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Lithium ion reinforced inert anode for molten salt electrolysis system and preparation method thereof

An inert anode and molten salt electrolysis technology, which is applied in the field of metallurgy, can solve the problems of selective dissolution of metal phases, loss of protection, and destruction of oxide films, etc., and achieve the effects of long electrode life, lower prices, and more selectivity

Active Publication Date: 2021-03-16
WUHAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

These inert anode materials are limited by their respective defects. For example, ceramic inert anodes have problems such as poor electrical conductivity, poor thermal shock resistance, and inconvenient connection, and metal-ceramic inert anodes have problems such as selective dissolution of metal phases, which are difficult to put into industrial applications.
[0005] It is known that a layer of metal oxide film is formed on the surface of metal materials by pre-oxidation, which can effectively improve the corrosion resistance of metal inert anodes, but fluoride ions or chloride ions will still penetrate into the oxide film during the anodic polarization process. It reacts with the metal matrix to form metal fluoride or chloride, which makes the anode corrode and destroys the oxide film, making it lose its protective effect and causing the pre-oxidized metal inert anode to fail

Method used

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  • Lithium ion reinforced inert anode for molten salt electrolysis system and preparation method thereof
  • Lithium ion reinforced inert anode for molten salt electrolysis system and preparation method thereof

Examples

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Effect test

Embodiment 1

[0020] Using 310S stainless steel as the substrate, chromium oxide and lithium oxide (mass ratio of chromium oxide:lithium oxide = 83.6:16.4) were used as coating materials, and a layer of 10 μm thick LiCrO was prepared on the surface of the stainless steel substrate by plasma spraying. 2 (Cr 2 o 3 · Li 2 O) oxide film layer, obtain the chromium oxide inert anode that the lithium ion of matrix is ​​strengthened with stainless steel.

[0021] At 750°C, with CaCl 2 -NaCl-CaO molten salt (molar ratio CaCl 2 :NaCl:CaO=48:48:4%) as electrolyte, with TiO 2 As the cathode, the service behavior of the lithium ion-enhanced chromium oxide inert anode was tested by means of 2.9V constant cell voltage electrolysis. The results show that the inert anode in CaCl 2 After working in the -NaCl-CaO system for 1000 hours, it can still maintain stable oxygen evolution.

Embodiment 2

[0023] Using metal nickel as the substrate, a layer of nickel oxide is formed on the surface by air pre-oxidation, and then a layer of 12 μm is prepared on the surface of nickel oxide by ion implantation with lithium oxide as the raw material and ion beam energy of 200keV. thick lithiated nickel oxide (Li 0.15 Ni 1.05 o 2 ) layer to obtain a lithium-ion-enhanced nickel oxide inert anode based on nickel metal.

[0024] The structure of the inert anode is as follows figure 1 As shown, its cross-sectional optical photograph is shown as figure 2 shown. It can be seen from the figure that the outer layer is a dense lithiated nickel oxide layer with a thickness of 12 μm, and there is a cross distribution layer of metal oxide and metal with a thickness of 30 μm between the lithiated nickel oxide layer and the metal substrate.

[0025] At 650°C, with LiCl-Li 2 O molten salt (molar ratio LiCl:Li 2 O=98:2) was used as the electrolyte, and the spent fuel oxide was used as the cat...

Embodiment 3

[0027] Using nickel-cobalt alloy as the substrate, a layer of 30 μm thick LiCoO was prepared on the surface by electrochemical pre-oxidation method. 2 (Co 2 o 3 · Li 2 O) to obtain a lithium-ion-enhanced cobalt oxide inert anode based on a nickel-cobalt alloy.

[0028] At 850°C, with CaCl 2 -CaO molten salt (molar ratio CaCl 2 :CaO=98:2) as electrolyte, with CaWO 4 As the cathode, at 200mA / cm 2 The service behavior of the lithium-ion-enhanced cobalt oxide inert anode was tested by constant current electrolysis under the condition of anodic current density. The results show that the inert anode in CaCl 2 - After working in the CaO system for 100 hours, it can still maintain stable oxygen evolution.

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Abstract

The invention relates to a lithium ion enhanced inertia anode for a molten salt electrolysis system and a preparing method of the lithium ion enhanced inertia anode. The inertia anode is composed of iron, nickel, titanium and other metal matrixes, a lithium ion enhanced metal oxide film layer attached to the surface of the iron, the nickel, the titanium and other metal matrixes and the like. The film layer is of a single-layer structure or a multi-layer structure. The outermost layer of the film layer is a solid solution or compound formed through combination of metal oxide and lithium oxide.Through the unique structure and outer layer components of the inertia anode, the inertia anode can effectively prevent fluorine and chlorine ions from seeping into the metal matrixes, metal matrix erosion is avoided, accordingly, the service life of an electrode is long, the usage cost is low, and the excellent corrosion resisting capability, electron conductivity and oxygen evolution catalysis activity are shown; and the lithium ion enhanced inertia anode is used in the molten salt electrolysis system so that stable oxygen evolution can be achieved, and the application range of the molten salt electrolysis system is enlarged.

Description

technical field [0001] The invention relates to the technical field of metallurgy, in particular to a lithium-ion reinforced inert anode for a molten salt electrolysis system and a preparation method thereof. Background technique [0002] Although the reserve of aluminum in the earth's crust is higher than that of iron, the price of aluminum metal is much higher than that of iron metal. The main reason is that the cost of aluminum smelting process is too high. At present, the Hall-Elu method is widely used in industry to electrolyze metal aluminum with fluoride molten salt as electrolyte, and the use of consumable carbon anode is the key factor of its high cost. Firstly, this method consumes a large amount of high-quality carbon materials during the smelting process, and the material cost accounts for about 14%-22% of the aluminum production cost; secondly, the consumable anode needs to be replaced regularly, which increases labor costs and reduces production efficiency; thi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C25C3/12
Inventor 汪的华杜开发汪沛霖朱华肖巍毛旭辉甘复兴
Owner WUHAN UNIV
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