CN108539309A - A kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material - Google Patents
A kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material Download PDFInfo
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- CN108539309A CN108539309A CN201810280294.6A CN201810280294A CN108539309A CN 108539309 A CN108539309 A CN 108539309A CN 201810280294 A CN201810280294 A CN 201810280294A CN 108539309 A CN108539309 A CN 108539309A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The present invention discloses a kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material.Waste and old nickle cobalt lithium manganate battery is disassembled, positive plate is crushed, hydrogen reducing in reduction furnace is put into after broken material sieving；Reducing material is obtained to be washed with hot pure water, cleaning solution and washed-residue are obtained, cleaning solution is passed through carbon dioxide, obtains lithia water and aluminum hydroxide precipitation, aluminium hydroxide is calcined to obtain ultra-fine alumina, and obtained lithium bicarbonate obtains battery-level lithium carbonate by pyrolytic；Hydrazine hydrate solution is added in washed-residue, then sodium hydroxide is added and is stirred to react filtering, obtain the second filtrate and the second filter residue, second filter residue is put into vacuum drying chamber and is dried in vacuo, it is dry after material obtain nickel-cobalt-manganese ternary alloy powder after sieve magnetic separation or be directly added into acid and dissolve to obtain nickel-cobalt-manganese ternary mixed solution.The present invention is at low cost, and can realize the separation and recycling of full constituent, and the rate of recovery is high, and added value of product is big.
Description
Technical field
The present invention relates to a kind of recovery methods of waste and old nickel-cobalt lithium manganate cathode material, belong at lithium battery material waste
Manage technical field.
Background technology
With the development of new-energy automobile, a large amount of waste lithium cell is will produce, the recycling market scale expedited the emergence of is very huge
Greatly.The recycling of waste lithium cell is worth, the metals such as ternary material, cobalt, lithium, nickel mainly wherein.It is estimated that 2020
Year, relevant market space is up to 10,000,000,000 ranks.In recent years, since especially 2017, the associated metals price amount of increase such as cobalt, lithium is bright
It is aobvious, waste lithium cell is processed and utilized, is just being become more and more valuable.
Nickle cobalt lithium manganate battery energy density highest, and with advances in technology, there has also been matter to leap for safety,
Applied on various tools, charger baby even electric vehicle.
For the recycling of nickel-cobalt lithium manganate cathode material, since it contains the noble metals such as cobalt nickel, so its recovery value phase
To height, but conventional recovery process cost recovery is high, technological process is long and profit is low, will produce a large amount of waste water.
Invention content
In view of this, the present invention provides a kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material, flow is short, technique
Simply, at low cost, and can realize the separation and recycling of full constituent, the rate of recovery is high, and finally obtained product purity is high, product
Added value is big.
The present invention solves above-mentioned technical problem by following technological means：
A kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material, is following steps：
(1) pre-process, waste and old nickle cobalt lithium manganate battery is disassembled, by positive plate be put into liquid nitrogen frozen crusher into
Row is broken, is then sieved, and 100-200 mesh sieve is crossed, and oversize, which returns, continues freezing crushing, and screenings is spare；
(2) screenings that step (1) obtains is put into reduction furnace, is passed through hydrogen and is restored, screenings is in reduction furnace
The interior residence time is 8-12 hours, and charging thickness of the screenings in saggar is 3-5cm, flowing speed of the hydrogen in reduction furnace
Degree is 3-5m/s, restores hydrogen content in furnace atmosphere and is more than 99.5%, reduction temperature is 400-450 DEG C, then in reduction furnace
In cooling section be cooled to 40 DEG C of temperature ＜ after come out of the stove to obtain reducing material；
(3) it step (2) is obtained reducing material is put into the Storage Box full of nitrogen to preserve, hot pure water is then added and is washed
It washs, solid-to-liquid ratio 1：10-15 obtains cleaning solution and washed-residue by three-level countercurrent washing, and cleaning solution is passed through carbon dioxide,
Then it filters, obtains lithia water and aluminum hydroxide precipitation, by aluminum hydroxide precipitation after the washing of 3 stage countercurrents, pass through
Calcining, obtains ultra-fine alumina, obtained lithium bicarbonate obtains battery-level lithium carbonate by pyrolytic；
(4) hydrazine hydrate solution is added in the washed-residue for obtaining step (3), and the pH that sodium hydrate regulator solution is then added exists
13-14 is subsequently poured into stirring grinding jar, and it is 75-85 DEG C to be warming up to temperature, is stirred to react 1-2 hours, after then pouring out material
Filtering, obtains the second filtrate and the second filter residue, and hydrazine hydrate solution, which is added, in the second filter residue carries out 3 stage countercurrent washings, is then placed in
It is dried in vacuo in vacuum drying chamber, the material after drying is mixed with the cobalt powder, nickel powder and manganese powder of outsourcing after sieving magnetic separation
Close dispensing obtain nickel-cobalt-manganese ternary alloy powder or be directly added into acid dissolving obtain nickel-cobalt-manganese ternary mixed solution.
