A negative electrode material for double perovskite sodium-ion battery synthesized by selective crystallization controlled by electric field and its preparation method

A sodium-ion battery, selective crystallization technology, applied in the direction of battery electrodes, negative electrodes, secondary batteries, etc., can solve the problems of complex mechanism of matrix action, high activation energy of sodium ion diffusion, affecting material reversibility, etc., to achieve accelerated migration ability And the rate of redox reaction, improve the conductivity of sodium ion, reduce the effect of electron migration resistance

Active Publication Date: 2018-10-23
HAIMEN THE YELLOW SEA ENTREPRENEURSHIP PARK SERVICE CO LTD
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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 During the alloying reaction, the compound 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 properties that are completely different from those of single metals. Therefore, ABO 3 type oxide has the potential to become a high-performance sodium-ion battery anode material, which may provide close to or more than 500mAh.g -1 The specific capacity, the volume change of the material that sodium ions enter or exit is also small; however, the research and development of this material in sodium ion batteries is basically blank
And its main problem is: 1, ionic conductivity and electron conductivity are lower; 2, the product sodium oxide after conversion reaction is electronic insulator and its sodium ion diffusion activation energy is also higher, causes larger electrochemical polarization; 3. The synthesis temperature is high, which is easy to cause the growth and agglomeration of grains
[0014] In response to these problems, changing the shape of the material can alleviate these problems to a certain extent. For example, reducing the particle size of the material to the nanometer scale can reduce the diffusion path of sodium ions, shorten the diffusion time of sodium ions, and improve the kinetics of the material. performance; too small particle size can easily cause difficulties in electronic conduction between particles; the same agglomeration between particles or too large particles can easily cause electrolyte penetration difficulties between particles, slow migration of sodium ions and other problems; ion doping Doping is also an effective way to adjust the microstructure of the lattice and change the transport characteristics of lattice electrons and ions. However, the mechanism of ion doping or even multi-ion synergistic doping on the matrix is ​​very complicated, and the effect is often unpredictable.

Method used

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  • A negative electrode material for double perovskite sodium-ion battery synthesized by selective crystallization controlled by electric field and its preparation method

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Experimental program
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Effect test

Embodiment 1

[0021] Embodiment 1: with barium nitrate, sodium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, zirconium nitrate pentahydrate, manganese nitrate tetrahydrate, ammonium molybdate tetrahydrate, nickel nitrate hexahydrate according to stoichiometric formula NaBa 0.3 La 0.3 K 0.4 Zr 0.8 Ni 0.1 mn 0.1 MoO 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 te...

Embodiment 2

[0022] Embodiment 2: barium nitrate, sodium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, zirconium nitrate pentahydrate, manganese nitrate tetrahydrate, ammonium molybdate tetrahydrate, nickel nitrate hexahydrate according to stoichiometric formula NaBa 0.3 La 0.3 K 0.4 Zr 0.8 Ni 0.1 mn 0.1 MoO 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 temperat...

Embodiment 3

[0023] Embodiment 3: barium nitrate, sodium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, zirconium nitrate pentahydrate, manganese nitrate tetrahydrate, ammonium molybdate tetrahydrate, nickel nitrate hexahydrate according to stoichiometric formula NaBa 0.3 La 0.3 K 0.4 Zr 0.8 Ni 0.1 mn 0.1 MoO 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 te...

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Abstract

The invention discloses an electric field regulated selective crystallization synthesized double perovsNaite sodium ion battery negative electrode material and a preparation method thereof. The material is characterized in that the composition of the negative electrode material is NaBa0.3La0.3K0.4Zr0.8Ni0.1Mn0.1MoO6, an electric field having a specific direction is applied during a high-temperature solid phase reaction in the preparation process to change the crystal characteristics of lattice defect crystals and grow cylindrical particles along the direction of the electric field; the non-uniform crystallization on the surfaces of the cylindrical particles maNaes a sintering aid non-uniformly adhered to the position having a large surface curvature radius and partially bonded to form a continuous porous morphology, and the morphology is in favor of reducing the crystal boundary resistance and the electron migration resistance and accelerating the migration ability of sodium ions in an electrolyte and crystal lattices and the oxidation reduction reaction rate; the material also has a certain structure rigidity, so the volume change of the material in the charge and discharge process is buffered; and the high-performance sodium ion battery negative electrode material is formed through the co-occupation of Na and La in an A position, the Ba and K doping in a La position and the Ni and Mn doping in a B position.

Description

technical field [0001] The invention relates to the technical field of a method for manufacturing an anode material of a sodium 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 vehicle exhaust are becoming more and more...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C01G53/00H01M4/485H01M4/62H01M10/054
CPCC01G53/006C01P2006/40H01M4/485H01M4/626H01M10/054H01M2004/021H01M2004/027Y02E60/10
Inventor 水淼
Owner HAIMEN THE YELLOW SEA ENTREPRENEURSHIP PARK SERVICE CO LTD
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