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MOFs-based precursor for cobalt-free lithium battery, and preparation method thereof, and positive electrode material and preparation method thereof

A cathode material and precursor technology, applied in the field of lithium battery cathode materials, can solve the problems of Li/Ni mixing, potential safety hazards, and expensive Co, and achieve the effects of reducing sintering temperature, improving rate performance, and improving development prospects.

Active Publication Date: 2021-04-06
JINGMEN GEM NEW MATERIAL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] With the wide application of ternary lithium batteries in new energy vehicles, it is urgent to solve the problem of high energy density and high safety. High nickel materials can improve the energy density of materials, but high Ni content will lead to Li / Ni mixes seriously, forming rock-salt phase, reducing the cycle performance of the material and bringing safety hazards at the same time
Medium and low nickel ternary cathode materials (NCM111, NCM523, NCM622) have higher safety and cycle performance than nickel (NCM811) materials, but the energy density cannot meet the battery life requirements, and Co is expensive

Method used

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  • MOFs-based precursor for cobalt-free lithium battery, and preparation method thereof, and positive electrode material and preparation method thereof
  • MOFs-based precursor for cobalt-free lithium battery, and preparation method thereof, and positive electrode material and preparation method thereof
  • MOFs-based precursor for cobalt-free lithium battery, and preparation method thereof, and positive electrode material and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Step 1, at 1m 3 Add the pure water of 500L in the reaction still, 3kg concentration is the liquid caustic soda solution that 1mol / L of 1mol / L and 6kg concentration are 2mol / L, and the volume ratio of toluene carboxylic acid solution and liquid caustic soda solution is 4:1, The pH of the test bottom solution is 11.4-11.6, and N is passed into the reaction kettle 2 , the flow rate is 0.6m 3 / h, the metal molar ratio is 70:30, metal concentration is the nickel-manganese mixed sulfate solution of 2mol / L with metering pump and joins in the reactor with the flow rate of 30L / h, simultaneously adds 1mol / L in the reactor The sodium hydroxide of phenylcarboxylic acid solution and 2mol / L, the flow rate is respectively 5L / h and 10L / h, the pH of the flow adjustment system is maintained between 11.2-11.6 by controlling the flow rate of ammoniacal liquor and sodium hydroxide in the reaction process, stirs The stirring rate of the paddle is 300-400r / min, the reaction temperature of th...

Embodiment 2

[0037] Step 1, at 1m 3 500L of pure water, 3kg concentration of 1.5mol / L 1,2,3,4-butane tetracarboxylic acid solution and 6kg concentration of 3mol / L liquid caustic soda solution were added in the reaction kettle, and the pH of the test bottom liquid was 10.4-11, and feed N into the reactor 2 , the flow rate is 2m 3 / h, the metal molar ratio is 50:50, the nickel-manganese mixed salt solution that metal concentration is 3mol / L joins in the reaction kettle with the flow rate of 40L / h with metering pump, adds 1.5mol / L in the reaction kettle simultaneously 1,2,3,4-butane tetracarboxylic acid solution and 3mol / L sodium hydroxide, the flow rates are 6L / h and 12L / h respectively, and the pH of the system is adjusted by controlling the flow rates of ammonia water and sodium hydroxide during the reaction Maintain between 10-10.6, the stirring speed of the stirring paddle is 150-200r / min, the reaction temperature of the system is 50°C, and the reaction time is 40h. During the reaction...

Embodiment 3

[0041] Step 1, at 1m 3 Add 500L of pure water, 3kg concentration of 2mol / L 5-hydroxyisophthalic acid solution and 6kg concentration of 4mol / L liquid caustic soda solution in the reaction kettle, test the pH of the bottom liquid to be 11.7-12, and to react N into the kettle 2 , the metal molar ratio is 25:75, and the nickel-manganese mixed salt solution with metal concentration of 4mol / L is added to the reactor with a flow rate of 50L / h by a metering pump, and 2mol / L of 5-hydroxyl is added to the reactor at the same time The sodium hydroxide of isophthalic acid solution and 4mol / L, flow rate is respectively 7.5L / h and 15L / h, by controlling the pH of the flow adjustment system of ammoniacal liquor and sodium hydroxide in the reaction process between 11.7-12, The stirring rate of the stirring paddle is 300-400r / min, and the reaction temperature of the system is 60°C for 80h. During the reaction, use a laser particle size analyzer to detect the particle size of the particles in ...

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Abstract

The invention discloses an MOFs-based precursor for a cobalt-free lithium battery, wherein the structural formula of the precursor is NixMnyAl1-x-yMOFs, the inner core of the precursor is a nickel-manganese-MOFs material, Ni accounts for 10-90% of the molar percentage of the total metal of the inner core, Mn accounts for 10-80% of the molar percentage of the total metal of the inner core, the shell of the precursor is made of a nickel-aluminum-MOFs material, Ni accounts for 70-99% of the molar percentage of total metal in the shell, and aluminum accounts for 1-30% of the molar percentage of the total metal in the shell. According to the MOF-based precursor formed in the invention, volatile gas is generated by organic matters during low-temperature pre-sintering, so that a porous structure is finally formed by the material, de-intercalation of Li is facilitated, the sintering temperature is reduced, the rate capability in a cyclic process can be improved, and the good development prospect is achieved.

Description

technical field [0001] The invention relates to a lithium battery cathode material, in particular to a MOFs-based precursor for a cobalt-free lithium battery, a cathode material and a preparation method thereof. Background technique [0002] In recent years, with the widespread application of rechargeable batteries in electric vehicles, there are currently high requirements for their energy density, safety performance, rate performance, and manufacturing cost. Due to its low cost, cobalt-free materials can meet the large demand of the market and have always been a hot topic in the new energy industry this year. However, because Co can stabilize the layered structure of the material in the ternary cathode material and reduce the mixing of Li / Ni, it is a type of element that is difficult to be replaced. It is precisely because of this key factor that the development and application of cobalt-free materials Facing great challenges. Therefore, it is necessary to improve the la...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G83/00H01M4/485H01M4/505H01M4/525H01M10/0525
CPCC08G83/008H01M4/505H01M4/525H01M4/485H01M10/0525H01M2004/028Y02E60/10
Inventor 许开华张坤薛晓斐李聪陈康黎俊孙海波范亮姣杨幸
Owner JINGMEN GEM NEW MATERIAL
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