with the test result.
Example 2:
the button cell type is 2450, the anode is a lithium sheet, and the cathode is a cell electrode made of silicon oxygen/silicon carbon/graphite material:
a method for evaluating a cycled lithium ion battery electrode material by using a button cell comprises the following steps:
s1, disassembling the lithium ion full battery as the lithium ion battery after the charge and discharge test, taking out the electrode plate of the battery, and wrapping the positive and negative electrode plates of the trichosanthes kirilowii with the taken-out electrode plate of the battery;
and S2, wiping the positive pole piece in the step S1 with NMP (N-methyl pyrrolidone), wiping one surface of the pole piece with deionized water, wherein the surface of the wiped pole piece is only required to be used as an active substance on one surface of the pole piece to exert capacity during assembling and fastening electricity. Baking at 20-115 deg.C under vacuum degree of 40-1000Pa for 3-36 hr, and baking to remove solvent;
s3, punching the pole piece obtained in the step S2, assembling the punched piece into a button cell, punching the pole piece into a circular pole piece matched with the model of the button cell, and sequentially assembling the pole piece into the button cell according to the sequence of a positive pole shell, the pole piece (one surface without active substances is contacted with the positive pole shell), a diaphragm, a lithium piece, a stainless steel piece, an elastic piece and a negative pole shell;
s4, carrying out charge and discharge tests on the button cell obtained in the step S3, wherein the charge and discharge multiplying power of the button cell assembled by the positive pole piece in the tests is 0.1-1C, the charge and discharge cutoff voltage is 2.75V and 4.3V respectively, the charge and discharge multiplying power of the button cell assembled by the negative pole piece is 0.03C, and the charge and discharge cutoff voltage is 1.5V and 0.05V respectively;
s5, evaluating the capacity exertion condition of the electrode material according to the electrical property test of the step S4;
the electrochemical test data for example 2 is shown in figure 3:
in FIG. 3, g-l show the charging and discharging curves of the silicon-oxygen, silicon-carbon and graphite cathode materials before and after 100 cycles in the full cell (NCM is the cathode material):
g) before the circulation of the silica material; h) after the silica material is circulated; i) before the silicon-carbon material is circulated; j) after the silicon-carbon material is circulated; k) before the graphite material is circulated; l) discharge curve of the graphite material after circulation.
As can be seen from fig. 3, the gram capacities of the silicon-oxygen, silicon-carbon and graphite negative electrode materials before circulating in the full battery are 542mAh/g, 430.8mAh/g and 349.4mAh/g, respectively, after circulating in the full battery for 100 weeks, the gram capacities of the silicon-oxygen, silicon-carbon and graphite materials are 471mAh/g, 379.2mAh/g and 323.6mAh/g, respectively, the gram capacity of the silicon-oxygen material after circulating is reduced to the greatest extent, which is 71mAh/g, the gram capacity loss of the silicon-carbon material is 51.6mAh/g, and the gram capacity of the graphite material after circulating is the lowest, which is 25.8 mAh/g. Because the three cathode materials are easy to generate volume expansion effect in the lithium intercalation process, the volume expansion effect of silicon oxygen and silicon carbon is strong, and the volume expansion effect of graphite is low, after the charge-discharge cycle is carried out in the full cell, the silicon oxygen material is easy to generate particle breakage due to the expansion effect and is accompanied with the formation of monocrystalline silicon, so that the gram capacity loss is maximum, the gram capacity loss of the silicon carbon material is less, the gram capacity loss of the graphite material is relatively minimum, and the test result is consistent with the test result.
Therefore, the testing method can well reflect the capacity exertion conditions of different electrode material systems after circulation (multiple charge-discharge reactions), and further explore the polarization conditions of the different electrode material systems in the electrochemical reaction.
It is to be understood that the present invention has been described with reference to certain embodiments, and that various changes in the features and embodiments, or equivalent substitutions may be made therein by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (8)
1. A method for evaluating a cycled lithium ion battery electrode material by using a button cell is characterized by mainly comprising the following steps:
s1, disassembling the lithium ion full battery, and taking out the electrode plate of the battery;
s2, wiping off one surface of the pole piece obtained in the step S1, and carrying out vacuum baking;
s3, punching the pole piece obtained in the step S2 and assembling the pole piece into a button cell;
s4, carrying out electrochemical performance test on the button cell obtained in the step S3;
s5, evaluating the capacity exertion condition of the electrode material according to the electrical property test of the step S4.
