Sulfide sodium ion solid electrolyte and preparation method thereof

A solid electrolyte and sodium ion technology, used in circuits, electrical components, secondary batteries, etc., can solve the problems of air sensitivity, solid electrolyte failure, and few types, reducing activation energy, improving electrochemical and chemical stability, The effect of improving ionic conductivity

Active Publication Date: 2019-06-14
HUAZHONG UNIV OF SCI & TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] In view of the defects of the prior art, the purpose of the present invention is to solve the problem that the existing sulfide solid electrolytes have few types of high ion conductivity, are very sensitive to air, and are prone to generate sulfide hydrogen when exposed to the air, which leads to the failure of solid electrolytes. question

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  • Sulfide sodium ion solid electrolyte and preparation method thereof
  • Sulfide sodium ion solid electrolyte and preparation method thereof
  • Sulfide sodium ion solid electrolyte and preparation method thereof

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preparation example Construction

[0032] According to another aspect of the present invention, a kind of preparation method of air stable sulfide sodium ion solid electrolyte is provided, comprising:

[0033] (1), the Na 2 S, MS, (M=Ge, Si), SnS 2 ,P 2 S,(N=P,Sb),Sb 2 S 3 ,S,NaX,(X=Cl,Br,I) according to Na 4-x-z [Sn 1-y m y ]N x S 4-z x z The mol ratio is uniformly mixed to obtain mixed raw materials;

[0034] (2) Perform solid-phase synthesis of the mixed raw materials under anaerobic conditions at 400°C to 650°C to obtain Na 4-x-z [Sn 1- y m y ]N x S 4-z x z , whose crystal structure satisfies I4 1 / acd space group; anaerobic conditions are vacuum conditions less than 100Pa.

[0035] Wherein, M is at least one of Si or Ge, N is at least one of P or Sb, X is at least one of Cl, Br, and I; 0≤x≤0.6, 0.30≤y≤0.35, 0 ≤ z ≤ 0.1.

[0036] Further, the solid-phase synthesis time is 8h-24h. High temperature is beneficial to the preparation reaction of sulfide solid electrolytes, increases the crys...

Embodiment 1

[0050] Na in an argon-protected glove box 2 S, P 2 S 5 , SnS 2 、SiS 2 Take Na 3.7 [Sn 0.67 Si 0.33 ] 0.7 P 0.3 S 4 The mol ratio is weighed and mixed as raw materials;

[0051] Put the raw materials and zirconia balls into a zirconia-substrated ball mill tank with a capacity, seal the container, perform ball mill mixing at a speed of 360r / min, and obtain a mixed powder after 18 hours;

[0052]Put the mixed powder in the glove box, take it out, and form it under 150MPa pressure in a powder tablet press, put it into a glass / quartz tube, evacuate it until the vacuum degree is less than 100Pa, seal it, and put it into a muffle furnace. The temperature rise rate of the muffle furnace is 100°C / hour, and then the solid phase reaction is carried out at 550°C for 24 hours, and the temperature is naturally cooled to obtain the product Na 4-x [Sn 1-y m y ]N x S 4 , the product in this example is Na 3.7 [Sn 0.67 Si 0.33 ] 0.7 P 0.3 S 4 .

[0053] In the glove box, th...

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Abstract

The invention discloses a sulfide sodium ion solid electrolyte and a preparation method thereof. A chemical formula of the sulfide sodium ion solid electrolyte is Na4-x-z[Sn1-yMy]NxS4-zXz, wherein M is at least one of Si and Ge, N is at least one of P and Sb, and X is at least one of Cl, Br and I; and x is greater than or equal to 0 and less than or equal to 0.6, and y is greater than or equal to0 and less than or equal to 0.35. A crystal structure of the sulfide sodium ion solid electrolyte is provided with an I41/acd space group; isolated [Sn/M]S4 and [Sn/M/N]S4 tetrahedrons form a framework; and sodium ions fill six non-full crystal positions. When x is equal to 0, the ionic conductivity is greater than 10<-5> S/cm; and when x is greater than 0 and less than or equal to 0.6, the ionicconductivity ranges from 10<-4> S/cm to 10<-3> S/cm. A solid electrolyte material provided by the invention has high ionic conductivity and high air stability; raw materials used in material synthesisare wide in source and relatively low in price; and a certain advantage exists in use cost.

Description

technical field [0001] The invention relates to the field of all-solid-state sodium-ion batteries, and more specifically, to a sulfide sodium-ion solid electrolyte and a preparation method thereof. Background technique [0002] Lithium-based batteries have developed rapidly since their discovery in 1970. Among them, lithium-ion batteries, which were first successfully developed by snoy in 1990, have been widely used in portable electronic devices such as mobile phones and computers due to their advantages such as high energy density, long cycle life, high working voltage, and no memory effect. With the demand for lithium-ion batteries in power vehicles and energy storage systems, the limitation of lithium resources in the earth's crust has put them to the test in terms of cost and popularization, and the development of new secondary batteries has become an inevitable trend. [0003] Sodium and lithium are in the same main group and have similar physical and chemical propert...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/0562H01M10/054
CPCY02E60/10
Inventor 谢佳贾欢欢孙玉龙
Owner HUAZHONG UNIV OF SCI & TECH
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