CN112698208A - System and method for in-situ measurement of Young modulus and partial molar volume of lithium battery material - Google Patents

System and method for in-situ measurement of Young modulus and partial molar volume of lithium battery material Download PDF

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CN112698208A
CN112698208A CN202011446833.2A CN202011446833A CN112698208A CN 112698208 A CN112698208 A CN 112698208A CN 202011446833 A CN202011446833 A CN 202011446833A CN 112698208 A CN112698208 A CN 112698208A
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electrode
quartz
cantilever beam
deformation
molar volume
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李大伟
余慧杰
刘兴宇
李江涛
谢立威
陈成
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University of Shanghai for Science and Technology
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01RMEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01BMEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B11/00Measuring arrangements characterised by the use of optical techniques
    • G01B11/16Measuring arrangements characterised by the use of optical techniques for measuring the deformation in a solid, e.g. optical strain gauge
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01BMEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B11/00Measuring arrangements characterised by the use of optical techniques
    • G01B11/24Measuring arrangements characterised by the use of optical techniques for measuring contours or curvatures
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84Systems specially adapted for particular applications
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84Systems specially adapted for particular applications
    • G01N2021/8411Application to online plant, process monitoring
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a system and a method for in-situ measurement of Young modulus and partial molar volume of a lithium battery material, which are characterized by comprising a quartz shell, a quartz block, a quartz cover plate, a cantilever beam structure electrode, a CCD camera, a computer, an active layer, a current collector, a diaphragm, a lug, a counter electrode, a diaphragm and a battery tester, wherein the cantilever beam structure electrode is of a double-layer cantilever beam structure and comprises an active layer and a current collector; the electrode with the cantilever beam structure, the diaphragm and the counter electrode are clamped tightly by the quartz block, the quartz block is adhered to the inner wall of the quartz shell by an adhesive tape, after electrolyte is added, the electrode with the cantilever beam structure and the counter electrode are connected with an external battery tester through tabs penetrating through a quartz cover plate to perform charge-discharge circulation, the CCD camera is used for in-situ recording the deformation of the electrode pole piece in the electrochemical circulation process and storing the deformation in a computer, and the relation between the curvature and material parameters, Young modulus and charging state in the deformation process is analyzed through a mechanical model.

Description

System and method for in-situ measurement of Young modulus and partial molar volume of lithium battery material
Technical Field
The invention relates to a system and a method for in-situ measurement of Young modulus and partial molar volume of a lithium battery material, which can be used for observing the evolution process of mechanical property of a composite electrode in the process of embedding/separating lithium ions in real time, and simultaneously obtaining the evolution rule of macroscopic deformation and microscopic property of the composite electrode material by combining a physical model, and belongs to the technical field of lithium battery measurement.
Background
Lithium batteries are the main energy source for electronic devices and electric vehicles, and are a hot spot of research today. With the rapid development of electric vehicles and the great demand of new energy in the country, the demand for a new generation of lithium batteries having higher power, higher capacity, longer life, and greater safety is greater.
Stress is an important factor affecting the capacity reduction and the life length of lithium batteries. In the process of lithium ion intercalation and deintercalation of the active material, structural changes of the active material are caused, and further volume changes and electrode deformation of the active material are caused, even plastic deformation, fracture, delamination and the like are caused. These factors further affect the capacity and life of the battery during cycling. Also, these factors have a greater impact on battery performance during high rate charging.
Since stress variation is an important factor affecting battery performance, a great deal of research work has been done to simulate the mechanical property variation of electrode materials under different conditions. At present, there are many experimental works for in-situ observation of the changes in shape, structure and volume of the electrode material during the intercalation/deintercalation of lithium ions, which is very important for the design and optimization of lithium ion batteries. The most ideal means for obtaining the deformation mechanism and stress change of the active electrode material in the electrochemical cycle process is an in-situ observation experiment. There are many in situ measurement devices for observing the structural, compositional and morphological changes of the electrode, including MOSS, Digital Image Correlation (DIC), Scanning Electron Microscope (SEM), Atomic Force Microscope (AFM), Nuclear Magnetic Resonance (NMR), and other testing instruments.