Saggar uses corundum, mullite or stainless steel saggar in the step (2).
The temperature of hot pure water washing reducing material process hot pure water is 75-90 DEG C in the step (3), is being passed through carbon dioxide
When carrying out precipitation of aluminium process, pH meter is inserted into cleaning solution, starts to be passed through carbon dioxide process, pH value continuously decreases, process production
It is raw to obtain aluminium hydroxide and lithium carbonate precipitation, then continuing to be passed through carbon dioxide, then the pH value of cleaning solution gradually rises, then
Until pH meter stops being passed through carbon dioxide after no longer changing, then it is filtered, aluminum hydroxide precipitation is after the washing of 3 stage countercurrents
Obtained washings are mixed with lithia water, and the mass ratio of washing process aluminum hydroxide precipitation and washings is 1:4, washing
The temperature of water is 35-45 DEG C, and the aluminum hydroxide precipitation calcination temperature after washing is 750-850 DEG C, and calcination time is 2-4 hours,
Temperature of the lithia water in pyrolytic is 95-99 DEG C, speed of agitator 150-200r/min, the resolving time 2.5
Hour, the filtrate after decomposition returns to washing reducing material, and obtained lithium carbonate is packaged to be battery-level lithium carbonate by drying sieving.
The mass ratio of a concentration of 0.5mol/L of hydrazine hydrate solution in step (4), washed-residue and hydrazine hydrate solution is 1:3,
The stirring of Ball-stirring mill is 30r/min, and the abrading-ball of addition is zirconium oxide material, and a diameter of 0.2-1cm of abrading-ball is passed through carbon dioxide
Gas make aluminum precipitation be aluminium hydroxide, aluminium hydroxide washing after with the aluminum hydroxide precipitation in step (3) it is admixed together into
Row calcining, a concentration of 0.06mol/L for the hydrazine hydrate solution that the second residue washing uses, the second filter residue process of vacuum drying are done
Dry temperature is 60-70 DEG C, and vacuum degree is -0.09~-0.08Mpa.
Nickel-cobalt-manganese ternary mixed solution return prepares nickel-cobalt lithium manganate cathode material in the step (4).
This patent is broken for fine particle by freezing crushing, by the aluminium foil for loading nickel-cobalt lithium manganate cathode material, then
Sieving, by hydrogen reducing at high temperature, while aluminium powder can also be reacted with the nickel cobalt manganese in nickle cobalt lithium manganate into line replacement, will
Nickel cobalt manganese is reduced to simple substance, and lithium exists in the form of an oxide, and then by washing, generation obtains lithium hydroxide solution, to
Quickly lithium is detached with cobalt nickel manganese, and washing process, it has part aluminium and is reacted with lithium hydroxide hence into lithium solution
In, then by being passed through carbon dioxide gas, aluminum precipitation is got off, while converting lithium hydroxide to lithium carbonate, is then proceeded to
It is passed through carbon dioxide, lithium carbonate is then converted into lithium bicarbonate and is dissolved into water again, realizes the separation of aluminium and lithium.
