CN109825714A - A kind of method that nickel protoxide reclaimed materials is used to synthesize lithium electricity anode material precursor raw material - Google Patents
A kind of method that nickel protoxide reclaimed materials is used to synthesize lithium electricity anode material precursor raw material Download PDFInfo
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- CN109825714A CN109825714A CN201910214873.5A CN201910214873A CN109825714A CN 109825714 A CN109825714 A CN 109825714A CN 201910214873 A CN201910214873 A CN 201910214873A CN 109825714 A CN109825714 A CN 109825714A
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- nickel
- lithium electricity
- reclaimed materials
- sulfuric acid
- protoxide
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Abstract
The present invention relates to waste recoveries to utilize field, discloses a kind of method that nickel protoxide reclaimed materials is used to synthesize lithium electricity anode material precursor raw material, described method includes following steps: (1) nickel protoxide reclaimed materials mechanical activation；(2) the nickel protoxide reclaimed materials after mechanical activation is leached with sulfuric acid；(3) sulfuric acid being soluble in the supplies consumption step (2) of the nickeliferous of sulfuric acid, cobalt, manganese is added in leachate, hydrogen peroxide is added to 4 or more pH value, nickel leachate is obtained after separation of solid and liquid；(4) the nickel leachate after taking step (3) consumption acid is configured to lithium electricity anode material precursor solution by nickel, cobalt, manganese lithium electricity positive electrode proportion requirement supplying vitriol.Process of the present invention is short, simple and easy, and the nickel protoxide rate of recovery is high, at low cost, small investment, it is easy to accomplish industrialization, economic and social benefits are obvious.
Description
Technical field
The invention belongs to waste recoveries to utilize field, and in particular to a kind of nickel protoxide reclaimed materials is positive for synthesizing lithium electricity
The method of material precursor raw material.
Background technique
Lithium ion battery is current chemical cell that can be best for Rechargeability industrialized in the world, often in recent years
The lithium ion battery that year produces has several hundred million, and is increased year by year with the speed for being more than 20%.Original needed for producing lithium ion battery
Expect nickel, the demand of cobalt increases rapidly also with the fast development of lithium ion battery industry, nickel cobalt manganese systems ternary lithium ion battery
Positive electrode has become the product of lithium ion battery mainstream, and nickelic lithium ion battery became the following lithium ion battery development in recent years
Direction, the demand to nickel raw material can also increase.
Nickel protoxide be light green or dark green powder shape solid, have good catalytic activity, ferromagnetism, temperature-sensitive air-sensitive and
Electroluminescent properties are a kind of important inorganic functional materials, are widely used in the national defence such as electronic information, metallurgy, chemical
Safety and social life field.For example, being used as the adhesive agent and colorant of enamel in ceramic industry, ceramic industry is used as colorant
Raw material, the raw material of nickel-zinc ferrite is used as in magnetic materials production, in glass industry dark-brown glass and picture tube glass bulb
Toner, and the material of manufacture nickel salt, Raney nickel and secondary cell.Domestic production nickel protoxide is mainly using spraying at present
The technology calcined after pyrolytic technique and chemical synthesis.Nickel protoxide product generally all passes through high-temperature process, and the oxidation after failure is sub-
The recycling difficulty of nickel is high, now also seldom to the research in the field.
Summary of the invention
To solve the problems, such as to give up in the prior art, nickel protoxide recycling difficulty is big and cost recovery is high, and the present invention provides
A kind of method that nickel protoxide reclaimed materials is used to synthesize lithium electricity anode material precursor raw material, described method includes following steps:
(1) nickel protoxide reclaimed materials mechanical activation；
(2) the nickel protoxide reclaimed materials after mechanical activation is leached with sulfuric acid；
(3) sulfuric acid being soluble in the supplies consumption step (2) of the nickeliferous of sulfuric acid, cobalt, manganese is added in leachate, oxidant is added
Or reducing agent obtains nickel leachate to 4.0 or more pH value after separation of solid and liquid；
(4) the nickel leachate after taking step (3) consumption acid is incorporated vitriol by nickel, cobalt, manganese lithium electricity positive electrode proportion requirement
It is configured to lithium electricity anode material precursor solution.
The mechanical activation is vibromill with equipment, and the time of mechanical activation is 10-30min, after activation material D50 0 ~
20μm。
It is 1.8 ~ 6.0mol/L that the condition that sulfuric acid is leached in the step (2), which is sulfuric acid concentration, liquid-solid ratio 2:1 ~ 7:
1,80-100 DEG C of temperature, 1.0 ~ 10h of extraction time.
