Lithium ion battery full life cycle lithium analysis distribution detection method
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium ion battery full life cycle lithium analysis distribution detection method.
Background
The concept of a self-rocking chair type chargeable and dischargeable lithium battery is proposed by Armand M et al in 1972, and the basic research of the lithium battery is carried out for 47 years. At present, basic research on lithium ion batteries is becoming more and more mature, however, the research on the problem of life decay of lithium ion batteries as one of the key parts of electric vehicles becomes a key point, for example: the phenomena of lithium analysis, thickening of an SEI film on the surface of a negative electrode, loss of recyclable lithium, damage of an active material structure and the like can cause the service life of the lithium battery to be reduced, but effective testing means are required to obtain the complex reaction process information, analyze the existing problems and provide a solution.
Disclosure of Invention
The invention aims to solve the technical problem of providing a lithium ion battery full-life cycle lithium analysis distribution detection method, which aims to solve the problem that the existing method can not effectively detect the lithium ion battery full-life cycle lithium analysis distribution in real time, and can visually observe the position distribution and the thickness of lithium precipitation without disassembling the battery, so that the method has important significance in further understanding the mechanism of the life attenuation of the lithium ion battery and developing a lithium battery with long service life.
The technical scheme of the invention is as follows:
a lithium ion battery full life cycle lithium analysis distribution detection method specifically comprises the following steps:
(1) carrying out accelerated life test on the lithium ion battery at room temperature, acquiring three-dimensional chromatographic images inside the lithium ion battery by using a neutron photography system at different life attenuation stages, and acquiring three-dimensional chromatographic images inside the lithium ion battery by using a CT (computed tomography) measurement system at different life attenuation stages;
(2) superposing and integrating three-dimensional chromatographic images obtained by the neutron photography test system and the three-dimensional chromatographic images obtained by the CT measurement system at different life attenuation stages so as to obtain three-dimensional chromatographic images inside the lithium ion battery;
(3) and (3) analyzing the distribution condition of lithium at different positions on the three-dimensional chromatographic image obtained in the step (2) in the lithium ion battery, and further finding out the key factors influencing the service life of the battery in the lithium ion battery.
In the step (1), the specific steps of the accelerated life test of the lithium ion battery are as follows: firstly, placing a lithium battery in a thermostat at 25 ℃, discharging the battery to 2.0V at a constant current of 1C, and standing for 1 hour; then charging to 3.65V at a constant current of 1C, converting to constant voltage charging, stopping charging after the charging current is reduced to 0.05C, and standing for 1 hour; and repeating the steps and circulating for N weeks, wherein N is 200, 400 and 600 ….
In the step (1), the neutron radiography system is used for acquiring the three-dimensional tomography image of the interior of the lithium ion battery every 200 weeks, and the X-ray CT three-dimensional imaging system is used for acquiring the three-dimensional tomography image of the interior of the lithium ion battery every 200 weeks.
In the step (1), the specific method for acquiring the three-dimensional tomographic image inside the lithium ion battery by the neutron radiography system is as follows: when neutron rays pass through the lithium ion battery, neutrons interact with atomic nuclei in the lithium ion battery, light emitted by transmitted neutrons striking the scintillation screen is reflected to the lens by the reflector and then focused on the CCD camera, and therefore a three-dimensional tomographic image inside the lithium ion battery is obtained.
The incident direction of the neutron rays is perpendicular to the lithium ion battery, and the imaging area is 10cm multiplied by 10 cm.
In the step (2), a specific method for obtaining the three-dimensional tomographic image inside the lithium ion battery by superposition and integration is as follows: and integrating the three-dimensional chromatographic image obtained by the neutron photography test system and the three-dimensional chromatographic image obtained by the CT measurement system by utilizing a matlab image superposition algorithm.
In the step (3), the distribution of lithium at different positions on the three-dimensional tomographic image specifically includes the concentration, shape and position information of lithium.
The invention has the advantages that:
the invention has the theoretical basis that neutrons are uncharged, can easily penetrate through an electron layer, can perform nuclear reaction with atomic nucleus, is sensitive to certain light elements and insensitive to heavy elements, lithium metal just belongs to the light elements, the distribution of lithium is easy to observe by neutron photography, X-ray three-dimensional CT is sensitive to the heavy elements and insensitive to the light elements, materials such as positive and negative electrodes and the like just belong to the heavy elements and can be identified by the X-ray three-dimensional CT, and three-dimensional chromatographic images obtained by combining the neutrons and the heavy elements can reflect the distribution condition of lithium on different positions. The invention overcomes the defects that the traditional analysis and test method needs to disassemble the battery to observe the battery interface and can not effectively observe the loss of the recyclable lithium (lithium precipitation and SEI film thickening) in the circulation process, and the invention can analyze and obtain the distribution of the lithium in the lithium ion battery on the premise of not damaging the structure of the lithium ion battery by the technology of combining neutron photography and CT, thereby realizing the direct detection of the key factors influencing the life attenuation.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A lithium ion battery full life cycle lithium analysis distribution detection method specifically comprises the following steps:
(1) carrying out accelerated life test on the lithium ion battery at room temperature, acquiring three-dimensional chromatographic images inside the lithium ion battery by using a neutron photography system at different life attenuation stages, and acquiring three-dimensional chromatographic images inside the lithium ion battery by using a CT (computed tomography) measurement system at different life attenuation stages;
(2) superposing and integrating three-dimensional chromatographic images obtained by the neutron photography test system and the three-dimensional chromatographic images obtained by the CT measurement system at different life attenuation stages so as to obtain three-dimensional chromatographic images inside the lithium ion battery;
(3) and (3) analyzing the distribution condition of lithium at different positions on the three-dimensional chromatographic image obtained in the step (2) in the lithium ion battery, and further finding out the key factors influencing the service life of the battery in the lithium ion battery.
The accelerated life test is to test the life attenuation of the lithium battery in an accelerated manner according to the cycle life test standard of the lithium battery.
It should be noted that, in this embodiment, the specific process of testing the lithium battery by combining the neutron photograph system and the CT measurement system is as follows: according to the cycle life test standard of the lithium battery, the attenuation of the lithium battery is tested in an accelerated mode, and in the attenuation process of the lithium battery, neutron photography test and X-ray three-dimensional CT are carried out on the lithium batteries with different attenuation degrees, so that key factors influencing life attenuation inside the lithium battery are further detected.
To lithium iron phosphate LiFePO4The method disclosed in this embodiment is described as follows:
(1) selecting 3 LiFePO square lithium batteries of 15 Ah;
(2) in a thermostat environment at 25 ℃, discharging the battery to 2.0V by using current with the circulation rate of 1C, namely 15A, and standing for 1 hour; then charging to 3.65V at a constant current of 15A, converting to constant voltage charging, stopping charging when the charging current is reduced to 0.75A, and standing for 1 hour after charging is finished;
and repeating the steps, and obtaining the distribution of lithium on the three-dimensional chromatographic image by using a neutron photography system and a CT measurement system together after each cycle of N is 200 weeks. The position distribution and the thickness of the lithium precipitation in the lithium ion battery are judged according to the three-dimensional chromatographic image, so that the real-time and nondestructive detection of the lithium precipitation distribution in the whole life cycle process of the lithium ion battery is realized, and the method has important practical significance for researching the degradation mechanism of the lithium ion battery.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.