Obtained nickel cobalt manganese is passed through in hydrazine hydrate and reacting in sodium hydroxide mixed solution, and aluminium can be completely dissolved, simultaneously
The oxidation for also avoiding nickel cobalt manganese is obtained using the ternary metal powder or addition sulfuric acid solution that obtain nickel cobalt manganese after magnetic separation
Nickel-cobalt-manganese ternary solution.
The present invention utilizes hydrogen reducing, to realize the separation of lithium and nickel cobalt manganese, compares using acid dissolving so that nickel cobalt manganese
Lithium fully enters for the method detached again in solution, and technological process is short, and the rate of recovery of lithium is high, the rate of recovery of nickel cobalt manganese
Also high, at low cost, the wastewater flow rate of generation is few, can simply obtain very much the lithium carbonate of LITHIUM BATTERY, and obtained nickel cobalt manganese also may be used
Nickel-cobalt lithium manganate cathode material is done to return.Aluminium therein can be also recycled simultaneously, obtains ultra-fine alumina.
The beneficial effects of the invention are as follows：Flow is short, simple process and low cost, and can realize the separation of full constituent and return
It receives, the rate of recovery is high, and finally obtained product purity is high, and added value of product is big, realizes recycling for material.
Specific implementation mode
Below with reference to specific embodiment, the present invention is described in detail, a kind of waste and old nickle cobalt lithium manganate of the present embodiment
The recovery method of positive electrode is following steps：
(1) pre-process, waste and old nickle cobalt lithium manganate battery is disassembled, by positive plate be put into liquid nitrogen frozen crusher into
Row is broken, is then sieved, and 100-200 mesh sieve is crossed, and oversize, which returns, continues freezing crushing, and screenings is spare；
(2) screenings that step (1) obtains is put into reduction furnace, is passed through hydrogen and is restored, screenings is in reduction furnace
The interior residence time is 8-12 hours, and charging thickness of the screenings in saggar is 3-5cm, flowing speed of the hydrogen in reduction furnace
Degree is 3-5m/s, restores hydrogen content in furnace atmosphere and is more than 99.5%, reduction temperature is 400-450 DEG C, then in reduction furnace
In cooling section be cooled to 40 DEG C of temperature ＜ after come out of the stove to obtain reducing material；
(3) it step (2) is obtained reducing material is put into the Storage Box full of nitrogen to preserve, hot pure water is then added and is washed
It washs, solid-to-liquid ratio 1：10-15 obtains cleaning solution and washed-residue by three-level countercurrent washing, and cleaning solution is passed through carbon dioxide,
Then it filters, obtains lithia water and aluminum hydroxide precipitation, by aluminum hydroxide precipitation after the washing of 3 stage countercurrents, pass through
Calcining, obtains ultra-fine alumina, obtained lithium bicarbonate obtains battery-level lithium carbonate by pyrolytic；
(4) hydrazine hydrate solution is added in the washed-residue for obtaining step (3), and the pH that sodium hydrate regulator solution is then added exists
13-14 is subsequently poured into stirring grinding jar, and it is 75-85 DEG C to be warming up to temperature, is stirred to react 1-2 hours, after then pouring out material
Filtering, obtains the second filtrate and the second filter residue, and hydrazine hydrate solution, which is added, in the second filter residue carries out 3 stage countercurrent washings, is then placed in
It is dried in vacuo in vacuum drying chamber, the material after drying is mixed with the cobalt powder, nickel powder and manganese powder of outsourcing after sieving magnetic separation
Close dispensing obtain nickel-cobalt-manganese ternary alloy powder or be directly added into acid dissolving obtain nickel-cobalt-manganese ternary mixed solution.
Saggar uses corundum, mullite or stainless steel saggar in the step (2).
