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When the weather gets cold, the capacity of lithium batteries that are originally full of energy will be reduced. Lithium batteries seem to have entered a state of hibernation, which brings a lot of trouble to users of new energy vehicles and digital products. The topic of today's article is the impact of low temperature on lithium batteries and the industry's research and development progress.
Is lithium battery most afraid of low temperature?
In tests conducted by AAA, an electric car had a range of 105 miles (169 kilometers) at 75 degrees Fahrenheit (about 24 degrees Celsius), which dropped to 20 degrees Fahrenheit (about 7 degrees Celsius). The drop is as high as 60% to 43 miles (approximately 69 kilometers). Batteries are somewhat similar to people. They become less active when the climate turns colder. Lead-acid batteries, lithium batteries and fuel cells will all be affected by low temperatures, but to varying degrees.
Take lithium iron phosphate batteries, which are most commonly used in electric buses, as an example. This type of battery is highly safe and has a long cell life, but its low-temperature performance is slightly worse than batteries of other technical systems. Low temperature has an impact on the positive and negative electrodes, electrolytes and adhesives of lithium iron phosphate. For example, the lithium iron phosphate cathode itself has poor electronic conductivity and is prone to polarization in low-temperature environments, thereby reducing battery capacity. Affected by low temperature, the graphite lithium insertion speed is reduced, and metallic lithium is easily precipitated on the surface of the negative electrode. If the battery is left alone for insufficient time after charging, When it is put into use, all the metallic lithium cannot be embedded inside the graphite again. Some metallic lithium continues to exist on the surface of the negative electrode, which is very likely to form lithium dendrites and affect the safety of the battery. At low temperatures, the viscosity of the electrolyte will increase, and the lithium ion migration resistance will also increase. In addition, in the production process of lithium iron phosphate, the adhesive is also a very critical factor, and low temperature will also have a great impact on the performance of the adhesive.
It is also a lithium battery, and lithium titanate battery has excellent low temperature resistance. The lithium insertion potential of the spinel-structured lithium titanate negative electrode material is about 1.5V, and lithium dendrites will not be formed. The volume strain during the charge and discharge process is less than 1%. Nanosized lithium titanate batteries can charge and discharge at high currents, achieving low-temperature fast charging while ensuring battery durability and safety. For example, Yinlong New Energy, which specializes in lithium titanate batteries, has normal charge and discharge capabilities at -50-60°C.
Although lithium-ion batteries with graphite as the negative electrode can be discharged at -40°C, it is more difficult to achieve conventional current charging at -20°C and lower temperatures. This is also an area that the industry is actively exploring.
The industry’s exploration of low-temperature resistant lithium batteries
Enterprises and scientific research institutions in the industry are exploring and researching the low-temperature resistance of batteries, mostly focusing on improving the process of existing positive and negative electrode materials, and creating conditions for the battery to work at low temperatures by increasing the local ambient temperature of the battery.
Today's battery materials are moving toward nanometerization. The particle size, resistance, and AB plane axis length of the material will affect the low-temperature characteristics of the battery. Waterma prepared lithium iron phosphate materials through three processes, using different processes to nanometerize and coat them. The results show that the increase in the AB plane axis length makes the lithium ion migration channel larger, which is beneficial to increasing the battery rate. Performance; Judging from the materials produced by the three processes, granular graphite with large interlayer spacing has relatively small body resistance and ion migration resistance; in terms of electrolyte, Waterma uses low-temperature additives based on a fixed solvent system and lithium salt to Discharge capacity increased from 85% to 90%. It is understood that as early as the end of 2016, Waterma has achieved a 0.5C charging constant current ratio of 62.9% in an environment of -20, -30, and -40°C, and a discharge of 94% at -20°C. At present, Waterma's low-temperature batteries have been widely promoted in Inner Mongolia, three northeastern provinces and other regions.
In addition, Penghui Energy’s power batteries can be used in an environment of -20~60℃ and do not require heating and cooling systems. The low-temperature resistance of Thornton New Energy's ternary batteries has been greatly improved. The batteries can be discharged normally in a -20°C environment, which can meet the needs of many vehicle companies.
Why does charging require more temperature than discharging?
Careful readers may find that many companies' battery products can achieve normal discharge at low temperatures, but at the same temperature, it is more difficult or even impossible to charge normally. Why?
According to industry insiders, when Li+ is embedded in graphite material, it must first be solvated. This process consumes a certain amount of energy and prevents Li+ from diffusing into the graphite. On the contrary, when Li+ comes out of the graphite material and enters the solution, there will be a solvation process. process, and solvation does not consume energy, Li+ can quickly escape from graphite. Therefore, the charge acceptance ability of graphite materials is significantly inferior to the discharge acceptance ability.
There are certain risks in battery charging in low temperature environments. Because as the temperature decreases, the dynamic characteristics of the graphite negative electrode worsen. During the charging process, the electrochemical polarization of the negative electrode is significantly intensified. The precipitated metallic lithium easily forms lithium dendrites, which penetrates the separator and causes short circuit of the positive and negative electrodes. .
Therefore, industry insiders recommend that you try to avoid charging lithium-ion batteries at low temperatures. When the battery must be charged at low temperatures, it is necessary to charge the lithium-ion battery with a small current (i.e. slow charge) as much as possible, and fully shelve the lithium-ion battery after charging to ensure that the metallic lithium precipitated from the negative electrode can react with the graphite. , re-embedded inside the graphite negative electrode.
Of course, lithium titanate batteries have material advantages. They can still achieve fast charging at low temperatures. This kind of willfulness is difficult to learn from batteries made of other materials.
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Lithium battery structure and voltage, capacity composition method
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