Multiphase composite high-nickel ternary positive electrode material and preparation method thereof

A positive electrode material and high-nickel technology, which is applied in the field of multi-phase composite high-nickel ternary positive electrode materials and its preparation, can solve the problems of increased Ni/Li mixing degree, reduced electrochemical performance of materials, poor structural stability, etc., to achieve Reduce particle breakage, improve the first charge and discharge efficiency, and stabilize the structure

Active Publication Date: 2019-10-18
HUNAN ZHENGYUAN ENERGY STORAGE MATERIALS & DEVICE INST
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  • Abstract
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  • Application Information

AI Technical Summary

Problems solved by technology

Although high-nickel ternary cathode materials have many advantages, there are also some problems: (1) Severe cation mixing
Ni 3+ is thermodynamically unstable with spontaneous reduction to Ni 2+ trend, Ni 2+ Radius (0.069nm) and Li + The radius (0.076nm) is close to that of Ni 2+ The continuous production of Ni / Li increases the degree of mixing, and gradually produces Li + The NiO-like phase with poor conductivity, the material is exposed to the air for a long time, and lithium precipitation occurs on the surface of the material. Lithium ions cover the surface of the ternary positive electrode material in the form of lithium carbonate and lithium hydroxide, resulting in capacity decay during the cycle. serious
(2) Ni in the high-nickel ternary cathode material 4+ The compatibility with the electrolyte is poor, and the reaction with the electrolyte will easily reduce the electrochemical performance of the material
For high-nickel ternary cathode materials, there are currently some defects in the material properties and preparation methods: the material has poor structural stability during cycling, poor high-temperature stability, and poor storage performance. The above factors restrict its further application, so the invention A multi-phase composite high-nickel ternary positive electrode material for improving the structural stability of the material and its preparation method are particularly important

Method used

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  • Multiphase composite high-nickel ternary positive electrode material and preparation method thereof
  • Multiphase composite high-nickel ternary positive electrode material and preparation method thereof
  • Multiphase composite high-nickel ternary positive electrode material and preparation method thereof

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Effect test

Embodiment 1

[0040] Carboxymethyl cellulose (CMC), sodium hydroxide, and urea were formulated into solutions A with mass fractions of 2%, 5%, and 10% respectively; lithium hydroxide, nickel sulfate, cobalt sulfate, and manganese sulfate were The molar ratio of metal elements is 1.02:0.8:0.1:0.1 dispersed in deionized water to prepare metal ion solution B; N-isopropylacrylamide, N,N'-methylene bisacrylamide and ammonium persulfate The mass fraction is respectively 6%, 0.3% and 0.8% solution C;

[0041] After synchronously adding solution A, solution B and solution C to the reactor, the temperature was raised to 30°C and the holding time was 12 hours; then the temperature was raised to 60°C and the holding time was 15 hours, and the composite solid D was obtained after cooling down. The composite solid D was transferred to a tube furnace, and was heat-treated at 800°C for 20 hours in a pure oxygen atmosphere to obtain a 3D cross-linked interpenetrating network high-nickel ternary cathode mat...

Embodiment 2

[0047] Prepare bagasse cellulose (SBC), sodium hydroxide, and urea into solutions A with mass fractions of 6%, 8%, and 16% respectively; lithium nitrate, nickel nitrate, cobalt nitrate, and manganese nitrate Molar ratio 1.06:0.85:0.12:0.03 Dispersed in deionized water, prepared as metal ion solution B; N-isopropylacrylamide, N,N'-methylenebisacrylamide, ammonium persulfate configured as mass fraction 1%, 0.1% and 0.1% solution C respectively;

[0048] After synchronously adding solution A, solution B and solution C to the reaction kettle, the temperature was raised to 50°C and the holding time was 6 hours; then the temperature was raised to 80°C and the holding time was 8 hours, and the composite solid D was obtained after cooling down. The composite solid D was transferred to a tube furnace, and heat-treated at a high temperature of 750°C for 15 hours in a pure oxygen atmosphere to obtain a 3D cross-linked interpenetrating network high-nickel ternary cathode material matrix. ...

Embodiment 3

[0051] Hydroxyethyl cellulose (HEC), sodium hydroxide, and urea were formulated into solutions A with mass fractions of 3%, 6%, and 13% respectively; lithium carbonate, nickel acetate, cobalt acetate, and manganese acetate were The element molar ratio is 1.12:0.9:0.07:0.03 dispersed in deionized water and prepared as metal ion solution B; Solutions C with fractions of 3%, 0.3% and 0.5%, respectively;

[0052] After synchronously adding solution A, solution B and solution C to the reaction kettle, the temperature was raised to 40°C and the holding time was 10 hours; then the temperature was raised to 70°C and the holding time was 10 hours, and the composite solid D was obtained after cooling down. The composite solid D was transferred to a tube furnace, and was heat-treated at 700°C for 15 hours in a pure oxygen atmosphere to obtain a 3D cross-linked interpenetrating network high-nickel ternary cathode material matrix.

[0053] Meta-bis(2,4-diaminobenzenesulfonate lithium), po...

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Abstract

The invention belongs to the field of batteries, and particularly relates to a multiphase composite high-nickel ternary positive electrode material and a preparation method thereof. The material is formed by bonding a 3D cross-linked interpenetrating netty high-nickel ternary positive electrode material matrix and a single-ion conductor polymer, and has a 3D cross-linked interpenetrating netty core-shell structure. The required preparation method comprises the following steps: 1) carrying out gradient temperature reaction on a solution A, a solution B and a solution C in a reaction kettle, andthen carrying out high-temperature treatment to obtain the 3D cross-linked interpenetrating netty high-nickel ternary positive electrode material matrix; and 2) carrying out in-situ growth on lithiumaminobenzenesulfonate, an alcohol polymer, isocyanate and the 3D cross-linked interpenetrating netty high-nickel ternary positive electrode material matrix in the reaction kettle, and carrying out annealing treatment to obtain the multi-phase composite high-nickel ternary positive electrode material. The multi-phase composite high-nickel ternary positive electrode material prepared by the preparation method is good in cycling performance, easy for size mixing of a lithium ion battery, excellent in rate performance and low-temperature performance, and stable in structure; and the process is simple and easy to operate, and is environment-friendly.

Description

technical field [0001] The invention belongs to the field of batteries, and in particular relates to a multiphase composite high-nickel ternary positive electrode material and a preparation method thereof. Background technique [0002] In recent years, lithium-ion batteries have been widely used due to their high energy density, high charging voltage, long cycle life, small self-discharge, wide temperature resistance, and environmental protection. The performance of lithium-ion batteries is mainly determined by their positive electrode materials. Decide. [0003] The ternary cathode material LiNixCoyMnzO2 (x+y+z=1) has the advantages of high energy density, simple preparation method, and relatively low raw material cost. It has become the most promising cathode material for power batteries after lithium iron phosphate. According to the requirements of the National Development and Reform Commission's "Three-Year Action Plan for Enhancing Manufacturing Core Competitiveness (2...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/36H01M4/505H01M4/525H01M4/62H01M10/0525
CPCH01M4/366H01M4/505H01M4/525H01M4/624H01M10/0525Y02E60/10
Inventor 尚雷李荐
Owner HUNAN ZHENGYUAN ENERGY STORAGE MATERIALS & DEVICE INST
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