The temperature of hot pure water washing reducing material process hot pure water is 75-90 DEG C in the step (3), is being passed through carbon dioxide
When carrying out precipitation of aluminium process, pH meter is inserted into cleaning solution, starts to be passed through carbon dioxide process, pH value continuously decreases, process production
It is raw to obtain aluminium hydroxide and lithium carbonate precipitation, then continuing to be passed through carbon dioxide, then the pH value of cleaning solution gradually rises, then
Until pH meter stops being passed through carbon dioxide after no longer changing, then it is filtered, aluminum hydroxide precipitation is after the washing of 3 stage countercurrents
Obtained washings are mixed with lithia water, and the mass ratio of washing process aluminum hydroxide precipitation and washings is 1:4, washing
The temperature of water is 35-45 DEG C, and the aluminum hydroxide precipitation calcination temperature after washing is 750-850 DEG C, and calcination time is 2-4 hours,
Temperature of the lithia water in pyrolytic is 95-99 DEG C, speed of agitator 150-200r/min, the resolving time 2.5
Hour, the filtrate after decomposition returns to washing reducing material, and obtained lithium carbonate is packaged to be battery-level lithium carbonate by drying sieving.
The mass ratio of a concentration of 0.5mol/L of hydrazine hydrate solution in step (4), washed-residue and hydrazine hydrate solution is 1:3,
The stirring of Ball-stirring mill is 30r/min, and the abrading-ball of addition is zirconium oxide material, and a diameter of 0.2-1cm of abrading-ball is passed through carbon dioxide
Gas make aluminum precipitation be aluminium hydroxide, aluminium hydroxide washing after with the aluminum hydroxide precipitation in step (3) it is admixed together into
Row calcining, a concentration of 0.06mol/L for the hydrazine hydrate solution that the second residue washing uses, the second filter residue process of vacuum drying are done
Dry temperature is 60-70 DEG C, and vacuum degree is -0.09~-0.08Mpa.
Nickel-cobalt-manganese ternary mixed solution return prepares nickel-cobalt lithium manganate cathode material in the step (4).
Embodiment 1
A kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material, is following steps：
(1) pre-process, waste and old nickle cobalt lithium manganate battery is disassembled, by positive plate be put into liquid nitrogen frozen crusher into
Row is broken, is then sieved, and 150 mesh sieve is crossed, and oversize, which returns, continues freezing crushing, and screenings is spare；
(2) screenings that step (1) obtains is put into reduction furnace, is passed through hydrogen and is restored, screenings is in reduction furnace
The interior residence time is 10 hours, and charging thickness of the screenings in saggar is 4.5cm, flowing velocity of the hydrogen in reduction furnace
For 4m/s, restores hydrogen content in furnace atmosphere and be more than 99.5%, reduction temperature is 425 DEG C, the then cooling in reduction furnace
Section comes out of the stove to obtain reducing material after being cooled to 40 DEG C of temperature ＜；
(3) it step (2) is obtained reducing material is put into the Storage Box full of nitrogen to preserve, hot pure water is then added and is washed
It washs, solid-to-liquid ratio 1：12, by three-level countercurrent washing, cleaning solution and washed-residue are obtained, cleaning solution is passed through carbon dioxide, then
Filtering, obtains lithia water and aluminum hydroxide precipitation, by aluminum hydroxide precipitation after the washing of 3 stage countercurrents, by calcining,
Ultra-fine alumina is obtained, obtained lithium bicarbonate obtains battery-level lithium carbonate by pyrolytic；
(4) hydrazine hydrate solution is added in the washed-residue for obtaining step (3), and the pH that sodium hydrate regulator solution is then added exists
13.5, it is subsequently poured into stirring grinding jar, it is 79 DEG C to be warming up to temperature, is stirred to react 1.8 hours, mistake after then pouring out material
Filter, obtains the second filtrate and the second filter residue, and hydrazine hydrate solution, which is added, in the second filter residue carries out 3 stage countercurrent washings, is then placed in true
It is dried in vacuo in empty drying box, the material after drying mixes after sieving magnetic separation with the cobalt powder of outsourcing, nickel powder and manganese powder
Dispensing obtain nickel-cobalt-manganese ternary alloy powder or be directly added into acid dissolving obtain nickel-cobalt-manganese ternary mixed solution.