The material of nickeliferous, cobalt, manganese is selected from lithium electricity positive electrode material precursor or lithium electricity anode material waste in the step (3)
Material or nickel powder, nickel button, cobalt powder, electrolytic manganese, in manganese powder any one or combinations thereof.
The present invention by the cooperation of mechanical activation and sulfuric acid system, overcome give up in the prior art the recycling of nickel protoxide difficulty and
The high problem of cost recovery, be it is a kind of simple, efficiently, be easy to the nickel protoxide reclaimed materials of bulk industrial for the positive material of lithium electricity
Expect synthetic method, for synthesizing lithium electricity positive electrode material precursor after recycling, process flow is short, does not need special reagent and sets
It is standby, it is at low cost, there is significant economic benefit.
Specific embodiment
In the present invention there are two types of nickel protoxide reclaimed materials, number 1#, 2#, ingredient is shown in Table 1.It can be seen by the data in table
Out, which is very pure nickel-containing material, and comparison synthesizes the raw material sulphuric acid nickel index of lithium electricity positive electrode material precursor,
Impurity index in the raw material can reach its requirement.
1 nickel protoxide reclaimed materials chemical component (%) of table
The spherical shape or ellipsoidal particle that nickel protoxide reclaimed materials in the present invention in step (1) is granularity 1mm or so, hardness is big,
Activity is low, purity is high, improves its activity using the method for mechanical activation to the material.Mechanical activation time 10-30min, oxidation
Sub- Nickel particle degree D50 is at 0 ~ 20 μm.
Sulfuric acid concentration described in step (2) is 1.8 ~ 6.0mol/L, liquid-solid ratio 2:1 ~ 7:1,80 ~ 100 DEG C of temperature, is leached
1.0 ~ 10h of time, the nickel concentration after leaching in solution are greater than 90g/L, do not have leached mud after leaching.
The raw material that the consumption acid of leachate described in step (3) uses is lithium electricity positive electrode material precursor or lithium electricity positive electrode
Waste material or nickel powder, nickel button, cobalt powder, electrolytic manganese, manganese powder be nickeliferous, the material of cobalt, manganese etc., after these raw materials consumption acid in solution
Impurity content to meet the requirement of impurity content in lithium electricity positive electrode material precursor synthesis material, suitable oxygen is added depending on material
Acid in nickel protoxide leachate is consumed to 4.0 or more pH value by agent or reducing agent.
Filter residue continues on for nickel protoxide leachate consumption acid after separation of solid and liquid described in the step (3).After consumption acid
Solution according to the type of synthesized lithium electricity positive electrode material precursor be added the sulfate such as cobaltous sulfate, manganese sulfate of scarce element etc. match
At the solution of synthesis lithium electricity positive electrode material precursor.
Embodiment 1
Nickel protoxide reclaimed materials is added water 1.45L, is heated to 100 DEG C, weighed with after vibromill mechanical activation 10min in beaker
Nickel protoxide after 700g mechanical activation is slowly added into beaker, is added dropwise to 98% sulfuric acid 500mL, leaches 10h, and nickel protoxide is complete
Portion's dissolution.Leachate adds water 4.35L to be diluted to nickel concentration 90g/L or so, is cooled to 60 DEG C, takes 10g lithium electricity positive material waste
It is added in beaker, first dissolves 0.5h, after solution acidity reduces, hydrogen peroxide 5mL is added dropwise, solution ph is 4.0 after consumption acid, solid-liquid point
From the solution is incorporated 947g cobaltous sulfate and 815g manganese sulfate, while being diluted with water to nickel in solution, cobalt, manganese total ion concentration
90g/L obtains liquid before lithium electricity anode material precursor, can be used for synthesizing lithium electricity positive electrode.
Embodiment 2
Nickel protoxide reclaimed materials is taken 1000g to be placed in 7L pure water, is added with 0.5L/h speed with after vibromill mechanical activation 30min
Enter concentrated sulfuric acid 715mL, leaches acid concentration 1.8mol/L, after being warming up to 80 DEG C, leaching 5h, nickel protoxide all dissolves, to
1.5L pure water is added in reaction vessel, 60 DEG C of reaction temperature, the useless ternary precursor material of 10g is added, after dissolving 0.5h, is added sub-
Sodium sulphate 3g, until solution ph is 4.6, filtering, filtrate is incorporated 427g cobaltous sulfate and 245g manganese sulfate, is diluted with water in solution
Concentration of metal ions 9090g/L obtains liquid before lithium electricity anode material precursor synthesizes, can be used for synthesizing lithium electricity positive electrode.
