A kind of template synthesis perovskite lithium ion battery negative electrode material and preparation method thereof

A technology for lithium-ion batteries and negative electrode materials, applied in battery electrodes, secondary batteries, chemical instruments and methods, etc., can solve the problems of slow migration speed of lithium ions, shorten the diffusion time of lithium ions, and difficulty in particle electron conduction, and achieve faster Lithium ion migration ability and the rate of redox reaction, the effect of reducing the resistance of electron migration and increasing the diffusion rate

Active Publication Date: 2019-04-05
HAIMEN THE YELLOW SEA ENTREPRENEURSHIP PARK SERVICE CO LTD
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  • Summary
  • Abstract
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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 oxides may become a high-performance lithium-ion battery anode material, which may provide close to or exceed 500mAh.g -1 The specific capacity, and its rate characteristics are superior to those of metal oxides, sulfides, phosphides, carbonates, and chlorides, and the volume change of the material that lithium ions enter or exit is also small; however, the research and development of this material is currently still in progress. very few
And its main problem is: 1, ionic conductivity and electronic conductivity are low; 2, the product lithium oxide after conversion reaction is electronic insulator and its lithium ion diffusion activation energy is also higher, causes greater electrochemical polarization; 3. The synthesis temperature is high, which is easy to cause the growth and agglomeration of grains
[0010] 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 lithium ions, shorten the diffusion time of lithium ions, and improve the kinetics of the material. performance; too small a particle size can also 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 lithium 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 kind of template synthesis perovskite lithium ion battery negative electrode material and preparation method thereof

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Embodiment 1

[0017] Embodiment 1: Lanthanum nitrate hexahydrate, lithium nitrate, cesium nitrate, manganese nitrate tetrahydrate, copper nitrate trihydrate, cadmium nitrate tetrahydrate are according to stoichiometric formula La 0.7 Li 0.2 Cs0.1 mn 0.8 Cu 0.1 Cd 0.1 o 3 The proportion of mixing, adding the amount of citric acid that is 5 times the amount of total metal ion substances and adding water to stir evenly to form a total metal ion concentration of 1mol L -1 The initial aqueous solution; mix and dissolve 6g acrylamide / 100mL water volume of acrylamide and 1g N,N'-methylenebisacrylamide / 100mL water volume N,N'-methylenebisacrylamide and water, and 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; use a polytetrafluoroethylene stirring paddle to stir at a speed of 1500rpm for 5 minutes, then raise it to 75°C at a speed of 5°C / min and maintain the temperature until it becomes a jell...

Embodiment 2

[0018] Embodiment 2: Lanthanum nitrate hexahydrate, lithium nitrate, cesium nitrate, manganese nitrate tetrahydrate, copper nitrate trihydrate, cadmium nitrate tetrahydrate are according to stoichiometric formula La 0.7 Li 0.2 Cs 0.1 mn 0.8 Cu 0.1 Cd 0.1 o 3 The proportion of mixing, the amount of substance added is citric acid which is 7 times the amount of total metal ion substance, and water is added to stir evenly to form a total metal ion concentration of 1.5mol L -1 The initial aqueous solution; mix and dissolve 6g acrylamide / 100mL water volume of acrylamide and 1g N,N'-methylenebisacrylamide / 100mL water volume N,N'-methylenebisacrylamide and water, and 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; use a polytetrafluoroethylene stirring paddle to stir at a speed of 1700rpm for 8 minutes, then raise it to 80°C at a speed of 8°C / min and maintain the temperature unti...

Embodiment 3

[0019] Embodiment 3: Lanthanum nitrate hexahydrate, lithium nitrate, cesium nitrate, manganese nitrate tetrahydrate, copper nitrate trihydrate, cadmium nitrate tetrahydrate are according to stoichiometric formula La 0.7 Li 0.2 Cs 0.1 mn 0.8 Cu 0.1 Cd 0.1 o 3 The proportion of mixing, the amount of substance added is citric acid 10 times the amount of total metal ion substances, and water is added to stir evenly to form a total metal ion concentration of 2.5mol L -1 The initial aqueous solution; mix and dissolve 6g acrylamide / 100mL water volume of acrylamide and 1g N,N'-methylenebisacrylamide / 100mL water volume N,N'-methylenebisacrylamide and water, and the acrylamide in the solution The amount of the substance is 1.1 times the amount of the total metal ion substance in the initial aqueous solution; use a polytetrafluoroethylene stirring paddle to stir at a speed of 1900rpm for 13 minutes, then raise it to 85°C at a speed of 9°C / min and maintain the temperature until it b...

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Abstract

The invention provides a perovskite negative electrode material prepared through template synthesis and used for a lithium ion battery, and a preparation method thereof. The invention is characterized in that the composition of the negative electrode material is La<0.7>Li<0.2>Cs<0.1>Mn<0.8>Cu<0.1> Cd<0.1>O<3>; the continuous channel structure of gel is employed as a template in the process of preparation, and a perovskite-structured product with continuous porous morphology and mutually bonded particle parts is formed, wherein such morphology is beneficial for reducing crystal boundary resistance; a continuous electron transfer network is formed, and electron transfer resistance is lowered; a contact area between the prepared perovskite negative electrode material and an electrolyte is increased, and the perovskite negative electrode material has certain structural rigidity; furthermore, through Li doping at position A, lattice imperfection is increased, so the material can improve the diffusion rate of lithium ions and can be used as a negative electrode material corresponding to a lithium-free lithium-ion-battery positive electrode material; the sintering properties of particles are improved in virtue of Cs doping; Cu and Cd doping at position B can improve the stability of a perovskite structure; and thus, the lithium ion battery negative electrode material with high performance is eventually formed.

Description

technical field [0001] The invention relates to the technical field of a method for manufacturing a negative electrode material of a lithium 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 becomi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C01G45/00H01M4/485H01M4/505H01M10/0525
CPCC01G45/006C01P2006/40H01M4/485H01M4/505H01M10/0525Y02E60/10
Inventor 水淼
Owner HAIMEN THE YELLOW SEA ENTREPRENEURSHIP PARK SERVICE CO LTD
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