Saggar uses corundum sagger in the step (2).
The temperature of hot pure water washing reducing material process hot pure water is 79 DEG C in the step (3), is being passed through carbon dioxide
When precipitation of aluminium process, pH meter is inserted into cleaning solution, starts to be passed through carbon dioxide process, pH value continuously decreases, and process generates
Aluminium hydroxide and lithium carbonate precipitation are obtained, then is continuing to be passed through carbon dioxide, then the pH value of cleaning solution gradually rises, then directly
Stop being passed through carbon dioxide after to pH meter no longer changing, then be filtered, aluminum hydroxide precipitation obtains after the washing of 3 stage countercurrents
The washings arrived are mixed with lithia water, and the mass ratio of washing process aluminum hydroxide precipitation and washings is 1:4, washings
Temperature be 39 DEG C, aluminum hydroxide precipitation calcination temperature after washing is 790 DEG C, and calcination time is 3 hours, lithia water
Temperature in pyrolytic is 98 DEG C, speed of agitator 180r/min, and the resolving time is 2.5 hours, and the filtrate after decomposition is returned
Reducing material is washed in back scrubbing, and obtained lithium carbonate is packaged to be battery-level lithium carbonate by drying sieving.
The mass ratio of a concentration of 0.5mol/L of hydrazine hydrate solution in step (4), washed-residue and hydrazine hydrate solution is 1:3,
The stirring of Ball-stirring mill is 30r/min, and the abrading-ball of addition is zirconium oxide material, and a diameter of 0.2-1cm of abrading-ball is passed through carbon dioxide
Gas make aluminum precipitation be aluminium hydroxide, aluminium hydroxide washing after with the aluminum hydroxide precipitation in step (3) it is admixed together into
Row calcining, a concentration of 0.06mol/L for the hydrazine hydrate solution that the second residue washing uses, the second filter residue process of vacuum drying are done
Dry temperature is 66 DEG C, and vacuum degree is -0.085Mpa.
Nickel-cobalt-manganese ternary mixed solution return prepares nickel-cobalt lithium manganate cathode material in the step (4).
Finally obtained lithium carbonate meets the requirement of professional standard YS/T 582-2013.Obtained nickel-cobalt-manganese ternary alloy
Powder monitoring data are as follows：
| Ni+Co+Mn | Fe | Al | Zn | Li |
| 99.28% | 34ppm | 38ppm | 8ppm | 29ppm |
| Na | Ca | Mg | S | O |
| 28ppm | 21ppm | 19ppm | 24ppm | 0.13% |
Obtained ultra-fine alumina monitoring data are as follows：
| Main content | Na | Co | Ni | Mn | Ca |
| 99.53% | 25ppm | 2ppm | 2ppm | 5.1ppm | 5.9ppm |
| D50 | D100 | Primary particle size | BET | Sulfate radical | Tap density |
| 0.7 micron | 2.2 micron | 28nm | 112m2/g | 68ppm | 0.4g/mL |
The rate of recovery 99.2% of final lithium synthesis, the rate of recovery 97.9% of aluminium, the rate of recovery of nickel cobalt manganese is respectively 99.3%,
99.5% and 99.3%.
