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Ce1-xZrxO2 nano solid solution homogenate modified lithium ion battery anode material and preparation method thereof

A positive electrode material and solid solution technology, applied in battery electrodes, secondary batteries, circuits, etc., can solve problems such as poor cycle performance, poor battery thermal stability, and reduced cycle performance, and achieve high initial capacity, good rate performance, and cycle life long effect

Active Publication Date: 2016-10-26
TIANJIN B&M SCI & TECH
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  • Description
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Problems solved by technology

1) The synthesis conditions are harsh, Ni 2+ Difficult to oxidize to Ni 3+ , forming non-stoichiometric compounds; 2) in the later stage of charging in Ni 4+ Strong oxidation, will decompose the electrolyte, corrode the current collector, release a large amount of gas and heat, resulting in poor thermal stability of the battery
3) Since part of the lithium sites are occupied, the Ni 2+ is oxidized to Ni with a smaller radius 3+ , leading to the collapse of the hierarchical structure of the material, resulting in a decrease in cycle performance
[0004] In order to solve LiNi x co y m (1-x-y) o 2 For the problem of poor cycle performance, literature reports mainly adopt two methods: doping can only inhibit lithium-nickel mixing, but the interface stability of the material and the rate performance of the material have not been significantly improved. In order to comprehensively improve the LiNiO 2 The overall performance requires the joint doping of multiple elements

Method used

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  • Ce1-xZrxO2 nano solid solution homogenate modified lithium ion battery anode material and preparation method thereof
  • Ce1-xZrxO2 nano solid solution homogenate modified lithium ion battery anode material and preparation method thereof
  • Ce1-xZrxO2 nano solid solution homogenate modified lithium ion battery anode material and preparation method thereof

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preparation example Construction

[0024] Ce of the present invention 1-x Zr x o 2 A method for preparing a nanocomposite solid solution homogeneously modified lithium ion cathode material, the method comprising the following steps:

[0025] (1) Weigh soluble cerium salt and zirconium salt according to a certain molar ratio, dissolve them in deionized water, and prepare a mixed solution so that the total concentration of metal ions in the solution is 0.2M-0.5M, and the molar ratio of the two metal elements Be Ce: Zr=(5-9):(1-5);

[0026] (2) LiNi x co y m (1-x-y) o 2 The positive electrode material is dispersed in deionized water to form a suspension, so that the solid-to-liquid mass ratio is 1: (1-3), and the solution temperature is maintained at 20-60 ° C, and a surfactant is added; LiNi x co y m (1-x-y) o 2 In terms of materials, the mass of surfactant added is 0.1%-0.5%, and after ultrasonic vibration for 10-60min, stir at room temperature for 1h-4h;

[0027] (3) According to the total mass of me...

Embodiment 1

[0041] 1) Prepare a mixed solution of cerium nitrate and zirconium nitrate according to the molar ratio of elements Ce:Zr=1:1 and dissolve it in deionized water to prepare a mixed solution of 200ml so that the total concentration of metal ions in the solution Zr and Ce is 0.5M. The concentration is 0.1M (NH 4 ) 2 CO 3 .

[0042] 2) 1000g LiNi 0.8 co 0.1 mn 0.1 o 2 (BMT910, an existing product of B&M) was put into deionized water and put into 1000ml of deionized water, and stirred with an electric stirrer to keep the solution temperature at 20°C. At the same time, 1g of PEG4000 was added, and after ultrasonication for 10min, stirred for 1h. During the stirring process, the Add 200ml of cerium nitrate and zirconium nitrate mixed solution dropwise to LiNi 0.8 co 0.1 mn 0.1 o 2 Material, continue to stir for 0.5h after dropwise addition.

[0043] 3) Add 0.1M (NH 4 ) 2 CO 3 Add the solution dropwise to the suspension, and stop the dropwise addition when the pH=8-9 (NH...

Embodiment 2

[0047] 1) Prepare a mixed solution of cerium nitrate and zirconium nitrate according to the molar ratio of elements Ce:Zr=0.7:0.3 and dissolve it in deionized water to prepare a mixed solution of 500ml so that the total concentration of metal ions in the solution Zr and Ce is 0.2M. Concentration of 0.5M NH 4 HCO 3 .

[0048] 2) 2000g LiNi 0.8 co 0.15 al 0.05 o 2 (B&M's existing product BMT920) was put into deionized water and put into 2000ml of deionized water, stirred with an electric stirrer, and kept the solution temperature at 40°C. At the same time, 2g of PEG4000 was added, and after ultrasonication for 20min, stirred for 2h. During the stirring process, 500ml The mixed solution of cerium nitrate and zirconium nitrate was added dropwise to LiNi 0.8 co 0.15 al 0.05 o 2 Material, continue to stir for 1h after dropwise addition.

[0049] 3) Add 0.5M NH 4 HCO 3 Add the solution to the suspension, stop adding NH when the pH=8~9 4 HCO 3 Solution, continue to stir ...

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Abstract

The invention belongs to the technical field of lithium ion battery material manufacturing process and discloses a Ce1-xZrxO2 nano solid solution homogenate modified lithium ion battery anode material and a preparation method thereof. A LiNixCoyM(1-x-y)O2 material preparation process includes: forming a coating of a nanoscale metal oxide according to a homogeneous precipitation method, wherein the nanoscale metal oxide refers to Ce1-xZrxO2 nano solid solution; after coating is finished, drying the coating, heating to 200-1000 DEG C at a heating temperature of 1-5DEG C / min, keeping the temperature for 2-20h, and naturally cooling to obtain the Ce1-xZrxO2 nano solid solution homogenate modified LiNixCoyM(1-x-y)O2 material. The prepared LiNixCoyM(1-x-y)O2 material has excellent high-temperature cycle performance and electrochemical interface stability. Compared with a traditional solid-phase method, the modification method is high in uniformity and reliability.

Description

technical field [0001] The present invention relates to a kind of preparation method of lithium ion battery cathode material, especially a kind of Ce 1-x Zr x o 2 The invention relates to a lithium-ion battery cathode material homogeneously modified by a nanometer solid solution and a preparation method thereof, belonging to the technical field of lithium-ion battery material manufacturing technology. Background technique [0002] Since the commercialization of lithium-ion batteries, they have been widely used in many fields such as portable electronic devices, and have begun to expand to fields such as electric vehicles and energy storage. The specific capacity of positive electrode materials in lithium-ion batteries is far lower than that of negative electrode materials. The capacity is ultimately determined by the cathode material. The current marketable cathode material LiCoO 2 , LiMn 2 o 4 The specific capacity is low and the cost is high, which makes it difficult...

Claims

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Application Information

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IPC IPC(8): H01M4/505H01M4/525H01M4/131H01M4/1391H01M10/0525
CPCH01M4/131H01M4/1391H01M4/505H01M4/525H01M10/0525Y02E60/10
Inventor 唐淼徐宁陈勃涛
Owner TIANJIN B&M SCI & TECH
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