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Lithium-ion batteries can be said to be the most mature and widely used new energy sources in the world at present, such as portable electronic products like mobile phones and computers, electric vehicles, electric tools, and energy storage projects. Especially the current Chinese government and other countries are investing to support the development of new energy vehicles and power battery industries. Looking ahead, the lithium industry has a long way to go, such as the development of high energy density systems. The problems of further reduction of cost, the resources recovery, and the utilization are in front of us.
This article will mainly explain what is a lithium battery, then introduce the current situation and future development of lithium-ion battery materials.
| III. Distinction Between Lithium-ion Battery & Polymer Lithium Battery |
| IV. Types and Characteristics of Material Used in Lithium Batteries |
"Lithium battery" is a kind of battery that takes lithium metal or lithium alloy as negative electrode material and using a non-aqueous electrolyte solution. In 1912, lithium-metal batteries were first proposed and studied by Gilbert N. Lewis. In the 1970s, M.S. Whittingham proposed and began to study lithium-ion batteries.
Because of the active chemical characteristics of lithium metal, the environmental requirements of the processing, preservation, and use of lithium metal are very high. Therefore, lithium batteries have not been applied for a long time. With the development of science and technology, lithium batteries have become the mainstream now.
Lithium batteries can be roughly divided into two categories: lithium metal batteries and lithium-ion batteries. Lithium-ion batteries do not contain metallic lithium and are rechargeable. The fifth generation of rechargeable lithium metal batteries was born in 1996. Its safety, specific capacity, self-discharge rate, and the ratio of performance to price are superior to those of lithium-ion batteries, which are now produced by a few companies in only a few countries due to their own high-tech constraints.
Li-ion batteries are secondary battery system in which two different kinds of lithium intercalated compounds that can be inserted and removed as positive and negative electrodes respectively. When charged, lithium-ions are removed from the lattice of cathode materials. After the electrolyte is inserted into the lattice of the anode material, the negative electrode is rich in lithium, and the positive electrode is poor in lithium.
When discharged, the lithium-ion is removed from the lattice of the anode material, and then inserted into the lattice of the positive electrode material after the electrolyte, so that the positive electrode material is extremely rich in lithium while the negative electrode is poor in lithium. In this way, the difference between the potential of the cathode material and the lithium-ion when inserted and removed from the lithium metal is the working voltage of the battery.
Li-ion battery is a new generation of green high-energy battery with excellent performance and has become one of the key points in the development of high-tech.
Li-ion battery has the following characteristics: high voltage, high capacity, low consumption, no memory effect, no pollution, small volume, small internal resistance, less self-discharge, and more cycle times.
Because of the above characteristics, the lithium-ion battery has been applied to many civil and military fields, such as mobile phones, notebooks computers, cameras, digital cameras, and so on.
The charging and discharging process of lithium battery is realized by the removal and embedding of lithium-ion in the positive and negative electrode of the battery. The reaction equation of the lithium-ion battery with iron phosphate liquid as an example is as follows:
Charging:

Discharging:

The electrode reaction of Li/PEO-LiClO4/Pan polymer lithium-ion battery is as follows:
Positive electrode reaction:

Negative electrode reaction:

The working schematic diagram of lithium battery:

Schematic-of-the-lithium-ion-battery-working-principle
1. The positive electrode structure:
LiMn2O4( lithium manganate ) + Conductive agent (acetylene black) + adhesive(PVDF) + Collector negative ( aluminium foil )electrode
2. The negative electrode structure:
Graphite+ Conductive agent (acetylene black) + adhesive(PVDF) + Collector negative ( copper foil )electrode
3. Charging process:
The battery is charged by the power supply, and the electron e on the positive electrode runs from the external circuit to the negative electrode. Positive lithium-ion Li+ "jumps" from the positive electrode to the electrolyte, "climb" through the winding hole in the diaphragm, then "swim" to the negative electrode and combine with the electron.
The reaction on the positive electrode is: LiMn2O4 ==Li1-xMn2O4+Xli++Xe (electron).
The reaction on the negative electrode is: 6C+XLi+Xe==LixC6
4. Discharging process
When the battery discharges, the electron e on the negative electrode runs from the external circuit to the positive electrode. Positive lithium-ion Li+ "jumps" from the negative electrode to the electrolyte, "climb" through the winding hole in the diaphragm, then "swim" to the positive electrode and combine with the electron.
The reaction on the positive electrode is: Li1-xMn2O4+xli++xe (electron) ==LiMn2O4
The reaction on the negative electrode is: LixC6 == 6C+xLi+xe
As the following table: Electrolyte for Polymer Lithium Battery
| Polymer | Electrolyte | |
| Pure solid polymer electrolyte | Gel polymer electrolyte | |
| PAn, PPY, PA, PPP | PEO, PPO | PAN,PMMA,PVdF |
As the following diagram: Different electrolytes are the main differences between lithium-ion batteries and polymer lithium batteries.

