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Template synthesized double perovskite magnesium-ion battery anode material and preparation method thereof

A magnesium ion battery, double perovskite technology, applied in battery electrodes, secondary batteries, circuits, etc., can solve the problems of shortening the diffusion time of magnesium ions, affecting the reversibility of materials, grain growth and agglomeration, etc. The rate of redox reaction, the effect of reducing electron transfer resistance, and improving the conductivity of magnesium ions

Inactive Publication Date: 2017-11-28
宁波吉电鑫新材料科技有限公司
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  • Application Information

AI Technical Summary

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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  • Template synthesized double perovskite magnesium-ion battery anode material and preparation method thereof

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Embodiment 1

[0021] Example 1: Magnesium nitrate hexahydrate, yttrium nitrate hexahydrate, europium nitrate hexahydrate, barium nitrate, chromium nitrate nonahydrate, zinc nitrate hexahydrate, ammonium tungstate hydrate, and ferric nitrate nonahydrate are in accordance with the stoichiometric formula Mg 0.9 Ba 0.1 Y 0.8 Eu 0.2 Cr 0.9 Zn 0.1 W 0.9 Fe 0.1 O 6 Mix in the ratio of, add citric acid 5 times the amount of total metal ions and add water and stir to form a total metal ion concentration of 1.0 mol·L -1 The initial aqueous solution; mix 6g acrylamide / 100mL water acrylamide and 1gN,N'-methylenebisacrylamide / 100mL water N,N'-methylenebisacrylamide and water, and dissolve the acrylamide in the solution The amount of the substance is 0.5 times the amount of the total metal ion substance in the initial aqueous solution; after stirring for 5 minutes at a speed of 1500 rpm using a polytetrafluoroethylene stirring blade, it is raised to 75°C at a speed of 5°C / min and maintained at this temperatu...

Embodiment 2

[0022] Example 2: Magnesium nitrate hexahydrate, yttrium nitrate hexahydrate, europium nitrate hexahydrate, barium nitrate, chromium nitrate nonahydrate, zinc nitrate hexahydrate, ammonium tungstate hydrate, and ferric nitrate nonahydrate are in accordance with the stoichiometric formula Mg 0.9 Ba 0.1 Y 0.8 Eu 0.2 Cr 0.9 Zn 0.1 W 0.9 Fe 0.1 O 6 Mix in the proportion of, add citric acid 10 times the amount of total metal ions and add water and stir to form a total metal ion concentration of 2.5mol·L -1 The initial aqueous solution; mix 6g acrylamide / 100mL water acrylamide and 1gN,N'-methylenebisacrylamide / 100mL water N,N'-methylenebisacrylamide and water, and dissolve the acrylamide in the solution The amount of the substance is 0.8 times the amount of the total metal ion substance in the initial aqueous solution; after stirring for 10 minutes at a speed of 1800 rpm with a polytetrafluoroethylene stirring blade, it is raised to 80°C at a speed of 7°C / min and maintained at this temp...

Embodiment 3

[0023] Example 3: Magnesium nitrate hexahydrate, yttrium nitrate hexahydrate, europium nitrate hexahydrate, barium nitrate, chromium nitrate nonahydrate, zinc nitrate hexahydrate, ammonium tungstate hydrate, and ferric nitrate nonahydrate according to the stoichiometric formula Mg 0.9 Ba 0.1 Y 0.8 Eu 0.2 Cr 0.9 Zn 0.1 W 0.9 Fe 0.1 O 6 Mix in the ratio, add citric acid 8 times the amount of total metal ions and add water and stir evenly to form a total metal ion concentration of 2mol·L -1 The initial aqueous solution; mix 6g acrylamide / 100mL water acrylamide and 1gN,N'-methylenebisacrylamide / 100mL water N,N'-methylenebisacrylamide and water, and dissolve the acrylamide in the solution The amount of the substance is 1.2 times the amount of the total metal ion substance in the initial aqueous solution; use a polytetrafluoroethylene stirring blade to stir at 2000rpm for 15 minutes, then increase it to 85°C at a speed of 10°C / min and maintain the temperature Until it becomes a jelly-l...

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Abstract

The invention discloses a template synthesized double perovskite magnesium-ion battery anode material and a preparation method thereof. The material is characterized by comprising Mg0.9Ba0.1Y0.8Eu0.2Cr0.9Zn0.1W0.9Fe0.1O6. In the preparation process, a continuous pore structure of gel is taken as a template, and a continuously porous morphology double perovskite structure product with particle parts mutually bonded is formed; the morphology facilitates reduction of the crystal boundary resistance and electron migration resistance; the magnesium ion migration capability is accelerated, and the oxidative reduction reaction speed is increased; the structure has certain structure rigidity, and buffer is formed for volume change of the material in the charge-discharge process; further, the electron conductivity is improved through joint occupation of Mg and Y at the site A, and the magnesium ion conductivity is improved through Ba doping in a part of the Mg position and Eu doping in the Y position; the stability of the perovskite structure is improved through Zn and Fe doping at the site B, and finally, the high-performance magnesium-ion battery anode material is formed.

Description

Technical field [0001] The invention relates to the technical field of a method for manufacturing a magnesium ion battery negative electrode material. Background technique [0002] Lithium-ion secondary batteries have absolute advantages such as volume, high weight-to-energy ratio, high voltage, low self-discharge rate, no memory effect, long cycle life, and high power density. At present, they have more than 30 billion US dollars / year share in the global mobile power market. Gradually increase 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 number of them are used at the same time to meet the needs of continuous power supply. Energy storage batteries; the urban air quality problem caused by automobile exhaust is becomin...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/48H01M4/38H01M4/46H01M4/525H01M10/0525
CPCH01M4/38H01M4/382H01M4/466H01M4/483H01M4/525H01M10/0525Y02E60/10
Inventor 水淼
Owner 宁波吉电鑫新材料科技有限公司
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