Embodiment 3
The sulfuric acid 3.75L that 6moL/L is previously added in 30L reaction kettle is preheated to 90 DEG C, opens stirring, and nickel protoxide reclaimed materials is used
After vibromill mechanical activation 20min, 1724g is weighed at once, is added in reaction kettle to be stirred and is leached 1.0h, nickel protoxide recycling
After dissolution, 7L pure water is all added into the reaction kettle for material, and 15g cobalt powder is added, and first dissolves 0.5h, after solution acidity reduces, drop
Add hydrogen peroxide 7mL, finally the pH value of the solution is 5.0, is incorporated 740g cobaltous sulfate and 425 manganese sulfates, is diluted with water in solution
Concentration of metal ions 90g/L obtains liquid before lithium electricity anode material precursor synthesizes, can be used for synthesizing lithium electricity positive electrode.
Embodiment 4
The sulfuric acid 3.75L that 6moL/L is previously added in 30L reaction kettle is preheated to 100 DEG C, opens stirring, and nickel protoxide reclaimed materials is used
After vibromill mechanical activation 10min, 1724g is weighed at once, is added in reaction kettle to be stirred and is leached 1.0h, nickel protoxide recycling
After dissolution, 7L pure water is all added into the reaction kettle for material, and 15g cobalt powder is added, and first dissolves 0.5h, after solution acidity reduces, drop
Add hydrogen peroxide 7mL, finally the pH value of the solution is 5.0, is incorporated 740g cobaltous sulfate and 425 manganese sulfates, is diluted with water in solution
Concentration of metal ions 90g/L obtains liquid before lithium electricity anode material precursor synthesizes, can be used for synthesizing lithium electricity positive electrode.
Embodiment 5
Nickel protoxide reclaimed materials is taken 1000g to be placed in 2L pure water, is added with 0.5L/h speed with after vibromill mechanical activation 30min
Enter concentrated sulfuric acid 715mL, leaches acid concentration 1.8mol/L, after being warming up to 80 DEG C, leaching 5h, nickel protoxide all dissolves, to
1.5L pure water is added in reaction vessel, 60 DEG C of reaction temperature, the useless ternary precursor material of 10g is added, after dissolving 0.5h, is added sub-
Sodium sulphate 3g, until solution ph is 4.6, filtering, filtrate is incorporated 427g cobaltous sulfate and 245g manganese sulfate, is diluted with water in solution
Concentration of metal ions 9090g/L obtains liquid before lithium electricity anode material precursor synthesizes, can be used for synthesizing lithium electricity positive electrode.
Embodiment 6
Nickel protoxide reclaimed materials is taken 1000g to be placed in 4L pure water, is added with 0.5L/h speed with after vibromill mechanical activation 30min
Enter concentrated sulfuric acid 715mL, leaches acid concentration 1.8mol/L, after being warming up to 80 DEG C, leaching 5h, nickel protoxide all dissolves, to
1.5L pure water is added in reaction vessel, 60 DEG C of reaction temperature, the useless ternary precursor material of 10g is added, after dissolving 0.5h, is added sub-
Sodium sulphate 3g, until solution ph is 4.6, filtering, filtrate is incorporated 427g cobaltous sulfate and 245g manganese sulfate, is diluted with water in solution
Concentration of metal ions 9090g/L obtains liquid before lithium electricity anode material precursor synthesizes, can be used for synthesizing lithium electricity positive electrode.
Nickel nickel protoxide reclaimed materials is the black spheric granules of 1mm or so in the present invention, purity is high, nickeliferous up to 77% or more,
To use rear deactivated material, the raw material is complete under the conditions of 90 DEG C of temperature with the sulfuric acid solution of 2-9mol/L in the prior art
It cannot leach entirely.300 DEG C or so high temperature are both needed to the sulfuric acid of high concentration and hydrochloric acid, 6h or more can just be leached.It is put after mechanical activation
It cannot be leached completely after setting 3h with the sulfuric acid of 2M, 20h or more low-concentration sulfuric acid can hardly leach after mechanical activation, develop such
The method of material rationally recycled has very big economic benefit and social benefit.The present invention be it is a kind of simple, efficiently,
It is easy to the nickel protoxide reclaimed materials of bulk industrial for lithium electricity positive electrode synthetic method, and method is simple, it is easily operated,
The rate of recovery is high, and for synthesizing lithium electricity positive electrode material precursor after recycling, process flow is short, does not need special reagent and equipment,
It is at low cost, there is significant economic benefit.
