How far is the industrialization of solid-state batteries?
Safety is always a sword at the top of the lithium battery. All major enterprises, including research institutes and universities in the lithium battery industry chain, have been spared no effort to solve this "difficult problem". Among them, research and production of all-solid-state lithium batteries is a new idea and new method proposed by the industry.
Chen Liquan, an academician of the Chinese Academy of Engineering, said: "In 2014, I proposed to strive for the industrialization of (all-solid-state lithium battery) for five years. All-solid-state batteries are a rare opportunity for us to achieve our leadership. China began research 40 years ago, and we have a foundation."
The high-tech lithium power grid has learned that the current solid-state lithium battery is still in the research and development stage, and some enterprises in China have already carried out technical research. What stage does the all-solid-state lithium battery development process reach? How far is it from the industrialization process? This article will help readers to more clearly understand the all-solid-state lithium battery and its industrialization process.
Technical principle
All solid-state lithium batteries, that is, battery units, including lithium-ion secondary batteries with positive and negative electrodes and electrolytes all using solid materials, have been developed since the 1950s, and their working principle is in line with the principle of liquid electrolyte lithium-ion batteries. .
At present, according to the electrolyte classification, all-solid lithium batteries mainly include two categories: one is an all-solid lithium battery composed of an organic polymer electrolyte, which is called a polymer all-solid lithium battery; the other is a lithium-ion battery composed of an inorganic solid electrolyte. It is called inorganic all-solid lithium battery, mainly including oxides and sulfides.
In terms of construction, an all-solid lithium battery is simpler than a conventional lithium ion battery, and the solid electrolyte acts as a separator in addition to conducting lithium ions. Therefore, in the all-solid lithium battery, the electrolyte, the electrolyte salt, the separator and the adhesive polyvinylidene fluoride are not required to be used, which greatly simplifies the construction steps of the battery.
The polymer all-solid lithium battery has the advantages of high safety, can not only be prepared into various shapes, but also is relatively easy to prepare by roll-to-roll; inorganic solid electrolyte materials used in inorganic all-solid lithium batteries have high mechanical strength, Contains flammable, volatile components, no leakage, and good temperature resistance.
At the same time, inorganic materials are easy to realize large-scale preparation to meet the needs of large-sized batteries, and can also be prepared into thin films, which are easy to miniaturize lithium batteries. The thin film inorganic solid electrolyte lithium batteries assembled by inorganic materials have an extremely long storage life and cycle performance. .
What are the obstacles to industrialization?
Dr. Li Wei, chief technology officer of Jiangsu Qingtao Energy Technology Co., Ltd. (hereinafter referred to as “Qingtao Energyâ€), said that there are two main problems that currently plague the industrialization of all solid-state batteries: First, the ionic conductivity of solid electrolytes at room temperature. Not high; second, the interface impedance between the solid electrolyte and the positive and negative electrodes is relatively large.
These problems are present in polymers, oxides, and sulfide solid electrolytes currently in use. Specifically, the polymer has insufficient temperature resistance and the interface problem is slightly better, but the electrochemical window is narrow, the stability is poor, and the ionic conductivity is low; the oxide interface resistance is relatively large, and the ionic conductivity is also low; Sulfide ions have a higher electrical conductivity, but the interface ion transport performance is not good, and the stability of the material itself is not good.
Previously, there were media reports that the French company Bollore had already launched 3,500 city rental cars in London, England. It is understood that these rental cars are all electric vehicles using all-solid lithium batteries. The battery system is Li/PEO/LFP, the battery pack weight is 300KG, the energy density is 100wh/kg, and the water output capacity is 1300 cycles. Reached 80%. Industry experts believe that due to the narrow temperature range of solid electrolytes, Bollore's electric vehicle needs a heating component to heat the battery to 80 degrees Celsius to start. After the temperature rises, the conductivity becomes better.
Unlike the usual direct engine car, the process of raising the battery temperature is not only cumbersome, but also consumes energy, which leads to a significant decrease in the effective energy density of the entire package of the battery pack. At the same time, due to the poor power performance of the polymer solid-state battery, it needs to be used with a high-power supercapacitor in actual use.
The more obvious defect is that the PEO-based polymer solid electrolyte has a narrow electrochemical stability window, generally below 4V, and the corresponding cathode material can only be selected as LFP, and its overall energy density is difficult to reach 300Wh/kg.
Positive business layout
Although solid-state electrolytes used in all-solid-state batteries face many problems, this does not affect the industry's confidence in industrializing all-solid-state batteries. In response to the difficulties, many companies have launched technology research and development models.
Sulfide solid electrolyte is an important research and development direction in the Ningde era. For a sulfur-based all solid state battery, there is a problem of interfacial reaction between the positive electrode interface and the negative electrode interface. For the positive electrode interface, the positive electrode coating modification method can be used, and the negative electrode interface can form a stable buffer layer on the surface of the lithium metal.
In practical applications, sulfides also have ionic conductive contact problems. The stability of contact with air and water is poor. When exposed to water, not only will the highly toxic hydrogen sulfide gas be released, but the smell is very odorous, if in the process of using the car. If this problem arises, people will not be able to bear it.
Dr. Liang Chengdu of Ningde Times New Energy Technology Co., Ltd. said that Ningde era improved the overall ionic conductivity of the battery system by using hot pressing to improve the interface contact, and improved the sulfide material to improve its stability. Further.
However, the manufacturing aspect is a big challenge. The production process and process are completely different from the traditional lithium-ion battery. The Ningde era has carried out a series of material research and process development, and has been active in the industrialization of solid-state batteries. layout.
“All roads lead to Romeâ€, each company will have its own choice in the development of electrolyte selection path for all solid-state lithium batteries. Li Wei said that the technical route of Qingtao Energy is a composite material made of polymer and oxide. Although it can partially avoid the common problem of solid electrolyte, it still needs improvement, and the corresponding positive and negative electrodes also need to be changed.
At present, there is a consensus in the industry that it is still too early to talk about the industrialization of all-solid-state lithium batteries, because the materials, equipment and processes they are supporting are still immature, and even the equipment produced is not. According to Li Wei, the purpose of the establishment of Qingtao Energy was to produce all-solid-state lithium batteries. The supporting equipment company’s nuclear name has been completed and is in the process of industrial and commercial registration.
According to analysts from the Institute of Advanced Research Institute of Lithium and Electricity (GGII), the theoretical value of energy density of all solid-state batteries is very high, but the current engineering capacity is not enough, the whole package is 100-200 wh / kg, there is still much room for improvement. To achieve large-scale industrialization of all-solid-state batteries, technological breakthroughs are critical, and materials, processes, and equipment need to be upgraded accordingly.
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