Magnesium ion battery negative electrode material MaEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6 and preparation method

A technology for magnesium ion batteries and negative electrode materials, applied in battery electrodes, circuits, electrical components, etc., can solve the problems of complex parent action mechanism, grain growth and agglomeration, shortening the diffusion time of magnesium ions, etc. The rate of redox reaction, the effect of improving the conductivity of magnesium ions, and reducing the resistance of electron transfer

Inactive Publication Date: 2017-10-24
宁波吉电鑫新材料科技有限公司
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  • Abstract
  • Description
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Problems solved by technology

However, it is still very difficult to take into account the rate performance and cycle capacity retention performance of the material.
The main reasons are as follows: 1. When the redox reaction occurs, the electrode material should have fast lithium ion intercalation and deintercalation and electronic conduction, that is, it should have good electronic conductivity and ion conductivity at the same time. Many negative electrode materials have high However, it is an electronic insulator, and some negative electrode materials are good electronic conductors, but the diffusion capacity of lithium ions is weak, which greatly increases the polarization of the battery; 2. Many electrode materials are intercalated with lithium ions and There is a large volume change during the deintercalation process, resulting in the breakage of electrode material particles and the loss of effective electrode materials during the cycle. The large volume change also brings about the transformation of the material lattice during the charging and discharging process to produce a second phase. seriously affect the performance of the battery
3. Lithium battery negative electrode material with conversion reaction mechanism, the electronic insulation of the reaction product lithium compound seriously affects the reversibility of the material
ABOs 3 When the alloy reaction is carried out, the oxide can react with two metals, which may produce alloy solid solutions in various phases. Due to the interaction of bimetals, it may also produce electrochemical characteristics that are completely different from those of single metals. Therefore, ABOs 3 Type oxide has the p

Method used

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  • Magnesium ion battery negative electrode material MaEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6 and preparation method

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Experimental program
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Effect test

Embodiment 1

[0021] Embodiment 1: Calcium nitrate tetrahydrate, magnesium nitrate hexahydrate, hafnium oxide, europium nitrate hexahydrate, copper nitrate trihydrate, zinc nitrate hexahydrate, ammonium tungstate hydrate according to the stoichiometric formula MgEu 0.7 Ca 0.3 f 0.8 Cu 0.1 Zn 0.1 WO 6 Put it into a ball mill, the mass ratio of the ball mill and the material is 20:1, and ball mill at a speed of 400 rpm for 20 hours. The ball-milled material is heated up to 900°C at a rate of 10°C / min in a tube furnace, and then a DC voltage of 900V is applied to both ends of the tube furnace. Cool the furnace to 30°C; grind the cooled material in a mortar for 12 minutes, and immerse it in a saturated solution of lithium metaborate at a constant temperature of 30°C under constant stirring at a speed of 1200 rpm with a polytetrafluoroethylene stirring paddle. The mass ratio of the immersed cooled material was 10:1. After stirring for 9 minutes, the constant temperature was lowered to 22° C...

Embodiment 2

[0022] Embodiment 2: Calcium nitrate tetrahydrate, magnesium nitrate hexahydrate, hafnium oxide, europium nitrate hexahydrate, copper nitrate trihydrate, zinc nitrate hexahydrate, ammonium tungstate hydrate according to the stoichiometric formula MgEu 0.7 Ca 0.3 f 0.8 Cu 0.1 Zn 0.1 WO 6 Put into the ball mill, the mass ratio of the ball mill and the material is 20:1, and ball mill for 15 hours at a speed of 400 rev / min. The ball-milled material is heated to 900°C at a rate of 8°C / min in a tube furnace, and then a DC voltage of 900V is applied to both ends of the tube furnace. Cool the furnace to 30°C; grind the cooled material in a mortar for 12 minutes, and immerse it in a saturated solution of lithium metaborate at a constant temperature of 30°C under constant stirring at a speed of 1000 rpm with a polytetrafluoroethylene stirring paddle. The mass ratio of the immersed cooled material was 10:1. After stirring for 7 minutes, the constant temperature was lowered to 18°C ​...

Embodiment 3

[0023] Embodiment 3: Calcium nitrate tetrahydrate, magnesium nitrate hexahydrate, hafnium oxide, europium nitrate hexahydrate, copper nitrate trihydrate, zinc nitrate hexahydrate, ammonium tungstate hydrate according to the stoichiometric formula MgEu 0.7 Ca 0.3 f 0.8 Cu 0.1 Zn 0.1 WO 6 Put it into a ball mill, the mass ratio of the ball mill to the material is 20:1, and ball mill for 10 hours at a speed of 200 rpm. The ball-milled material is heated to 800°C at a rate of 2°C / min in a tube furnace, and then a DC voltage of 600V is applied to both ends of the tube furnace. Cool the furnace to 30°C; grind the cooled material in a mortar for 6 minutes, and immerse it in a saturated solution of lithium metaborate at a constant temperature of 30°C under constant stirring at a speed of 900 rpm with a polytetrafluoroethylene stirring paddle. The mass ratio of the mass to the immersed cooled material was 10:1. After stirring for 5 minutes, the constant temperature was lowered to ...

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Abstract

The invention provides a magnesium ion battery negative electrode material MaEu0.7Ca0.3Hf0.8Cu0.1Zn0.1WO6 and a preparation method. The magnesium ion battery negative electrode material is characterized in that the negative electrode material is of a double perovskite structure; in the preparation process, the crystallization characteristic of crystals with lattice defects is changed by applying an electric field in the specific direction during a high-temperature solid state reaction, and columnar particles grow in the electric field direction; meanwhile, by means of non-uniform crystallization of the surfaces of the columnar particles, a sintering aid is non-uniformly adhered to the parts with large surface curvature radius, so that the particles are partially bonded to form continuous porous morphology; the morphology is beneficial for reducing the crystal boundary resistance and the electron migration resistance, improving the magnesium iron migration capacity and increasing the rate of a redox reaction and has the certain structure rigidity to form buffer for material volume changes generated in the charging and discharging process; and furthermore, by means of Mg and Eu common occupy at the A position, Ca doping at the Eu position and Cu and Zn doping at the B position, the high-performance magnesium ion battery negative electrode material is prepared.

Description

technical field [0001] The invention relates to the technical field of a method for manufacturing a negative electrode material of a magnesium ion battery. Background technique [0002] Lithium-ion secondary batteries have the absolute advantages of high volume, weight-to-energy ratio, high voltage, low self-discharge rate, no memory effect, long cycle life, and high power density. Currently, the global mobile power market has an annual share of more than 30 billion US dollars and Gradually grow at a rate of more than 10%. Especially in recent years, with the gradual depletion of fossil energy, new energy sources such as solar energy, wind energy, and biomass energy have gradually become alternatives to traditional energy sources. Among them, wind energy and solar energy are intermittent, and a large amount of energy is used simultaneously to meet the needs of continuous power supply. Energy storage batteries; urban air quality problems caused by automobile exhaust are beco...

Claims

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Application Information

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IPC IPC(8): H01M4/485H01M4/131H01M4/1391
CPCH01M4/131H01M4/1391H01M4/485Y02E60/10
Inventor 水淼
Owner 宁波吉电鑫新材料科技有限公司
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