Preparation method of electrolytic manganese dioxide for low-potassium low-sodium lithium manganate

A technology of electrolytic manganese dioxide and lithium manganate, applied in manganese oxide/manganese hydroxide, electrochemical generators, circuits, etc., can solve problems such as affecting battery capacity and cycle performance, reducing EMD density, and hidden dangers in production safety. , to improve battery capacity and cycle performance, good economic and social benefits, and achieve the effect of recycling

Pending Publication Date: 2021-03-16
广西下田锰矿有限责任公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Potassium impurities in electrolytic manganese dioxide tend to form cryptopotassium manganese-type MnO 2 Octahedral crystal, this kind of potassium ion located in the center of the lattice hinders the migration of protons during battery discharge, reduces the density of EMD, and makes the discharge process difficult, especially during high current discharge; when the Na+ content When it is too high, the residual sodium ions will be released through battery discharge, which will cause the exchange of sodium and lithium in the electrolyte of the battery. Because Na+ will hinder the movement of Li+, it will seriously affect the battery capacity and cycle performance.
[0004] In view of the above problems, the prior art application number is CN201010183376.2 The production method of low-sodium electrolytic manganese dioxide discloses the use of lithium hydroxide or lithium carbonate instead of baking soda or sodium hydroxide as a neutralizing agent to prepare lithium manganate type electrolytic manganese dioxide. The technical solution of manganese oxide, although this technical solution solves the problem of high sodium in the product, due to the strong corrosiveness of lithium hydroxide, a strong corrosive solution is formed in the water; lithium hydroxide can burn eyes and skin, and inhalation can cause larynx, bronchi Inflammation, convulsions, chemical pneumonia, pulmonary edema, etc. During use and storage, a little carelessness will pollute water sources, air, and soil. Lithium hydroxide and lithium carbonate must be operated in a confined space, and operators must pass strict inspection procedures. Training, strict protection, and operation according to strict operating procedures will bring hidden dangers to safe production, and it is difficult to apply them in actual production

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Embodiment 1—Preparation method of electrolytic manganese dioxide for low-potassium and low-sodium lithium manganate

[0034] It includes the following steps:

[0035] A. Leaching: Mix waste condensed water, waste water from waste rinsing water and waste anolyte produced during the preparation of electrolytic manganese dioxide and tested to be unqualified for electrolysis, and put them into a compound reactor to detect the waste water and waste liquid H in the mixture 2 SO 4 The content is 0.3mol / L and is Mn 2+The content of the manganese carbonate is 0.30mol / L, and the manganese carbonate powder and sulfuric acid are put into the compound reactor to carry out the compound reaction, the reaction temperature is controlled at 95°C-98°C, and the pH value is controlled at 1.5-2.5; The weight ratio of manganese powder to the sulfuric acid is 1:0.65, the liquid-solid ratio is 9.6:1, the manganese carbonate powder has a manganese content of 18%, and the processing particle ...

Embodiment 2

[0046] Embodiment 2—Preparation method of electrolytic manganese dioxide for low-potassium and low-sodium lithium manganate

[0047] It includes the following steps:

[0048] A. Leaching: Mix waste condensed water, waste water from waste rinsing water and waste anolyte produced during the preparation of electrolytic manganese dioxide and tested to be unqualified for electrolysis, and put them into a compound reactor to detect the waste water and waste liquid H in the mixture 2 SO 4 The content is 0.32mol / L and is Mn 2+ The content of the manganese carbonate is 0.35mol / L, and the manganese carbonate powder and sulfuric acid are put into the compound reactor to carry out the compound reaction, the reaction temperature is controlled at 95°C-98°C, and the pH value is controlled at 1.5-2.5; The weight ratio of manganese powder to the sulfuric acid is 1:0.68, the liquid-solid ratio is 12:1, the manganese carbonate powder has a manganese content of 20%, and the processing particle...

Embodiment 3

[0059] Embodiment 3—Preparation method of electrolytic manganese dioxide for low-potassium and low-sodium lithium manganate

[0060] It includes the following steps:

[0061] A. Leaching: Mix waste condensed water, waste water from waste rinsing water and waste anolyte produced during the preparation of electrolytic manganese dioxide and tested to be unqualified for electrolysis, and put them into a compound reactor to detect the waste water and waste liquid H in the mixture 2 SO 4 The content is 0.40mol / L and is Mn 2+ The content is 0.42mol / L, and at the same time, manganese carbonate powder and sulfuric acid are put into the compound reactor for compound reaction, the reaction temperature is controlled at 95°C-98°C, and the pH value is controlled at 1.5-2.5; wherein, the carbonic acid The weight ratio of manganese powder to the sulfuric acid is 1:0.72, the liquid-solid ratio is 17:1, the content of the manganese carbonate powder is 22%, and the processing particle size-20...

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PUM

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Abstract

The invention discloses a preparation method of electrolytic manganese dioxide for low-potassium low-sodium lithium manganate. The method comprises the following steps: carrying out a combination reaction on wastewater and waste liquid generated in the preparation process of electrolytic manganese dioxide, manganese carbonate powder and sulfuric acid to prepare a solution, removing potassium, sodium and iron elements accompanied by acidolysis of raw materials by utilizing the principles of yellow potassium iron vanadium and yellow sodium iron vanadium in a high-temperature acidic environment in the solution preparation process, neutralizing, and carrying out solid-liquid separation to obtain a crude manganese sulfate solution; purifying and removing various harmful heavy metals in three steps, electrolyzing to obtain an electrolytic manganese dioxide semi-finished product, rinsing, grinding and magnetizing by using manganese hydroxide as a neutralizer to remove elemental iron, uniformly mixing, and packaging to obtain the finished product. The electrolytic manganese dioxide is single in crystal form, the crystal form structure is pure gamma-shaped, the activity is high, and the physical and chemical properties are better; and because the impurity content is low and the contents of potassium and sodium are below 100ppm, the requirements of low potassium and low sodium of the electrolytic manganese dioxide for lithium manganate are met, and the battery capacity and the cycle performance of the lithium ion battery can be effectively improved.

Description

technical field [0001] The invention belongs to the technical field of metallurgy and battery material preparation, and in particular relates to a method for preparing electrolytic manganese dioxide for low-potassium and low-sodium lithium manganate. Background technique [0002] Electrolytic manganese dioxide is an excellent depolarizer for batteries. Compared with dry batteries produced by natural discharge manganese dioxide, it has the characteristics of large discharge capacity, strong activity, small size, and long life. It is mixed with 20%-30% The discharge capacity of dry batteries made of electrolytic manganese dioxide can be increased by 50% to 100% compared with dry batteries made of natural MnO2, and 50% to 70% of electrolytic manganese dioxide is mixed in high-performance zinc chloride batteries. The capacity can be increased by 2 to 3 times, and the discharge capacity of alkaline manganese batteries made entirely of electrolytic manganese dioxide can be increas...

Claims

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Application Information

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IPC IPC(8): C01G45/02H01M4/505H01M10/0525
CPCC01G45/02H01M4/505H01M10/0525Y02E60/10
Inventor罗冰陈其胜覃丽丽涂忠益黄朝辉梁彩玲
Owner广西下田锰矿有限责任公司