The in-situ measurement technology can provide the change of the electrode material in the electrochemical cycle process, and can promote the deep understanding of the deformation process and the reaction mechanism caused by electrochemical diffusion. Based on these factors, Mukhopadhyay et al use optical measurement methods to observe the curvature distortion of the thin film electrode in situ. By combining with the Stony formula, the stress change in the electrode in the electrochemical cycle process can be obtained, and the relation between the stress change and the potential and the pressure is researched. However, for common commercial batteries, such as electrodes containing binders, conductive agents, and active particles, the measurement of stress during lithiation remains a problem. Therefore, the device is not suitable for researching the mechanical-electrochemical coupling performance evolution process of the commercial electrode and cannot directly provide a quantitative value of the stress. Therefore, the invention provides a new testing method which can measure the deformation of the commercial porous composite electrode in the charging and discharging processes in situ, further obtain the change rule of the material performance parameters in the deformation process and provide parameter guidance for stress measurement.
Disclosure of Invention
The invention aims to provide a system and a method for in-situ measurement of the Young modulus and the partial molar volume of a lithium battery material, aiming at the defects in the prior art.
In order to achieve the above, the technical scheme of the invention provides a system for in-situ measurement of Young modulus and partial molar volume of a lithium battery material, which is characterized by comprising a quartz shell, a quartz block, a quartz cover plate, a cantilever beam structure electrode, a CCD camera, a computer, an active layer, a current collector, a diaphragm, a lug, a counter electrode, a diaphragm and a battery tester, wherein the cantilever beam structure electrode is of a double-layer cantilever beam structure and comprises an active layer and a current collector; the electrode with the cantilever beam structure, the diaphragm and the counter electrode are clamped tightly by the quartz block, the quartz block is adhered to the inner wall of the quartz shell by an adhesive tape, after electrolyte is added, the electrode with the cantilever beam structure and the counter electrode are connected with an external battery tester through tabs penetrating through a quartz cover plate to perform charge-discharge circulation, the CCD camera is used for in-situ recording the deformation of the electrode pole piece in the electrochemical circulation process and storing the deformation in a computer, and the relation between the curvature and material parameters, Young modulus and charging state in the deformation process is analyzed through a mechanical model.
Preferably, the model battery is prevented from being corroded by electrolyte, and the test result is ensured to be accurately measured.
Preferably, the quartz cover plate is consistent with the top of the quartz battery shell in size, so that a test system can be conveniently packaged, and external interference is reduced.
Preferably, the rectangular holes on the quartz cover plate are enough to pass through the lugs, so that electrochemical circulation is facilitated.
Preferably, the electrodes with cantilever beam structure are fixed by quartz block, and simultaneously the size structure of the electrodes is designed, and CCD camera is used for recording the deformation of different electrodes in the electrochemical circulation process.
Preferably, the physical mechanical model is used for analyzing the relation between bending deformation and material performance and structure parameters during cantilever beam activity recording.
Preferably, constant current charge-discharge circulation is carried out on the cantilever beam structure electrode in the glove box, and the stability of the reaction environment is ensured.
The technical scheme of the invention also provides a method for in-situ measuring the Young modulus and the partial molar volume of the lithium battery material, which is operated by adopting the test system for in-situ measuring the Young modulus and the partial molar volume of the lithium battery material as claimed in claim 1 and is characterized by comprising the following operation steps,
designing a model battery;
combining an image acquisition means, and recording the evolution process of the bending curvature of the cantilever beam electrode in situ;
designing electrodes with different structure sizes, and analyzing the influence of the thickness of an active layer on bending deformation;
and (3) analyzing the relation between the curvature and material parameters, Young modulus and charging state in the deformation process by using a mechanical model.
The invention has the advantages of designing a model battery convenient for directly observing the electrode reaction process and simultaneously designing the real reaction environment for the battery to work. In combination with image processing, the bending deformation process containing the commercial porous composite electrode was recorded in real time. On the basis of experimental tests, theoretical models and analysis methods corresponding to experimental processes are established. The method can be used for effectively analyzing the relationship among the structural parameters, the performance parameters, the lithium ion concentration and the electrode bending curvature of the composite electrode. And (4) designing the size of the electrode structure by combining a physical model, and deeply analyzing the relation between the electrode structure and the micromechanics performance. In summary, the system can perform in-situ detection of partial molar volume and young's modulus of a commercial composite electrode during electrochemical cycling. This is very important for further in-depth systematic analysis of the mechanical-electrochemical coupling behavior of high capacity electrode materials.