2. The method of claim 1, wherein the lithium ion battery is a battery subjected to a charge-discharge test, and the extracted battery electrode piece comprises positive and negative electrode pieces of trichosanthes kirilowii.
3. The method for evaluating the electrode material of the lithium ion battery after the cycling by using the button cell as claimed in claim 1, wherein the positive electrode of the lithium ion battery in the step S1 is a ternary material, and the negative electrode is any one of silicon-oxygen, silicon-carbon and graphite material.
4. The method for evaluating the cycled lithium ion battery electrode material of any one of claims 1 to 3, wherein the positive electrode sheet is wiped with N-methylpyrrolidone and the negative electrode is wiped with deionized water on one side of the sheet in the step S2.
5. The method for evaluating the lithium ion battery electrode material after the circulation by using the button cell as claimed in claim 4, wherein the baking temperature in the step S2 is 20-115 ℃, the vacuum degree is 40-1000Pa, and the time is 3-36 h.
6. The method for evaluating the cycled lithium ion battery electrode material by the button cell as claimed in claim 1 or 2, wherein the diameter of the punched piece in the step S3 is phi 5-50mm, and the battery case model is 2450.
7. The method of claim 1, wherein the electrochemical performance of step S4 is charge and discharge test.
8. The method of claim 1, wherein the button cell assembled by the positive electrode plate in the electrical property test has a charge/discharge rate of 0.1-1C, a charge/discharge cut-off voltage of 2.75V and 4.3V, respectively, a button cell assembled by the negative electrode plate has a charge/discharge rate of 0.03C, and a charge/discharge cut-off voltage of 1.5V and 0.05V, respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911155651.7A CN110927593A (en) | 2019-11-22 | 2019-11-22 | Method for evaluating electrode material of lithium ion battery after circulation by button cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911155651.7A CN110927593A (en) | 2019-11-22 | 2019-11-22 | Method for evaluating electrode material of lithium ion battery after circulation by button cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110927593A true CN110927593A (en) | 2020-03-27 |
Family
ID=69850685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911155651.7A Pending CN110927593A (en) | 2019-11-22 | 2019-11-22 | Method for evaluating electrode material of lithium ion battery after circulation by button cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110927593A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111781252A (en) * | 2020-06-18 | 2020-10-16 | 合肥国轩高科动力能源有限公司 | Method for detecting electrochemical stability of lithium ion battery binder |
| CN111856293A (en) * | 2020-06-03 | 2020-10-30 | 天津力神电池股份有限公司 | Method for testing capacity of silicon negative electrode material of lithium ion battery |
| CN112162200A (en) * | 2020-09-08 | 2021-01-01 | 合肥国轩高科动力能源有限公司 | Method for accurately measuring SOC (state of charge) of lithium ion battery |
| CN112327187A (en) * | 2020-09-18 | 2021-02-05 | 合肥国轩高科动力能源有限公司 | Evaluation method for cycle performance of electrode material |
| CN112379294A (en) * | 2020-08-05 | 2021-02-19 | 万向一二三股份公司 | Method for analyzing performance attenuation of lithium ion battery |
| CN112526370A (en) * | 2020-11-10 | 2021-03-19 | 深圳市拓邦锂电池有限公司 | Voltage testing method of three-electrode lithium ion battery |
| 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 |
| CN113358428A (en) * | 2021-04-26 | 2021-09-07 | 万向一二三股份公司 | Lithium battery pole piece processing method |
| CN114280482A (en) * | 2021-12-06 | 2022-04-05 | 上海空间电源研究所 | Full cell and silicon-based material intrinsic cycle stability evaluation method based on full cell |
| CN114965654A (en) * | 2022-06-17 | 2022-08-30 | 合肥国轩高科动力能源有限公司 | Method for evaluating gram capacity and NP ratio of positive and negative electrode materials in lithium battery |
-
2019
- 2019-11-22 CN CN201911155651.7A patent/CN110927593A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111856293A (en) * | 2020-06-03 | 2020-10-30 | 天津力神电池股份有限公司 | Method for testing capacity of silicon negative electrode material of lithium ion battery |
