CN111443243B - Detection method for conductivity of lithium ion battery binder - Google Patents
Detection method for conductivity of lithium ion battery binder Download PDFInfo
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- CN111443243B CN111443243B CN202010185897.5A CN202010185897A CN111443243B CN 111443243 B CN111443243 B CN 111443243B CN 202010185897 A CN202010185897 A CN 202010185897A CN 111443243 B CN111443243 B CN 111443243B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R27/00—Arrangements for measuring resistance, reactance, impedance, or electric characteristics derived therefrom
- G01R27/02—Measuring real or complex resistance, reactance, impedance, or other two-pole characteristics derived therefrom, e.g. time constant
- G01R27/22—Measuring resistance of fluids
Abstract
The invention provides a method for detecting the conductivity of a lithium ion battery binder, which comprises the steps of obtaining a solid binder to be detected, and manufacturing a battery structure adopting the binder to be detected; and performing EIS test on the battery structure, and calculating the conductivity of the binder to be tested according to the test result. The method for detecting the conductivity of the lithium ion battery binder provided by the invention provides very important performance parameters for selecting a proper binder, and the method is accurate in test result, simple and rapid, and easy to operate.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a method for detecting the conductivity of a lithium ion battery binder.
Background
Because of its high energy density, lithium ion batteries have played an increasingly important role in new energy sources, the capacity of lithium ion batteries is determined by the active lithium ions of the positive electrode material and the lithium-intercalation/deintercalation capability of the negative electrode material, and the stability of the positive electrode and the negative electrode in various environments determines the performance of the batteries, even seriously affecting the safety of the batteries. In order to further improve the performance of lithium ion batteries, researchers have tried to find new electrode materials, electrolytes and additives, however, the efficiency of lithium ion batteries depends largely on the optimization of the electrode preparation conditions, and one of the important aspects is to find the most suitable binder for the electrode. In the electrode, the binder is an important component in the anode and cathode materials of the lithium battery, can tightly bond the active material, the conductive agent and the current collector in the electrode material, enhances the electronic contact between the active material and the conductive agent as well as between the active material and the current collector, better stabilizes the structure of the pole piece, and plays an important role in buffering the volume expansion/contraction in the charge-discharge process of the anode and the cathode of the lithium battery. The selection and the use of the electrode significantly influence the macroscopic electrochemical performance of the electrode, and the optimization of the electrode is an important factor which must be considered for manufacturing the electrode plate of the high-performance lithium ion battery. Therefore, a suitable binder is one of the key points for the success of lithium ion power cells.
The method has the advantages that a proper lithium ion battery binder is selected, the lithium ion battery binder is required to have stable performance in electrolyte, no expansion, no loosening, no powder falling and small ohmic resistance, so that the development of a simple and accurate test method for the conductivity of the battery binder is very important, and very important performance parameters are provided for the selection of a proper binder.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for detecting the conductivity of a lithium ion battery binder.
The invention provides a method for detecting the conductivity of a lithium ion battery binder, which comprises the steps of obtaining a solid binder to be detected, and manufacturing a battery structure adopting the binder to be detected; and performing EIS test on the battery structure, and calculating the conductivity of the binder to be tested according to the test result.
Preferably, the binder to be tested has a sheet structure.
Preferably, the method for obtaining the solid binder to be tested comprises the following steps: and coating the liquid binder on the surface of the copper foil, drying at the drying temperature of 60-120 ℃ for 4-12 h, and then cutting a binder membrane to be used as the binder to be tested.
Preferably, the binder to be detected is a circular membrane with the diameter of 12-18 mm and the thickness of L20-200 um.
Preferably, the battery structure comprises a battery negative electrode shell, a first stainless steel sheet, a copper foil, a binder to be tested, a diaphragm, a second stainless steel sheet, a spring gasket and a battery positive electrode shell from bottom to top.
The method for detecting the conductivity of the lithium ion battery binder provided by the invention provides very important performance parameters for selecting a proper binder, and the method is accurate in test result, simple and rapid, and easy to operate.
Drawings
FIG. 1 is a flow chart of a method for detecting the conductivity of a binder of a lithium ion battery according to the present invention;
FIG. 2 is a schematic diagram of a battery structure in a method for detecting conductivity of a binder of a lithium ion battery according to the present invention;
fig. 3 is a line graph of conductivity test data for the lithium ion battery binder of example 1.
Detailed Description
Referring to fig. 1, according to the method for detecting the conductivity of the binder of the lithium ion battery, a solid binder to be detected is obtained, and a battery structure using the binder to be detected is manufactured; and performing EIS test on the battery structure, and calculating the conductivity of the binder to be tested according to the test result.
Specifically, the battery structure in this embodiment is composed of a battery negative electrode case, a first stainless steel sheet, a copper foil, a to-be-tested binder, a diaphragm, a second stainless steel sheet, a spring washer, and a battery positive electrode case from bottom to top. The EIS test can be completed by placing the battery structure in electrolyte, or adding the electrolyte into a closed space formed by a battery negative electrode shell and a battery positive electrode shell.
According to the specific embodiment of the method, the EIS test frequency range is 1-500 KHz, the amplitude is 5mV, and the test temperature is room temperature. The test result of the test group is recorded as R1The reference group test result is recorded as R0. According to the formula Δ Rct ═ R1-R0The electrical conductivity σ of the adhesive was calculated as L/(Δ Rct × a), where a is the area of the adhesive film piece and L is the thickness of the adhesive film piece. 3-5 button cells are manufactured and measured according to the steps, and the average value is taken as the conductivity test result of the adhesive.