Diagram
(This is a tutorial on the Lithium Battery Explorer provides an overview of Li-ion battery technology and the properties that are relevant to battery researchers.)
1.Lithium manganate (LMO)
LMO, as a kind of lithium battery material with a long history, has high safety, especially strong resistance to overcharge, which is a prominent advantage.
Because of the good structural stability of lithium manganate, the amount of cathode material does not have to exceed the negative electrode in the design of the electric core.
In this way, the number of active lithium ions in the whole system is small, and after the negative electrode is filled, there will not be too many lithium ions in the positive electrode. Even if overcharge occurs, there will not be a large number of lithium ions deposited in the negative electrode to form crystallization. Therefore, the overcharge resistance of lithium manganate is the best in common materials.
In addition, its material price is low, and the production process requirements are relatively low. It is a relatively early widely used cathode material.
But it also has obvious defects. The elevated temperature property of spinel lithium manganese oxide is poor. The existence of oxygen defect makes the core prone to capacity decay at the high voltage stage, at the same time, the cycle use at high temperature would cause a similar capacity decay. The reason is that the trivalent manganese ion which causes the disproportionation effect. The main way to prevent high-temperature attenuation is to reduce the trivalent manganese.
Lithium manganese, limited by its high-temperature performance, is generally not used in high-power or high-temperature environments, such as high-speed passenger vehicles, plug-in cars, and so on. But for electric buses, local logistics vehicles, and so on, lithium manganese is completely competent.
2. Lithium iron phosphate (LFP)
The advantages of lithium iron phosphate are mainly reflected in its safety and cycle life. The main determinants are the olivine structure of lithium iron phosphate, which, on the one hand, leads to the lower ion diffusion capacity of lithium iron phosphate. On the other hand, it also has good high-temperature stability and good cycle performance.
The disadvantages of lithium iron phosphate are also obvious, such as low energy density, poor consistency, and poor low-temperature performance.
a) The low energy density is determined by the chemical properties of the material itself. A lithium iron phosphate macro-molecule can accommodate only one lithium-ion.
b)The consistency, especially poor batch stability, is related to not only the level of production management but also its own chemical properties. Lithium iron phosphate is one of the more difficult materials for the preparation of cathode materials for lithium-ion batteries.
The difficulty of consistency and uniformity in this chemical reaction raises another problem at the same time: The impurity of iron and iron in the lithium iron phosphate material always exists, which brings hidden trouble to the battery.
Lithium iron phosphate battery, because of its high safety, although The energy density part affects its range of use., but it is still the main power lithium battery variety of electric vehicle in our country at present, especially buses involving the safety of a large number of people, the national police enforce the use of lithium iron phosphate batteries.
3.Ternary lithium
The ternary lithium cathode material synthesizes the advantages of LiCoO2、LiNiO2 and LiMnO2 and forms a synergistic effect within the same core. It combines three requirements of stability and activity of material structure and lower cost, which is one of the three main cathode materials with the highest energy density. The low-temperature performance is also obviously better than the lithium iron phosphate battery.
The higher the content of Ni in the three elements, the higher the energy density of the core and the lower the safety of the core will be. In practical application, the proportion relation of three kinds of materials in the electric core has been changing with the passage of time. The pursuit of energy density is higher and higher, so the proportion of Ni is higher and higher.
The most mentioned disadvantage of ternary material is safety. During the process of thermal runaway, the side reaction product contains a lot of gas, which greatly improves the risk of accident and the ability to spread.
Secondly, the cycle life of ternary materials is also a bottleneck, which has not reached the level of lithium iron phosphate. Last but not least, due to the special microstructure of ternary materials, it is not suitable for high-pressure compaction operation, thus the popular way to increase the energy density is not applicable to it.
The market share of ternary materials is gradually expanding, mainly driven by the pursuit of vehicle range. To catch up with or even surpass that of fuel vehicles, electric vehicles must have as much power as possible in a limited space.
This makes energy density particularly important. The improvement of the safety performance of the battery itself and the improvement of system monitoring and handling accident capability will also promote the expansion of the lithium ternary battery market.
1. Lithium Iron Phosphate is the most suitable cathode material for Power Battery
After introducing the Types and characteristics of Lithium batteries above, now we will discuss about the most suitable cathode material for power supply.
Since 1996, when the Japanese NTT first exposed lithium iron phosphate cathode materials of olivine structure, John.B.Goodenough professor at Texas University also reported the characteristics of reversible intercalation and removal of lithium from LiFePO4 in 1997.
Since then, lithium iron phosphate has gradually become one of the low-cost, multi-element, and environmentally friendly cathode materials. Compared with traditional cathode materials, spinel LiMn2O4 of spinel structure and layered LiCoO2, the LiMPO4 of olivine structure is extremely stable.
The bond with oxygen is very strong, it will not explode because of the short circuit, the capacity is up to 170 mAh / g, the raw material is more extensive and the price is lower. Because of the similar structure of LiFePO4 and FePO4, the crystal structure of LiFePO4 has almost no rearrangement after the release/embedding of lithium-ion.
Therefore, LiFePO4 has better cycling performance, lithium-ion can enter and exit freely and can charge and discharge more than 1,000 times. It is also reported that lithium iron phosphate can be modified more than 10,000 times.
According to the following picture: Performance comparison of Lithium batteries with different cathode Materials.

