CN111443243A - Detection method for conductivity of lithium ion battery binder - Google Patents

Detection method for conductivity of lithium ion battery binder Download PDF

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CN111443243A
CN111443243A CN202010185897.5A CN202010185897A CN111443243A CN 111443243 A CN111443243 A CN 111443243A CN 202010185897 A CN202010185897 A CN 202010185897A CN 111443243 A CN111443243 A CN 111443243A
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binder
conductivity
lithium ion
ion battery
battery
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CN111443243B (en
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梁栋栋
谢李昭
林少雄
蔡桂凡
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01RMEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R27/00Arrangements for measuring resistance, reactance, impedance, or electric characteristics derived therefrom
    • G01R27/02Measuring real or complex resistance, reactance, impedance, or other two-pole characteristics derived therefrom, e.g. time constant
    • G01R27/22Measuring 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

Detection method for conductivity of lithium ion battery binder
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 and 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 is as follows: 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-R0Calculating the conductivity sigma of the adhesive, wherein A is the area of an adhesive membrane and L is the thickness of the adhesive membrane, and the sigma is L/(delta Rct × A). The button cell is manufactured and measured by the steps, and the average value is taken as the adhesionConductivity test results for the agent.
In specific implementation, in order to ensure the stability of the battery structure, the binder to be detected adopts a sheet structure.
Specifically, in the embodiment, the method for obtaining the solid binder to be tested comprises the steps of coating the liquid binder on the surface of the copper foil, drying at the drying temperature of 60-120 ℃ for 4-12 hours, and then cutting a binder membrane to be used as the binder to be tested, wherein the binder to be tested is specifically selected to be 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 binding performance, fluorinated rubber, lithium polyacrylate (L i-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 the surface of copper foil with modified SBR emulsion with good bonding performance and liquid bonding agent with sample number AB, drying at 60 ℃ for 12h, and manufacturing 5 bonding agent membranes with the diameter of 12mm by using a punching machine, wherein the membrane area A is 113.097mm2The thickness of the copper foil was measured to be 0.01mm using a micrometer, and the thicknesses L of the 5 adhesive films (the thickness of the adhesive minus the thickness of the copper foil) were 0.0774mm, 0.0754mm, 0.0714mm, 0.0718mm, and 0.0762mm, respectively.
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.
The average value R of the EIS test results of 5 2032 button cells can be calculated0Is 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, as σ -L/(Δ Rct × a).
Table 1 lithium ion battery binder conductivity test results of example 1.
Figure BDA0002414157890000041
Figure BDA0002414157890000051
Example 2
The method for detecting the conductivity of the lithium ion battery binder comprises the following specific steps:
the first step is as follows: coating polyacrylic acid (PAA) and a liquid adhesive with the sample number of AP on the surface of a copper foil, drying at 60 ℃ for 12h, and manufacturing 5 adhesive films with the diameter of 12mm by using a punching machine, wherein the area A of each adhesive film is 113.097mm2The thickness of the copper foil was measured to be 0.01mm using a micrometer, and the thickness of the adhesive film was L.
The second step is that: the 2032 type button cell is assembled by 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, wherein the electrolyte uses a silicon-carbon special electrolyte, and 5 binder membranes are assembled into 5 2032 type button cells.
The third step: and carrying out EIS test on the assembled battery, wherein the EIS test frequency range is 1-500 KHz, the amplitude is 5mV, and the test temperature is room temperature. EIS test result average R of 5 cells0Is 2.8843. According to the formula Δ Rct ═ R1-R0Calculation of σ L/(Δ Rct × a)The electrical conductivity of the binder.
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 (5)

1. The method for detecting the conductivity of the lithium ion battery binder is characterized in that a solid binder to be detected is obtained, and a battery structure adopting 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.
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.
5. The method for detecting the conductivity of the lithium ion battery binder according to claim 1, wherein the battery structure comprises 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.
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