Lithium-rich antiperovskite sulfides, solid electrolyte materials including them, and applications thereof

Abstract

The invention discloses lithium-enriched anti-perovskite sulfides and a solid electrolyte material. The general formula of the lithium-enriched anti-perovskite sulfides is (LimMn)3-xS1-y(XaYb)1-z, wherein m is more than 0 and less than or equal to 1, n is more than or equal to 0 and less than to 0.5, (m+n) is less than or equal to 1, a is more than 0 and less than or equal to 1, b is more than or equal to 0 and less than 1, (a+b) is less than or equal to 1, x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5 and x=2y+z; M is H, Na, K, Rb, Mg, Ca, Sr, Ba, Y, La, Ti, Zr, Zn, B, Al, Ga, In, C, Si, Ge, P, S or Se; and X is Fe, Cl, Br or I, and Y is a negative ion. The solid electrolyte material has high ion conductivity and thermal stability and a wide working temperature range, and can be applied to lithium ion batteries, rechargeable metal lithium batteries, lithium liquid flow batteries or lithium ion capacitors.

Description

technical field [0001] The invention relates to the technical field of electrolyte materials, in particular to a lithium-rich antiperovskite sulfide, a solid electrolyte material comprising the same and applications thereof. Background technique [0002] Due to the shortage of oil resources and urgent environmental problems, "green environmental protection" has become the focus of people's increasing attention. The core of green environmental protection is "new energy", and the core of new energy is chemical power. It has been more than 200 years since the invention of chemical power sources. It can be traced back to the "Leyden bottle" in the 1840s and 1850s. It has experienced the initial "volt pile", Zn-Cu "Daniel battery", fuel cell, and voltaic battery. , to lead-acid batteries, and then to zinc-manganese dry batteries, nickel-cadmium batteries, nickel-iron batteries, nickel-zinc batteries, nickel-metal hydride batteries, until secondary lithium-ion batteries. Seconda...

AI Technical Summary

Problems solved by technology

However, polymers still have the following problems: (1) The mechanical strength is still poor; (2) The rate performance of the battery still cannot meet the actual needs, and the conductivity of the electrolyte needs to be further improved; (3) The preparation of gel-type polymer electrolytes The process is complex and has high requirements on the environment, which increases its preparation cost

However, this type of electrolyte still has the following problems: (1) the cost is high, and now ionic liquids are mostly synthesized in laboratory scale, the raw materials are expensive, and the finished products are more expensive; (2) the viscosity is relatively high, and the viscosity of ionic liquids at room temperature is that of water Dozens of times to hundreds of times, the ionic liquid is easy to adhere to the wall of the device in use, and there are problems such as slow diffusion; (3) the synthesis conditions are harsh, and the separation and purification of reaction products are difficult, which limits its large-scale production and application; (4) the ionic liquid The basic data of the liquid is lacking, and thousands of ionic liquids have been reported. However, even the ionic liquids that have been studied more often lack the detailed physical and chemical properties necessary for engineering design; (5) ionic liquids are non-volatile and toxic. , the most likely way for it to enter the environment is to enter the water system, and it is difficult to remove after entering the water system, so special work is needed to determine its impact on the water environment

Therefore, this material system has the following disadvantages: (1) The electrochemical window is narrow, and the working voltage is generally limited to 1.3V-2V, which is about half of the general non-aqueous lithium-ion battery, which also affects the energy density of the system battery; (2) There are protons in the aqueous electrolyte, and their activity is relatively high, which may be limited to the lithium ion deintercalation reaction; (3) it is not easy to form Li 2 CO 3 The passivation film (Solid-Electrolyte Interface, SEI), which is an important part, often affects the cycle life of the battery

Another disadvantage similar to perovskite-type solid electrolytes is that the material is also prone to react with metallic lithium

[0052] So far, there is no material, including pure phase, single phase and composite materials, that can meet all the following conditions at the same time, including: high ionic conductivity, negligible electronic conductivity, wide electrochemical window, and electrode materials. Chemical matching (including no reaction with the electrode, and lower impedance at the interface with the electrode material), mutual matching with the stress and strain of the electrode material during the process of deintercalating lithium and thermal expansion, low cost of raw materials and low environmental pollution, manufacturing Low cost and easy industrial production, stable materials in the preferred environment

Therefore, the current all-solid-state energy storage devices have not yet entered commercialization

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