| CN111856293B (en) * | 2020-06-03 | 2022-12-06 | 天津力神电池股份有限公司 | Method for testing capacity of silicon negative electrode material of lithium ion battery |
| CN111781252A (en) * | 2020-06-18 | 2020-10-16 | 合肥国轩高科动力能源有限公司 | Method for detecting electrochemical stability of lithium ion battery binder |
| CN112379294A (en) * | 2020-08-05 | 2021-02-19 | 万向一二三股份公司 | Method for analyzing performance attenuation of lithium ion battery |
| CN112162200A (en) * | 2020-09-08 | 2021-01-01 | 合肥国轩高科动力能源有限公司 | Method for accurately measuring SOC (state of charge) of lithium ion battery |
| CN112327187A (en) * | 2020-09-18 | 2021-02-05 | 合肥国轩高科动力能源有限公司 | Evaluation method for cycle performance of electrode material |
| CN112526370B (en) * | 2020-11-10 | 2022-07-29 | 深圳市拓邦锂电池有限公司 | Voltage testing method of three-electrode lithium ion battery |
| CN112526370A (en) * | 2020-11-10 | 2021-03-19 | 深圳市拓邦锂电池有限公司 | Voltage testing method of three-electrode lithium ion battery |
| 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 |
| CN113358428A (en) * | 2021-04-26 | 2021-09-07 | 万向一二三股份公司 | Lithium battery pole piece processing method |
| CN114280482A (en) * | 2021-12-06 | 2022-04-05 | 上海空间电源研究所 | Full cell and silicon-based material intrinsic cycle stability evaluation method based on full cell |
| CN114965654A (en) * | 2022-06-17 | 2022-08-30 | 合肥国轩高科动力能源有限公司 | Method for evaluating gram capacity and NP ratio of positive and negative electrode materials in lithium battery |
| CN114965654B (en) * | 2022-06-17 | 2024-02-09 | 合肥国轩高科动力能源有限公司 | Method for evaluating gram capacity and NP ratio of anode and cathode materials in lithium battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110927593A (en) | Method for evaluating electrode material of lithium ion battery after circulation by button cell | |
| CN109839598B (en) | Nondestructive testing method for reversible lithium loss of positive electrode of lithium ion battery | |
| CN109728252B (en) | Positive plate, preparation method thereof and sodium ion battery | |
| CN101533900B (en) | Phosphorus composite material used for electrochemistry reversible lithium storage and preparation method thereof | |
| CN110988086B (en) | Method for detecting structural stability of electrode material in battery cycle process | |
| US20180301289A1 (en) | Lithium ion capacitor and formation method therefor | |
| CN110767880A (en) | Lithium supplement slurry for lithium secondary battery and preparation method of lithium secondary battery | |
| US20180366720A1 (en) | Positive active material and lithium-ion secondary battery | |
| CN112433159B (en) | Detection method for lithium ion battery graphite negative electrode lithium separation | |
| CN108336353B (en) | Mixed lithium/sodium ion battery | |
| CN105449166A (en) | Manufacturing method for negative electrode pole piece for sodium ion battery | |
| CN115312774A (en) | Method for determining and controlling pre-lithium amount of negative electrode lithium supplement electrode piece | |
| CN102427123A (en) | Lithium ion secondary battery and anode sheet thereof | |
| CN104993168A (en) | High-capacity 9-V rechargeable lithium battery and manufacturing method | |
| CN106532031B (en) | A kind of Li4Ti5O12Negative electrode material and its manufactured lithium titanate battery | |
| CN108258244B (en) | Novel lithium ion/potassium ion battery negative electrode material and preparation method thereof | |
| CN107482181B (en) | Composite lithium ion battery anode material Li3V2(PO4)3/C and preparation method thereof | |
| CN116031494A (en) | Battery and preparation method thereof | |
| CN109841800A (en) | A kind of fluorophosphoric acid vanadium sodium and carbon complex and its preparation and application | |
| CN101771144A (en) | Method for improving capacity and cycle performance of spinel LiMn2O4 as anode material of lithium-ion battery | |
| CN112271342A (en) | Preparation method of zinc ion battery ZIB based on vanadium oxide positive electrode material | |
| CN111653724A (en) | Surface-modified lithium nickel manganese oxide positive electrode material and preparation method thereof | |
| CN117199575B (en) | Negative electrode plate, preparation method thereof and sodium ion battery | |
| CN109742455B (en) | Method for manufacturing lithium ion battery | |
| JP6233252B2 (en) | Method for producing solid electrolyte battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |