With the growth of energy demand and the improvement of environmental protection requirements, the markets demand for high-efficiency rechargeable battery energy storage systems is increasingly urgent, especially in solar energy and wind energyWait for the field of renewable energy storage.Lithium ion batteries (LIBS) are considered one of the best candidates due to their high working voltage, high -rate energy, portability, good low temperature performance and long life.However, problems such as electrolyte leakage, fire and explosion caused by liquid electrolytes have limited its long -term development.Therefore, using inorganic solid -state electrolytes (SSE) to replace organic liquid state electrolytes, the assembly of solid -state lithium -ion battery (SSLBS) with high safety, high recycling and widely used range has become the main research direction.
Liu Sijie, Shenzhen Tsinghua University Research Institute, and Professor Kristiaan NEYTS of Hong Kong University of Science and Technology, Advanced Energy Materials summarized the sulfide/polymer composite solid electrolyte and itsApplication of full solid lithium ion battery.In order to achieve the high -energy density of SSLB, SSE must meet the conditions such as thin and compact electrolytes, compacking, electrolytes and stable electrode structures, and continuous conduction channel networks.A single type of SSE cannot meet all conditions, so it has an advantage in combining with two or three SSE advantages.
The preparation method of sulfide-polymer composite SSES includes dry and wet method.The dry method is to mix the vulcosine electrolyte powder with the organic electrolyte powder, without adding any liquid additives, and then perform high -temperature solid -state reactions, mechanical chemistry methods and melting quenching methods.The wet method is an electrolyte that uses organic solvents or room temperature as a liquid polymer, and then the electrolyte and polymer electrolyte of vulcanization and polymers are mixed in the liquid medium for follow -up experiments.The classification of sulfide-organic matter composite SSES is based on the ratio of sulfide to organic matter. There are four types: "sulfide-organic matter", "instant", "sulfide in organic matter" and "layer by layer".
Figure 1 The performance attributes of SSES and the radar chart of the classification diagram
Figure 2 Sulfide-Preparation Method of Organic Composite SSES
Table 1.Summary table
Figure 3 sulfide-schematic diagram of organic matter composite SSE
Figure 4 (A) Sulicon/SBR composite material for sulfen/sBR composite materials prepared by dry method and (B) wet method;) 7.5 mg · cm-2 methylistide SEPM method SEM; (E) the amplification interface of polytamide and electrolyte; (f) section; (g) C-k energy spectrum; (h) section p-k; (i)Cross section s-k.
Figure 5 (a) li7p3s11 after adding the color changes of different solvents;XRD diagram dispersed in CAN, DCM, TOL, and Xyl.
Figure 6 (A) The theory and geometry of SEPM membrane consisting of 80%75LI2S · 25P2S5 and 20%polyamide; (B) Linear streaming measurement of composite electrolyte.The frequency dependencies of the storage modulus and loss modulus of the composite electrolyte measured at 30 ° C; (C) the pipe band test of 2.5% HNBR;The stress-strain curve of the PEO content electrolyte particles; (f) the stress-strain curve of different preparation of the electrolyte;
Figure 7 (A) The contact angle of the contact angle of the contact angle of the polymer;b) It is used to measure the installation of H2S gas during hydrolysis of 100mg li7p3s11 in the air; (C) The fixed volume air is exposed to 100 mg naked li7p3s11 and 100 mg hydrophphic SEBS polymer composite material.)-(E) LI7P3S11 naked state before and after soaking;
Figure 8 (a) SS/LPS-PT-24/LI battery CV curve; (B) Lithium/LPS/Stainless Steel Battery and Lithium LI/LPS-AEO-LICLO4/Stainless Steel battery CV; (C) The electrochemical stable window with a scanning rate of 0.25 mv/s and the temperature of the LSV curve when the temperature is 60 ° C; (D) 80 ° CThe LSV and CV curves of polymer electrolyte; (E) The electrochemical stable window of the LSV curve at 40 ° C; (f) the LSV curve of each electrolyte at room temperature.