In specific implementation, in order to ensure the stability of the battery structure, the binder to be detected adopts a sheet structure.
Specifically, in this embodiment, the method for obtaining the solid binder to be tested includes: and coating the liquid binder on the surface of the copper foil, drying at the drying temperature of 60-120 ℃ for 4-12 h, and then cutting a binder membrane to be used as the binder to be tested. Specifically, the binder to be measured is a circular membrane with the diameter of 12-18 mm and the thickness of L20-200 um.
The method is suitable for binders such as polyvinyl alcohol (PVA), polyacrylic acid (PAA) and salts thereof, Polytetrafluoroethylene (PTFE), Polyimide (PI), sodium carboxymethylcellulose (CMC), polyolefins (PP, PE and other copolymers), (PVDF/NMP) or other solvent systems, PVDF-based fluorine-containing polymers, polyelectrolyte polymers, Styrene Butadiene Rubber (SBR), modified SBR rubber with good bonding performance, fluorinated rubber, lithium polyacrylate (Li-PAA) or other ionic polymer binders, polyurethane and the like.
The invention is demonstrated below with reference to two specific examples.
Example 1
The method for detecting the conductivity of the lithium ion battery binder comprises the following specific steps:
the first step is as follows: coating a liquid binder with sample number AB on the surface of a copper foil of the modified SBR emulsion with good bonding performance, drying at 60 ℃ for 12h, manufacturing 5 binder membranes with the diameter of 12mm by using a punching machine, wherein the membrane area A is 113.097mm2, the thickness of the copper foil is measured by using a micrometer to be 0.01mm, and the thickness L (the thickness of the binder minus the thickness of the copper foil) of the 5 binder membranes is respectively 0.0774mm, 0.0754mm, 0.0714mm, 0.0718mm and 0.0762 mm.
The second step is that: the 2032 type button cell is assembled, the 2032 type button cell is composed of a cell cathode shell (with a plastic sealing ring), a stainless steel sheet, a copper foil, a binder membrane, a diaphragm, a stainless steel sheet, a spring gasket and a cell anode shell from bottom to top, and the electrolyte uses a special electrolyte for silicon carbon.
The third step: respectively carrying out EIS test on 5 2032 type button cells, wherein the EIS test frequency range is 1-500 KHz, the amplitude is 5mV, the test temperature is room temperature, and the test result R of a test group is14.0175, 3.9570, 3.9050, 3.9159, 3.9746, respectively.
Calculating the average value R of the EIS reference group test results of 5 2032 button cells0Is 2.8843. According to the formula Δ Rct ═ R1-R0The conductivity σ of the binder was calculated to be 6.15E-04, see table 1 for details.
Table 1 lithium ion battery binder conductivity test results of example 1.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention are equivalent to or changed within the technical scope of the present invention.
Claims (4)
1. A detection method for conductivity of a lithium ion battery binder is characterized in that a solid binder to be detected is obtained, a battery structure is composed of a battery negative electrode shell, a first stainless steel sheet, a copper foil, a binder to be detected, a diaphragm, a second stainless steel sheet, a spring gasket and a battery positive electrode shell from bottom to top, and the battery structure adopting the binder to be detected is manufactured; performing EIS test on the battery structure, and calculating the conductivity of the binder to be tested according to the test result;
the test result of the test group is recorded as R1The test results of the reference group are recorded as R0(ii) a According to the formula Δ Rct ═ R1-R0The electrical conductivity σ of the adhesive was calculated as L/(Δ Rct × a), where a is the area of the adhesive film piece and L is the thickness of the adhesive film piece.
2. The method for detecting the conductivity of the lithium ion battery binder according to claim 1, wherein the binder to be detected has a sheet structure.
3. The method for detecting the conductivity of the lithium ion battery adhesive according to claim 1, wherein the method for obtaining the solid adhesive to be detected comprises the following steps: and coating the liquid binder on the surface of the copper foil, drying at the drying temperature of 60-120 ℃ for 4-12 h, and then cutting a binder membrane to be used as the binder to be tested.
4. The method for detecting the conductivity of the lithium ion battery adhesive according to claim 3, wherein the adhesive to be detected is a circular membrane with a diameter of 12-18 mm and a thickness of L20-200 um.
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| US7581434B1 (en) * | 2003-09-25 | 2009-09-01 | Rockwell Automation Technologies, Inc. | Intelligent fluid sensor for machinery diagnostics, prognostics, and control |
| CN105720300B (en) * | 2016-03-31 | 2019-06-21 | 成都国珈星际固态锂电科技有限公司 | Gel polymer lithium ion battery and preparation method thereof and electric vehicle |
| EP3540419A1 (en) * | 2018-03-12 | 2019-09-18 | Consejo Superior De Investigaciones Científicas (CSIC) | A device and a method for sensing the conductivity of a fluid |
| CN109616691A (en) * | 2018-11-09 | 2019-04-12 | 哈尔滨工业大学无锡新材料研究院 | A kind of test method for the assembling equipment and the solid electrolyte conductivity being assembled into solid state battery using solid electrolyte |
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| CN103173161A (en) * | 2013-03-08 | 2013-06-26 | 东莞新能源科技有限公司 | Preparation method of lithium ion battery cathode sheet adhesive emulsion |
| CN106935904A (en) * | 2017-02-28 | 2017-07-07 | 中山大学 | A kind of lithium single-ion conductor polymer dielectric based on functionalization lithium borate salt |
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