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Dual-perovskite magnesium ion battery negative electrode material by one-step synthesis and preparation method thereof

A magnesium ion battery, double perovskite technology, applied in battery electrodes, secondary batteries, circuits, etc., can solve the problems of complex parent action mechanism, material lattice transformation, large electrochemical polarization, etc., and achieve accelerated migration ability. and redox reaction rate, improve the electronic conductivity, improve the effect of exercise ability

Inactive Publication Date: 2017-11-24
宁波吉电鑫新材料科技有限公司
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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 potential to become a high-performance magnesium-ion battery anode material, which may provide close to or more than 300mAh.g -1 The specific capacity, the volume change of the material that magnesium ions enter or exit is also small; however, the research and development of this material in magnesium ion batteries is basically blank
And its main problem is: 1, ionic conductivity and electron conductivity are lower; 2, the product magnesium oxide after conversion reaction is electronic insulator and its magnesium 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 morphology 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 magnesium ions, shorten the diffusion time of magnesium 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 magnesium 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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  • Dual-perovskite magnesium ion battery negative electrode material by one-step synthesis and preparation method thereof
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Embodiment 1

[0023] Embodiment 1: Magnesium nitrate hexahydrate, neodymium oxide, lithium nitrate, zinc nitrate hexahydrate, ferric nitrate nonahydrate, niobium pentoxide, copper nitrate trihydrate are according to stoichiometric formula MgNd 0.8 Li 0.2 Fe 0.9 Cu 0.1 Nb 0.9 Zn 0.1 o 6 Put into a ball mill, the mass ratio of the ball mill and the material is 20:1, and ball mill for 11 hours at a speed of 200 rpm. The material after ball milling is sent into such as figure 1 In the synthesizer shown, the flow velocity of the air is 0.5m 3 min -1 ; The synthesis device consists of four parts: an ultrasonic atomizer, a droplet area, a tube furnace and a cyclone separator; at the same time, start the ultrasonic atomizer and immerse in 1.0mol L -1 An immersion ultrasonic transducer with a power of 250W in potassium nitrate aqueous solution produces a large number of mist droplets and the flow rate is 0.5L min -1 The mixed gas of oxygen and argon with a volume ratio of 20:80 is carried f...

Embodiment 2

[0024] Embodiment 2: Magnesium nitrate hexahydrate, neodymium oxide, lithium nitrate, zinc nitrate hexahydrate, ferric nitrate nonahydrate, niobium pentoxide, and copper nitrate trihydrate are according to the stoichiometric formula MgNd 0.8 Li 0.2 Fe 0.9 Cu 0.1 Nb 0.9 Zn 0.1 o 6 Put into the ball mill, the mass ratio of the ball mill and the material is 20:1, and ball mill for 19 hours at a speed of 400 rev / min. The material after ball milling is sent into such as figure 1 In the synthesizer shown, the air velocity is 3.5m 3 min -1 ; The synthesis device consists of four parts: ultrasonic atomizer, drop zone, tube furnace and cyclone separator; at the same time, start the ultrasonic atomizer and immerse in 1.5mol L -1 An immersed ultrasonic transducer with a power of 250W in potassium nitrate aqueous solution produces a large number of mist droplets and the flow rate is 3.5L min -1 The mixed gas of oxygen and argon with a volume ratio of 20:80 is carried from below t...

Embodiment 3

[0025] Embodiment 3: Magnesium nitrate hexahydrate, neodymium oxide, lithium nitrate, zinc nitrate hexahydrate, ferric nitrate nonahydrate, niobium pentoxide, copper nitrate trihydrate according to the stoichiometric formula MgNd 0.8 Li 0.2 Fe 0.9 Cu 0.1 Nb 0.9 Zn 0.1 o 6 Put into ball mill, the mass ratio of ball mill and material is 20: 1, with the speed ball mill of 300 rev / mins 15 hours. The material after ball milling is sent into such as figure 1 In the synthetic device shown, the flow rate of nitrogen is 3.0m 3 min -1 ; The synthesis device consists of four parts: an ultrasonic atomizer, a droplet area, a tube furnace and a cyclone separator; at the same time, start the ultrasonic atomizer and immerse in 1.2mol L -1 An immersion ultrasonic transducer with a power of 250W in potassium nitrate aqueous solution produces a large number of droplets and the flow rate is 2.5L min -1 The mixed gas of oxygen and argon with a volume ratio of 20:80 is carried from below t...

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Abstract

The invention relates to a dual-perovskite magnesium ion battery negative electrode material by one-step synthesis and a preparation method thereof. The constituent of the negative electrode material is MgNd<0.8>Li<0.2>Fe<0.9>Cu<0.1>Nb<0.9>Zn<0.1>O6; and during the preparation method, a sintering additive is non-uniformly pasted onto a rapidly-atomized sintering additive region by carrying a reaction raw material in gas flow, a product is continuously obtained in a high-temperature tubular furnace in one step, and particle parts of the product are bonded to form continuous and porous morphology by non-uniformly pasting the sintering additive. By such morphology, the gain boundary resistance and the electron transfer resistance are favorably reduced, and the oxidization-reduction reaction ratio is accelerated; the material also has certain structural rigidity; and the high-performance magnesium ion battery negative electrode material is finally formed further by joint occupancy of Mg and Nd at A positions and doping of Zn and Cu at B positions.

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): H01M4/48H01M4/52H01M10/054C04B35/50C04B35/622
CPCC04B35/50C04B35/622C04B2235/3203C04B2235/3206C04B2235/3251C04B2235/3272C04B2235/3281C04B2235/3284C04B2235/6562C04B2235/6567C04B2235/658C04B2235/6583C04B2235/661C04B2235/768C04B2235/96H01M4/483H01M4/523H01M10/054Y02E60/10
Inventor 水淼
Owner 宁波吉电鑫新材料科技有限公司
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