Figure 9 (A) Symmetrical li/li6PS5Cl-X%PEO/LI battery at a voltage distribution when current density is 0.3 mA/cm2Figure; (B) The effect of LPS and PGMA-LPS 50%on the electrochemical performance of the symmetrical lithium battery; (C) the current density is 0.5 mA · CM− 2 time li | PGMA-LPS 50%| LI symmetrical batterys long-term cycle performance; (((((((((((d) LI+plating/peeling potential of lithium symmetrical battery.
The development of sulfide SSE is hindered by the easy interface reaction of the negative electrode and the positive electrode.In SSB, sulfide SSE is a lithium ion conductor, and the oxide cathode is the most commonly used commercial cathode material.This shows that there is a chemical potential difference between the oxide cathode and sulfide SSE. When the lithium ion is tightly exposed, they move from sulfide SSE to the cathode to achieve balance and form a spatial charge layer.It is important to understand and improve the interface of cathode/sulfide SSE to improve electrochemical performance.
Figure 10 (a) schematic diagram of the dual electrolyte layer battery;; (D)-(e) cold pressure of cathode electrolyte.
Organic substances are used as mechanical enhancement and LI+conductivity. At the same time, it is important to choose appropriate organic substances as adhesives.Inada et al. Compared the composite SSES properties of two sulfide electrolytes and different organic adhesives, and found that organic silicon composite materials have the highest conductivity.The higher molecular weight adhesive can enhance the structural integrity of the SSE film, but they can also cause the crystal resistance to increase and decrease the critical current density.
Figure 11 (a) liquid S-LI battery unit; (b) traditional solid S-LI battery monomer; (C) solid stateThe structure of the S-LI battery single 135; (D)-(E) The circulation performance of PEO-1% LSPS electrolytes and PEO/Litfsi electrolytes on lithium batteries at 60 ° C.
sulfide-Organic composite SSES has obtained the advantages of the lithium battery in solid lithium batteries due to its high ion conductivity, wide-electrical chemical window, good interface contact and effectively suppressing lithium branches crystals.Wide application.Although the vulcab-organic composite SSESs conductivity at high temperature or room temperature can reach 10-3 ~ 10-4s · CM-1, it is still lower than the conductivity of liquid electrolyte, which is not enough to meet many practical applications.Therefore, the conductivity of sulfides-organic matter composite SSES should be further improved.The enhancement mechanism of the vulcosion-organic composite SSES system is not completely clear, and further research and enhancement mechanisms need to be further studied.
sulfide-the synthesis process of organic matter composite SSES needs to be further optimized, which is an important step towards practical and large-scale SSLBS.This optimization is critical, and there are several reasons.First of all, scalable synthesis methods are critical to consistent quality and performance in large -scale production, because current technology can usually only produce limited number of high -quality composite materials.In addition, improving these processes can reduce production costs and make SSLBS more competitive with traditional lithium -ion batteries.Improve SSESs electrochemical performance to a large extent on their micro structure, ionic conductivity and mechanical properties.Optimized synthesis can bring better ion transmission and better cycle stability.In addition, the improvement of interface compatibility between electrolytes and electrodes can minimize the side effects of resistance and performance.Optimization strategies include controlling synthetic conditions, choosing a proper preface, implementing synthetic processing, and using automated and high -throughput technologies.By paying attention to these fields, we can promote the development of sulfide-organic composite SSES and integrate it into a practical large-scale SSLBS.
Deputy Director and Associate Researcher of the low -carbon energy and energy -saving technology key laboratory of the Shenzhen Tsinghua University Research Institute, assistant researcher (cooperation) Liu Sijie of the Hong Kong University of Science and Technology as the first author and communication author.Other main contributors are the director of the National Key Laboratory of advanced display and optoelectronics technology, Kristiaan NEYTS, a professor at the Hong Kong University of Science and Technology; Zhou Le, assistant researcher at the Hong Kong University of Science and Technology;Studies have been funded by Shenzhen Sustainable Development Project.
Thesis link:
https://onlinelibrary.wiley.com/doi/10.1002/aenm.202403602