Claims (4)
1. a kind of method that nickel protoxide reclaimed materials is used to synthesize lithium electricity anode material precursor raw material, which is characterized in that described
Method includes the following steps:
(1) nickel protoxide reclaimed materials mechanical activation；
(2) the nickel protoxide reclaimed materials after mechanical activation is leached with sulfuric acid；
(3) sulfuric acid being soluble in the supplies consumption step (2) of the nickeliferous of sulfuric acid, cobalt, manganese is added in leachate, oxidant is added
Or reducing agent obtains nickel leachate to 4.0 or more pH value after separation of solid and liquid；
(4) the nickel leachate after taking step (3) consumption acid is incorporated vitriol by nickel, cobalt, manganese lithium electricity positive electrode proportion requirement
It is configured to lithium electricity anode material precursor solution.
2. the method that nickel protoxide reclaimed materials according to claim 1 is used to synthesize lithium electricity anode material precursor raw material,
It is characterized by: the mechanical activation is vibromill with equipment, the time of mechanical activation is 10-30min, material D50 after activation
At 0 ~ 20 μm.
3. the method that nickel protoxide reclaimed materials according to claim 1 is used to synthesize lithium electricity anode material precursor raw material,
It is characterized by: it is 1.8 ~ 6.0mol/L that the condition that sulfuric acid is leached in the step (2), which is sulfuric acid concentration, liquid-solid ratio 2:1 ~
7:1,80-100 DEG C of temperature, 1.0 ~ 10h of extraction time.
4. the method that nickel protoxide reclaimed materials according to claim 1 is used to synthesize lithium electricity anode material precursor raw material,
It is characterized by: the material of nickeliferous, cobalt, manganese is selected from lithium electricity positive electrode material precursor or lithium electricity positive electrode in the step (3)
Waste material or nickel powder, nickel button, cobalt powder, electrolytic manganese, in manganese powder any one or combinations thereof.
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| CN201910214873.5A CN109825714B (en) | 2019-03-20 | 2019-03-20 | Method for synthesizing precursor raw material of lithium battery positive electrode material by using nickel protoxide reclaimed material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110468289A (en) * | 2019-09-12 | 2019-11-19 | 金川集团股份有限公司 | A kind of method that three sections of counter current acid leachings recycle after spherical shape nickel protoxide mechanical activation |
| CN110607439A (en) * | 2019-09-12 | 2019-12-24 | 金川集团股份有限公司 | Spherical nickel protoxide sectional oxidation acid leaching treatment method |
| CN115353160A (en) * | 2022-09-22 | 2022-11-18 | 福建常青新能源科技有限公司 | Preparation method of battery-grade nickel-cobalt-manganese ternary sulfate solution |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545504A (en) * | 2013-10-17 | 2014-01-29 | 江西赣锋锂业股份有限公司 | Preparation method of ternary anode material precursor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103545504A (en) * | 2013-10-17 | 2014-01-29 | 江西赣锋锂业股份有限公司 | Preparation method of ternary anode material precursor |
Non-Patent Citations (1)
| Title |
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| 于振涛等: "废镍催化剂的回收利用", 《当代化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110468289A (en) * | 2019-09-12 | 2019-11-19 | 金川集团股份有限公司 | A kind of method that three sections of counter current acid leachings recycle after spherical shape nickel protoxide mechanical activation |
| CN110607439A (en) * | 2019-09-12 | 2019-12-24 | 金川集团股份有限公司 | Spherical nickel protoxide sectional oxidation acid leaching treatment method |
| CN115353160A (en) * | 2022-09-22 | 2022-11-18 | 福建常青新能源科技有限公司 | Preparation method of battery-grade nickel-cobalt-manganese ternary sulfate solution |
| CN115353160B (en) * | 2022-09-22 | 2024-06-14 | 福建常青新能源科技有限公司 | Preparation method of battery-grade nickel-cobalt-manganese ternary sulfate solution |
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