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A new type of silicon graphite double ion battery

At present, lithium battery has become an important energy conversion and storage device in portable electronic devices, electric vehicles, renewable energy systems and other fields. Although the energy density of commercial lithium battery has improved, its manufacturing cost is high and it is not easy to recycle. It is difficult to meet the performance requirements of portable electronic equipment, renewable and clean energy, power grid peak shaving and other fields for high energy density, low cost and environmental energy storage devices.

Recently, the research team of Tang Yongbing, a researcher at the Research Center of Functional Thin Film Materials of the Shenzhen Institute of Advanced Technology (hereinafter referred to as the Shenzhen Institute of Advanced Technology) of the Chinese Academy of Sciences, and the team of Zheng Zijian, a professor at the Hong Kong Polytechnic University, successfully developed a new type of silicon graphite double ion battery.

The single voltage drop of the battery is only 0.0015% during tens of thousands of bends, and the capacity retention rate is up to 97% after 2000 cycles at 10C magnification, which shows a good application prospect in the field of flexible energy storage. Tang Yongbing told China Science Daily. Relevant papers have been published in Advanced Materials recently.

Starting from aluminum-graphite dual-ion battery

In 2007, Tang Yongbing received his doctorate from the Institute of Metals of the Chinese Academy of Sciences, and then went to the City University of Hong Kong for visiting research at the recommendation of his mentor, Researcher Cheng Huiming (elected as an academician of the Chinese Academy of Sciences in 2013), and joined the Shenzhen Advanced Academy in September 2013.

Mr. Cheng believes that only by developing new efficient and low-cost energy storage devices and their key materials can we really promote the development of sodium, potassium and other non-lithium batteries. Tang Yongbing told reporters that under the guidance of Cheng Huiming, he began to lead his team in the research and development of new energy storage devices and materials. In March 2016, Tang Yongbing's team published the first research results on aluminum-graphite dual-ion batteries in Advanced Energy Materials.

As for the previously reported dual-ion battery, due to the use of graphite materials for both positive and negative electrodes, the vibrational density of graphite is low, and the specific capacity of graphite as positive and negative electrodes is not high, resulting in the low energy density of the dual-carbon battery. The research and development of dual-ion battery is slow.

In response, Tang Yongbing's team put forward the design idea of active material/fluid collection integration. He introduced that compared with the existing traditional graphite anode, aluminum and other alloyed metal anode has higher theoretical specific capacity and has advantages in improving energy density. In addition, aluminum has excellent conductivity and ductility, and is cheap and rich in reserves. Therefore, we have constructed a new type of aluminum-graphite dual-ion battery using aluminum foil of integrated design as both active material and conductive collector.

In the follow-up research work, in order to improve the stability of aluminum anode in the new battery, Tang Yongbing's team also carried out structural modification and interface control of aluminum anode, and developed three-dimensional porous aluminum/carbon anode, aluminum anode with hollow interface structure, carbon-coated nano-aluminum anode, active material/fluid collector/diaphragm integrated electrode, ultra-fast charge-discharge integrated flexible battery, etc.

We further expand this new integrated design idea to sodium, potassium and calcium based dual-ion battery systems that do not rely on limited lithium resources, and open up new ideas for the development of new high-efficiency and low-cost energy storage devices. Tang Yongbing said.

Joint research to improve energy density

At present, the important technical difficulty of the dual-ion battery is that its working voltage is high (more than 4.2 V), and the conventional carbonate electrolyte is easy to oxidize and decompose, resulting in the reduction of battery charging efficiency.

It is urgent to design and develop a high voltage electrolyte system to solve the gas generation phenomenon and improve the charging efficiency of the dual-ion battery. Tang Yongbing said that there are two important ways to improve its energy density. One is to develop high-capacity positive and negative electrode materials for dual-ion systems; The second is to develop a high concentration electrolyte system to reduce the amount of electrolyte and improve the energy density.

As far as the anode is concerned, silicon has high theoretical specific capacity and abundant reserves, which is an ideal anode material for improving the energy density of dual-ion batteries. Problems also arose. Tang Yongbing's team found that the serious volume expansion of silicon anode restricted its application in dual-ion batteries.

Although researchers have proposed various modification methods such as nano-meter, porous structure, composite structure, etc., most of them use metal materials as fluid collectors. The rigid interface contact between the silicon anode and the fluid collector causes the interface stress concentration, which leads to the interface cracking and even the peeling of active materials, making the cyclic performance difficult to meet the practical application requirements.

In this regard, Tang Yongbing's team proposed a flexible interface design strategy, and proposed to build silicon negative electrode on the surface of flexible polymer fabric, so as to effectively control the interface stress. He said: to achieve a good interface construction of silicon anode on the flexible polymer surface, an interface buffer layer with good conductivity should be designed between the two.

Zheng Zijian's team has a good working foundation in the field of flexible conductive fabrics, so the two sides carried out joint research. Zheng Zijian's team is responsible for the preparation and research of flexible conductive fabrics, so as to supply flexible conductive substrate materials for silicon anode; Tang Yongbing's team, based on flexible conductive fabric, carried out research work on the preparation of flexible silicon anode, battery assembly, in-situ stress and electrochemical performance testing.

In addition, at present, Tang Yongbing's team has also made a breakthrough in the research and development of high concentration electrolyte, and has developed a high concentration and high voltage electrolyte system, which is expected to further improve the energy density and stability of the dual-ion battery.

It is expected to be put into demonstration application as soon as possible

In recent years, Tang Yongbing's team has carried out a series of research work in the field of energy material chemistry, especially in the fields of new batteries, flexible batteries, and new cathode materials. In addition to the relevant research results listed above, the team also adopted the multi-ion hybrid strategy to improve the rate performance of sodium, potassium, calcium and other battery systems by introducing a small number of ions with high dynamic performance, providing a new solution for improving the dynamic performance of sodium, potassium, calcium and other new battery systems.

In addition, in order to develop new cathode materials with high efficiency, low cost and environmental protection, Tang Yongbing's team also took the lead in developing new cathode materials such as oxalate system and mixed polyanion system and studying their electrochemical reaction mechanism.

From the perspective of current development, the future application of dual-ion batteries is mainly in the field of energy storage. Tang Yongbing is optimistic about the future of dual-ion batteries, such as household energy storage, UPS, communication base stations, distributed energy storage systems and other fields. However, he cautioned that the specific application of dual-ion batteries in the future also depends on whether the technical maturity can meet the technical requirements of relevant fields.

At present, Tang Yongbing's team has cooperated with large local companies in Shenzhen to gradually carry out research on industrialization technology of dual-ion batteries, and has made expected progress, and has entered the pilot phase. With the continuous maturity of the dual-ion battery technology, he hopes that in the next three to five years, the product will gradually expand from the application demonstration of small energy storage systems to the application and promotion of other energy storage systems.

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