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Why the maximum voltage of lithium-ion batteries cannot exceed 4.2V ?

The voltage of a lithium ion battery is determined by the electrode potential. Voltage, also known as potential difference, is a physical quantity that measures the energy difference of electric charges in an electrostatic field due to different potentials. The electrode potential of lithium ion is about 3V, and the voltage of lithium ion batteries varies with different materials. For example, a general lithium-ion battery has a rated voltage of 3.7V and a full-charge voltage of 4.2V; while a lithium iron phosphate battery has a rated voltage of 3.2V and a full-charge voltage of 3.65V. In other words, the potential difference between the positive electrode and the negative electrode of a lithium-ion battery in practical use cannot exceed 4.2V, which is an element based on material and use safety.

maximum voltage of a lithium ion battery


If the Li/Li+ electrode is used as the reference potential, μA is the relative electrochemical potential of the negative electrode material, μC is the relative electrochemical potential of the positive electrode material, and the electrolyte potential interval Eg is the lowest electron unoccupied energy level and the highest electron occupied energy of the electrolyte. The difference between the levels. So, it is the three factors of μA, μC, and Eg that determine the highest voltage value of a lithium-ion battery.

The difference between μA and μC is the open circuit voltage (the highest voltage value) of the lithium-ion battery. When this voltage value is in the Eg range, the electrolyte can be guaranteed to work normally. Normal work means that the lithium-ion battery moves back and forth between the positive and negative electrodes through the electrolyte, but does not undergo oxidation-reduction reactions with the electrolyte, thereby ensuring the stability of the battery structure. The electrochemical potential of the positive and negative materials causes the electrolyte to work abnormally in two forms:

1. When the electrochemical potential of the negative electrode is higher than the lowest electron unoccupied energy level of the electrolyte, the electrons of the negative electrode will be captured by the electrolyte, and the electrolyte will be oxidized, and the reaction product will form a solid-liquid interface layer on the surface of the negative electrode material particles. The negative electrode may be damaged.

2. When the electrochemical potential of the positive electrode is lower than the highest electron-occupied energy level of the electrolyte, the electrons in the electrolyte will be captured by the positive electrode and oxidized by the electrolyte. The reaction product forms a solid-liquid interface layer on the surface of the positive electrode material particles, resulting in The positive electrode may be damaged.

However, this possibility of damage to the positive or negative electrode is due to the existence of the solid-liquid interface layer, which prevents the further movement of electrons between the electrolyte and the positive and negative electrodes, and instead protects the electrode material. That is to say, the lighter solid The liquid interface layer is protective. The premise of this protection is that the electrochemical potential of the positive and negative electrodes can slightly exceed the Eg interval, but not too much. For example, the reason why most of the current lithium ion battery anode materials use graphite is because the electrochemical potential of graphite related to Li/Li+ electrodes is about 4.2V, which is slightly beyond the Eg range (1V~4.5V), but because of its protective properties The solid-liquid interface layer prevents the electrolyte from being further reduced, thereby stopping the continued development of the polarization reaction. However, the 5V high-voltage cathode material exceeds the Eg range of the current commercial organic electrolyte by too much, so it is easily oxidized during the charge and discharge process. As the number of charge and discharge increases, the capacity decreases and the service life decreases.

Now I understand that the open circuit voltage of the lithium-ion battery was chosen to be 4.2V because the range of the electrolyte Eg of the existing commercial lithium-ion battery is 1V~4.5V. If the open circuit voltage is set to 4.5V, the output of the lithium-ion battery may be improved. Electricity, but also increases the risk of overcharging the battery, and the hazards of overcharging have been explained by a lot of data, so I won't say more here.



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