Performance comparison
Lithium iron phosphate is the most ideal cathode material at present. In comparison, the biggest problem of LiCoO is that it is easy to explode at a low temperature of 150C, and its cost is high (cobalt price is about 500,000 yuan/ton, and the price of LiCoO containing 60% cobalt will be over 400,000 yuan/ton). Also, it has a short cycle life.
The safety of lithium manganese oxide is much better than that of lithium cobaltate, but the cycle life in a high-temperature environment is even worse than that in a high-temperature environment(500 times).
With the advantages of high discharge power, low cost (about 18.3 million yuan/ton), rapid charging and long cycle life of more than 1000 times, the high stability of high temperature and high heat environment, and the good safety performance, lithium iron phosphate is the most ideal lithium cathode material for power vehicles.
At present, though the lithium iron phosphate battery is developing rapidly in China, there are several problems, including patent hidden trouble, low conductivity, and low capacitance, poor low-temperature performance, and low yield.
Polymer Lithium Battery: one of the Future Development directions
In addition to pure solid or gel polymer electrolytes, the principle and charge-discharge process of polymer lithium-ion batteries are consistent with those of liquid lithium-ion batteries.
Polymer lithium battery features include plastic flexible, more stable, safer, and less flammable, longer cycle life, higher energy density, high volume utilization(10-20% higher than lithium-ion batteries), no need to use traditional diaphragm materials, and easier for large scale production.
Polymer electrolyte is a kind of functional polymer material with ionic conductivity in solid-state which is formed by complexation of strong polar polymer and metal salt through acid-base reaction. Pure solid-state electrolyte dissolves lithium salts such as LiPF6, LiClO4, and LiBF4 in polymer bulk such as PEO and PPO as solid solvents. Gel electrolytes are electrolytes in a gel state by mixing more liquid solvents with polymer bulk.
Because there is no liquid flowing in the electrolyte, there is no leakage of the battery, so the problems such as burning and explosives are avoided. In order to reduce the thickness of the battery, a polymer lithium battery is usually packaged with aluminum plastic film with a thickness of only 0.1 mm, so it has a higher specific capacity than the ordinary lithium-ion battery.
Lithium batteries feature primary cell construction. This means that they are single-use—or non-rechargeable. Ion batteries, on the other hand, feature secondary cell construction. This means that they can be recharged and used over and over again.
Despite its overall advantages, lithium-ion has its drawbacks. It is fragile and requires a protection circuit to maintain safe operation. Built into each pack, the protection circuit limits the peak voltage of each cell during charge and prevents the cell voltage from dropping too low on discharge.
Li-ion batteries are able to be recharged hundreds of times and are more stable. They tend to have a higher energy density, voltage capacity and lower self-discharge rate than other rechargeable batteries. This makes for better power efficiency as a single cell has longer charge retention than other battery types.
about two to three years. The typical estimated life of a Lithium-Ion battery is about two to three years or 300 to 500 charge cycles, whichever occurs first. One charge cycle is a period of use from fully charged, to fully discharged, and fully recharged again.
Lithium-ion batteries should not be frequently fully discharged and recharged ("deep-cycled"). You may need to discharge it fully occasionally to recalibrate the capacitiy measuring electronics in the accumulator. Every 30 cycles or so should be enough.
If the battery is dead or at the end of life, then it won't take charge anymore. If the battery is dead or at the end of life, the battery will swell a bit. The battery starts to heat up very quickly is also one of the indication that your battery is at the end of life.
Zinc-ion: A competitive alternative to lithium-ion for stationary energy storage. Lithium-ion batteries are the leading battery technology for both electric vehicles (EVs) and the renewable energy industry.
Lithium Ion batteries "go bad" when they are stored in discharged state. It is all about battery voltage. If voltage is too low - undesireable chemical reactions will happen and battery will degrade. If battery is not empty and not used for long time - it will be fine.
At temperatures above +60°C the Li-ion battery loses capacity constantly and thus performance capability.
3.4V. The voltage starts at 4.2 maximum and quickly drops down to about 3.7V for the majority of the battery life. Once you hit 3.4V the battery is dead and at 3.0V the cutoff circuitry disconnects the battery (more on that later. You may also run across 4.1V/3.6V batteries.
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