Drawings
FIG. 1 is a schematic view of a battery housing and cover plate model of the present invention;
FIG. 2 is a schematic view of an in situ observation system according to the present invention;
FIG. 3 is a schematic view of the deformation of an electrode during electrochemical cycling;
FIG. 4 is the evolution of the partial molar volume of a commercial graphite composite electrode with the state of charge;
FIG. 5 is the evolution of Young's modulus with the state of charge of a commercial graphite composite electrode;
the device comprises a quartz shell, a quartz block, a quartz cover plate, a cantilever beam structure electrode, a CCD camera, a computer, an active layer, a current collector, a diaphragm, a polar lug and a counter electrode, wherein the quartz shell is 1, the quartz block is 2, the quartz cover plate is 3, the cantilever beam structure electrode is 4, the CCD camera is 5, the computer is 6, the active layer is 7, the current collector is 8, the diaphragm is 9, the polar.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Examples
The structure characteristics of the image acquisition and Young modulus and partial molar volume in-situ measurement system are as follows:
a perspective battery model is designed, and the deformation process of the composite electrode can be conveniently recorded in real time through the design of a quartz window. Wherein, the model battery for in-situ observation is mainly processed by quartz and stainless steel. The composite electrode for testing is mainly prepared by uniformly mixing an active substance, a binder and conductive carbon black and then coating the mixture on a metal current collector. In the experiment, the prepared electrode is of a cantilever beam structure, and meanwhile, the quartz block is used for fixing and is immersed in the electrolyte, so that the electrode structure is allowed to swing freely in the electrolyte.
An electrode structure for deformation observation and mechanical-electrochemical coupling performance analysis is designed. The influence of the thickness of the electrode active layer on the mechanical-electrochemical response of the electrode active layer is observed in real time by adjusting the thickness ratio of the electrode active layer to the current collector. Meanwhile, a physical model is developed to correspond to the electrode deformation process, and the reaction mechanism in the electrode deformation process is further disclosed. And obtaining the analytic solutions of curvature, strain, partial molar volume and Young modulus in the electrode bending process.
The electrodes in the binding experiment were built in a double layer electrode structure as shown in fig. 3. Here, h1And hcThe thicknesses of the active layer and the current collector are indicated, respectively. Lithium ions can be freely inserted and extracted in the electrode, accompanied by expansion and contraction of the electrode active layer. In general, the ratio of the volume of the composite material after lithiation to the initial state is defined as JcIt can be assumed that the function of the lithium ion concentration c is as shown in the following equation:
Figure BDA0002831215350000041
here, Ω is the partial molar volume of the active material, f is the volume fraction of the active particles in the composite electrode, cmaxIndicating the state of concentration of the active material after full charge, and SOC indicating the state of charge of the electrode. The direct relationship between the wire elongation ratio and strain versus volume change for the composite graphite electrode can be given by equation 2:
Figure BDA0002831215350000042
from equation 2, the expansion strain of the composite electrode can be derived:
εs=λs-1=(Jc)1/3-1=(1+fΩcmaxSOC)1/3-1 (3)
although the active layer is a composite electrode prepared from active particles, a conductive agent and a binder, it is assumed here to be macroscopically isotropic and uniformly distributed. For commonly used active materials, such as graphite and LiFePO4, the deformation that occurs during lithiation is small, and thus this part of the theory is defined as bending under elastic conditions. The counter electrode is charged and discharged at a relatively small charge rate, and the concentration distribution of lithium ions in the thickness direction can be assumed to be constant. Under small deformation, the relationship between the electrode bending curvature and the material thickness variation, young's modulus and diffusion concentration is shown as follows:
Figure BDA0002831215350000051
here, Rh=h1/hcAnd RE=E1/EcRespectively represents the thickness ratio and Young modulus ratio of the active layer and the current collector, REh=RERh. For the above equation, there are two main unknowns, young's modulus ratio and partial molar volume. In this case, the problem can be solved by designing electrodes with two different thicknesses. For different Rh1And Rh2The relationship between the curvature, thickness ratio and Young's modulus is as follows:
Figure BDA0002831215350000052
here, ai、bi(i ═ 1,2), etc. are parameters relating to the thickness of the material. The expression is as follows:
Figure BDA0002831215350000053
b2=6(Rh2+1)Rh22hc(4+3Rh2)Rh2
b1=6(Rh1+1)Rh11hc(4+3Rh1)Rh1 (6a-d)
the formula 5 is collated to obtain a quadratic equation of a single element about curvature, thickness and Young's modulus, and the expression is shown as the following formula:
(b2κ1Rh1 4-a1κ1κ2hcRh2 4-b1κ2Rh2 4+a2κ2κ1hcRh1 4)RE 2
(a1b2κ11κ2hcRh2 4-a2b1κ22κ1hcRh1 4)RE
κ1b22b1=0 (7)
here, w1~w3The specific expression form is shown in formulas 8 a-c:
w1=b2κ1Rh1 4-a1κ1κ2hcRh2 4-b1κ2Rh2 4+a2κ2κ1hcRh1 4
w2=a1b2κ11κ2hcRh2 4-a2b1κ22κ1hcRh1 4
w3=κ1b22b1 (8a-c)
and solving the formula 5 to obtain the solution of the one-dimensional quadratic equation. The expression of young's modulus is shown in equation 9:
Figure BDA0002831215350000054
through the solution of the equation and the combination of the curvature deformation monitored in the experimental process, the in-situ measurement of the Young modulus of the electrode in the electrochemical cycle process can be obtained. The results show that the electrode bending curvature is closely related to the relevant parameters of the electrode material. The expansion strain of the electrode during electrochemical cycling is:
Figure BDA0002831215350000061
combining the above formula with formula 5.3, the molar volume of the graphite electrode in different charging states can be obtained:
Figure BDA0002831215350000062
compared with the prior art, the invention has the beneficial effects that:
the deformation evolution of the commercial composite electrode caused by the diffusion of the lithium ions can be measured in situ;
the evolution process of the Young modulus and the partial molar volume of the commercial composite electrode can be accurately tested;
the non-contact measurement of the macroscopic deformation and the microscopic property of the energy source material can be carried out.
And observing the deformation, Young modulus and partial molar volume evolution process of the commercial graphite composite electrode caused by lithium ion diffusion in real time.
As shown in fig. 1 and fig. 2, the measuring system includes a quartz casing 1, a quartz block 2, a quartz cover plate 3, a cantilever structure electrode 4, a CCD camera 5, a computer 6, an active layer 7, a current collector 8, a diaphragm 9, a tab 10, and a counter electrode 11.
The size designed for the test electrode in the experiment accords with a double-layer cantilever beam structure, and the test electrode comprises a commercial graphite electrode (with the theoretical capacity of 330mAh/g) as a reaction electrode and a LiFePO4 electrode (with the theoretical capacity of 127mAh/g) as a corresponding electrode. Here, graphite electrodes of different thickness ratios were used as the reaction electrodes, the thicknesses of which were 94 micrometers and 41 micrometers, respectively. The collector of the reaction electrode was a copper foil with a thickness of 9 μm. It was cut into a double-layered beam having a length of 2mm and a width of 0.2mm, used as a reaction electrode and subjected to curvature measurement. A separator (Celgard 2400, 2 microns) was placed between the anode and cathode to avoid shorting. The model cell was then filled with electrolyte (Ethylene carbonate to Diethyl carbonate, 1: 1 by volume) containing 1M LiPF6 until the reaction electrode was completely immersed. All battery materials in the experiment were purchased from Shenzhenjian science and technology. All assembly processes are completed in a glove box environment.
