Preparation methods of lithium ion battery composite positive electrode, flexible lithium battery and solid-state lithium battery

A technology for lithium ion batteries and composite positive electrodes, applied in battery electrodes, secondary batteries, circuits, etc., can solve the problems of low lithium-conducting activity of the coating layer, unfavorable lithium ion transmission, etc., and achieve low cost, improved cycle performance, and preparation. simple method effect

Inactive Publication Date: 2017-08-11
UNIV OF SCI & TECH BEIJING
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Some studies have used metal oxides to coat and modify positive electrode materials (patent 105932251A 201610389932.9), but the lithium-conducting activity of the coating layer is

Method used

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  • Preparation methods of lithium ion battery composite positive electrode, flexible lithium battery and solid-state lithium battery
  • Preparation methods of lithium ion battery composite positive electrode, flexible lithium battery and solid-state lithium battery

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1: Li 7 La 3 Zr 2 o 12 coated LiNi 0.5 mn 1.5 o 4 Positive electrode for all-solid-state batteries

[0026] Step (1) Add 0.57g of lithium nitrate, 1.54g of lanthanum nitrate, 0.55g of zirconium nitrate, 0.8g of ethylene glycol, and 3g of citric acid into a 25ml beaker, and stir at room temperature for 5 hours. According to the mass ratio of inorganic fast lithium ion conductor and unmodified positive electrode material is 1:200, the LiNi of 20g 0.5 mn 1.5 o 4 The powder is added to the above-mentioned inorganic fast lithium ion conductor Li 7 La 3 Zr 2 o 12 Mix the two evenly at room temperature, and sonicate in an ultrasonic disperser for 1h, repeat the ultrasonic step and the stirring step alternately, ultrasonic for 10min, and stir for 10min to ensure the mixing uniformity and Dispersion among materials.

[0027] Step (2) The mixed solution in step (1) was placed at 60° C. and stirred for 5 h. With the volatilization of the solvent in the mixed...

Embodiment 2

[0030] Example 2: Li 7 La 3 Zr 0.15 mn 0.05 o 12 coated LiNi 0.5 mn 0.3 co 0.2 o 2 Positive electrode for all-solid-state batteries

[0031] Step (1) lithium carbonate, lanthanum oxide, zirconium oxynitrate, manganese nitrate with Li 7 La 3 Zr 0.15 mn 0.05 o 12 The stoichiometric ratio (5% excess lithium carbonate) pre-prepared 0.2g of Li 7 La 3 Zr 0.15 mn 0.05 o 12 . Add the above several raw materials into a 25ml beaker, add 2g of citric acid, 5mL of ethylene glycol, and 10mL of dilute nitric acid into the beaker and stir at 50°C for 5 hours. In above-mentioned solution, add according to the mass ratio of inorganic fast lithium ion conductor and unmodified cathode material be 1:100, the LiNi of 10g 0.5 mn 0.3 co 0.2 o 2 The powder is added to the above-mentioned inorganic fast lithium ion conductor Li 7 La 3 Zr 0.15 mn 0.05 o 12 Mix the two evenly at room temperature, and sonicate in an ultrasonic disperser for 1h, repeat the ultrasonic step and th...

Embodiment 3

[0035] Example 3: Li 6.7 al 0.1 La 3 Zr 2 o 12 coated LiNi 0.5 mn 0.3 co 0.2 o 2 Positive electrode for liquid battery

[0036] Step (1) lithium carbonate, lanthanum oxide, zirconium oxynitrate, aluminum nitrate with Li 6.7 al 0.1 La 3 Zr 2 o 12 The stoichiometric ratio (5% excess of lithium carbonate) pre-prepared 0.08g of Li 6.7 al 0.1 La 3 Zr 2 o 12 . Add the above several raw materials into a 25ml beaker, add 2g of citric acid, 5mL of ethylene glycol, and 10mL of dilute nitric acid into the beaker and stir at 40°C for 5 hours. According to the mass ratio of the inorganic fast lithium ion conductor to the unmodified positive electrode material is 1:100, 10g of LiNi 0.5 mn 0.3 co 0.2 o 2 The powder is added to the above-mentioned inorganic fast lithium ion conductor Li 6.7 al 0.1 La 3 Zr 2 o 12 Mix the two evenly at room temperature, and sonicate in an ultrasonic disperser for 1h, repeat the ultrasonic step and the stirring step alternately, ultras...

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Abstract

The invention relates to preparation methods of a lithium ion battery composite positive electrode, a flexible lithium battery and a solid-state lithium battery. A composite positive electrode material of which a surface is coated with an inorganic rapid lithium ion conductor is obtained by uniformly mixing a precursor liquid of the rapid lithium ion conductor and a lithium ion battery positive electrode material under a certain temperature, and an inorganic rapid lithium ion conductor coated composite positive electrode material is obtained after thermal processing is performed on the composite positive electrode, wherein the inorganic rapid lithium ion conductor is a high-electrical conductivity garnet-shaped solid-state electrolyte Li<5+x>N<x>La<3-x>M<2>O<12> (X is more than or equal to 0 but less than or equal to 2, M is Nb, Ta, Sb or Bi, and N is Ca, Ba, Sr or Ge) and a modified compound thereof Li<7+x>(La<2-x>M<x>)B<2>O<12> (X is more than or equal to 0 but less than or equal to 2, M is Ca, Ba, Sr or Ge, and B is Zr, Hf or Sn), or Li<7-x>La<3>Zr<2-x>Ta<x>O<12> (X is more than or equal to 0 but less than or equal to 2); and/or the inorganic rapid lithium ion conductor is LiM<2>O<4> with a spinel structure, and M is Ni and/or Mn; and/or the inorganic rapid lithium ion conductor is LiMO<2> with a layered structure, and M is at least one of Ni, Co, Mn and Al; and/or the inorganic rapid lithium ion conductor is a lithium-rich manganese-based positive electrode material (x)Li<2>MnO<3>.(1-x)LiMO<2>, x is more than 0.1 but less than 0.9, and M is one of Ni, Co and Mn. By the composite positive electrode material, the cycle performance, the high-temperature performance and the rate performance of the lithium ion battery positive electrode material can be improved.

Description

technical field [0001] The invention belongs to the field of lithium ion batteries, and relates to positive electrode materials of lithium ion batteries, specifically lithium ion battery positive electrode materials coated with inorganic fast lithium ion conductors and a preparation method thereof, and lithium ion batteries coated with the inorganic fast lithium ion conductors Application of positive electrode materials in lithium-ion batteries and lithium metal all-solid-state batteries. Background technique [0002] The current lithium-ion battery cathode materials, especially high-voltage cathode materials, such as lithium cobalt oxide, spinel lithium manganese oxide, etc., still have some key problems to be solved urgently, except for the first large irreversible capacity, poor rate performance, In addition to the common problems such as severe cycle capacity fading, when high-voltage cathode materials are used in solid-state batteries, a series of problems will also ari...

Claims

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Application Information

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IPC IPC(8): H01M4/131H01M4/1391H01M4/36H01M4/505H01M4/525H01M4/62H01M10/0525H01M10/0562
CPCH01M4/131H01M4/1391H01M4/366H01M4/505H01M4/525H01M4/624H01M10/0525H01M10/0562Y02E60/10
Inventor 范丽珍李丹张博晨
Owner UNIV OF SCI & TECH BEIJING
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