In order to observe the bending of the cantilever-structured electrode 4, the diaphragm 9 and the counter electrode 11 are clamped by using the quartz block 2, and the quartz block 2 is adhered to the inner wall of the quartz shell 1 by using an adhesive tape. After the electrolyte is added, the quartz shell 1 is packaged by the quartz cover plate 3, and the size of the opening at the top of the quartz cover plate 3 is consistent with that of the opening at the top of the quartz shell 1, so that the quartz cover plate is convenient to wind and package by using an adhesive tape. Connecting the cantilever structure electrode 4 with an external battery tester 13 by using a tab 10 penetrating through the quartz plate 3 so as to perform constant current charge-discharge cycle, wherein the voltage window is 0.01V-2V, and the current density is 142.1 muA/cm2(C/20). In the constant current charging and discharging process, along with the continuous embedding of lithium ions, the embedded lithium concentration is increased, the active layer 7 expands, and due to the constraint action of the current collector 8, the mismatch strain exists between the active layer 7 and the current collector 8, so that the cantilever beam structure electrode 4 is subjected to bending deformation. CCD Camera 5 (J)AI) for in situ recording of the cantilever structure electrode 4 deformation during electrochemical cycling. And (3) measuring the curvature change of the cantilever beam structure electrode 4 by combining with an image acquisition program in the computer 6, thereby obtaining the mechanical property and the stress change of the material of the cantilever beam structure electrode 4. Fig. 4 is the evolution of the partial molar volume of the graphite composite electrode along with the change of the specific capacity in the second charging and discharging process, and fig. 5 is the evolution of the young modulus of the graphite composite electrode along with the change of the specific capacity in the second charging and discharging process.

Claims (8)

1. The system for in-situ measurement of the Young modulus and the partial molar volume of the lithium battery material is characterized by comprising a quartz shell, a quartz block, a quartz cover plate, a cantilever beam structure electrode, a CCD camera, a computer, an active layer, a current collector, a diaphragm, a lug, a counter electrode, a diaphragm and a battery tester, wherein the cantilever beam structure electrode is of a double-layer cantilever beam structure and comprises an active layer and a current collector; the electrode with the cantilever beam structure, the diaphragm and the counter electrode are clamped tightly by the quartz block, the quartz block is adhered to the inner wall of the quartz shell by an adhesive tape, after electrolyte is added, the electrode with the cantilever beam structure and the counter electrode are connected with an external battery tester through tabs penetrating through a quartz cover plate to perform charge-discharge circulation, the CCD camera is used for in-situ recording the deformation of the electrode pole piece in the electrochemical circulation process and storing the deformation in a computer, and the relation between the curvature and material parameters, Young modulus and charging state in the deformation process is analyzed through a mechanical model.
2. The system for in-situ measurement of young's modulus and partial molar volume of lithium battery material as claimed in claim 1, wherein said model battery is protected from corrosion by electrolyte to ensure accurate measurement of test results.
3. The system for in situ measurement of young's modulus and partial molar volume of lithium battery material as claimed in claim 1, wherein said quartz cover plate is of a size consistent with the top of the quartz battery case, facilitating packaging of the test system and reducing external interference.
4. The system for in situ measurement of young's modulus and partial molar volume of a lithium battery material as claimed in claim 1, wherein said quartz cover plate has rectangular holes of a size sufficient to allow the tabs to pass through for electrochemical cycling.
5. The system for in-situ measurement of young's modulus and partial molar volume of lithium battery material as claimed in claim 1, wherein cantilever beam structure electrodes are fixed by quartz blocks while electrode size structure is designed and CCD camera is used to record the deformation of different electrodes during electrochemical cycling.
6. The system for in-situ measurement of young's modulus and partial molar volume of lithium battery material as claimed in claim 1, wherein the physical mechanical model is used to analyze the relation between cantilever bending deformation and material performance and structure parameters.
7. The system for in-situ measurement of the Young modulus and the partial molar volume of a lithium battery material as claimed in claim 1, wherein constant current charge-discharge circulation is performed on the electrode with the cantilever structure in a glove box, so as to ensure the stability of a reaction environment.
8. The method for in-situ measuring the Young modulus and the partial molar volume of the lithium battery material is operated by adopting the test system for in-situ measuring the Young modulus and the partial molar volume of the lithium battery material as claimed in claim 1, and is characterized in that the operation steps are as follows,
1) designing a model battery;
2) combining an image acquisition means, and recording the evolution process of the bending curvature of the cantilever beam electrode in situ;
3) designing electrodes with different structure sizes, and analyzing the influence of the thickness of an active layer on bending deformation;
4) and (3) analyzing the relation between the curvature and material parameters, Young modulus and charging state in the deformation process by using a mechanical model.
CN202011446833.2A 2020-12-11 2020-12-11 System and method for in-situ measurement of Young modulus and partial molar volume of lithium battery material Pending CN112698208A (en)

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