Embodiment 2
A kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material, is following steps：
(1) pre-process, waste and old nickle cobalt lithium manganate battery is disassembled, by positive plate be put into liquid nitrogen frozen crusher into
Row is broken, is then sieved, and 120 mesh sieve is crossed, and oversize, which returns, continues freezing crushing, and screenings is spare；
(2) screenings that step (1) obtains is put into reduction furnace, is passed through hydrogen and is restored, screenings is in reduction furnace
The interior residence time is 11 hours, and charging thickness of the screenings in saggar is 4.2cm, flowing velocity of the hydrogen in reduction furnace
For 4.5m/s, restores hydrogen content in furnace atmosphere and be more than 99.5%, reduction temperature is 440 DEG C, then cold in reduction furnace
But section comes out of the stove to obtain reducing material after being cooled to 40 DEG C of temperature ＜；
(3) it step (2) is obtained reducing material is put into the Storage Box full of nitrogen to preserve, hot pure water is then added and is washed
It washs, solid-to-liquid ratio 1：13, by three-level countercurrent washing, cleaning solution and washed-residue are obtained, cleaning solution is passed through carbon dioxide, then
Filtering, obtains lithia water and aluminum hydroxide precipitation, by aluminum hydroxide precipitation after the washing of 3 stage countercurrents, by calcining,
Ultra-fine alumina is obtained, obtained lithium bicarbonate obtains battery-level lithium carbonate by pyrolytic；
(4) hydrazine hydrate solution is added in the washed-residue for obtaining step (3), and the pH that sodium hydrate regulator solution is then added exists
13.8, it is subsequently poured into stirring grinding jar, it is 79 DEG C to be warming up to temperature, is stirred to react 1.5 hours, mistake after then pouring out material
Filter, obtains the second filtrate and the second filter residue, and hydrazine hydrate solution, which is added, in the second filter residue carries out 3 stage countercurrent washings, is then placed in true
It is dried in vacuo in empty drying box, the material after drying mixes after sieving magnetic separation with the cobalt powder of outsourcing, nickel powder and manganese powder
Dispensing obtain nickel-cobalt-manganese ternary alloy powder or be directly added into acid dissolving obtain nickel-cobalt-manganese ternary mixed solution.
Saggar uses mullite sagger in the step (2).
The temperature of hot pure water washing reducing material process hot pure water is 79 DEG C in the step (3), is being passed through carbon dioxide
When precipitation of aluminium process, pH meter is inserted into cleaning solution, starts to be passed through carbon dioxide process, pH value continuously decreases, and process generates
Aluminium hydroxide and lithium carbonate precipitation are obtained, then is continuing to be passed through carbon dioxide, then the pH value of cleaning solution gradually rises, then directly
Stop being passed through carbon dioxide after to pH meter no longer changing, then be filtered, aluminum hydroxide precipitation obtains after the washing of 3 stage countercurrents
The washings arrived are mixed with lithia water, and the mass ratio of washing process aluminum hydroxide precipitation and washings is 1:4, washings
Temperature be 39 DEG C, aluminum hydroxide precipitation calcination temperature after washing is 790 DEG C, and calcination time is 3 hours, lithia water
Temperature in pyrolytic is 98 DEG C, speed of agitator 180r/min, and the resolving time is 2.5 hours, and the filtrate after decomposition is returned
Reducing material is washed in back scrubbing, and obtained lithium carbonate is packaged to be battery-level lithium carbonate by drying sieving.
The mass ratio of a concentration of 0.5mol/L of hydrazine hydrate solution in step (4), washed-residue and hydrazine hydrate solution is 1:3,
The stirring of Ball-stirring mill is 30r/min, and the abrading-ball of addition is zirconium oxide material, and a diameter of 0.2-1cm of abrading-ball is passed through carbon dioxide
Gas make aluminum precipitation be aluminium hydroxide, aluminium hydroxide washing after with the aluminum hydroxide precipitation in step (3) it is admixed together into
Row calcining, a concentration of 0.06mol/L for the hydrazine hydrate solution that the second residue washing uses, the second filter residue process of vacuum drying are done
Dry temperature is 66 DEG C, and vacuum degree is -0.085Mpa.
Nickel-cobalt-manganese ternary mixed solution return prepares nickel-cobalt lithium manganate cathode material in the step (4).
Finally obtained lithium carbonate meets the requirement of professional standard YS/T 582-2013.Obtained nickel-cobalt-manganese ternary alloy
Powder monitoring data are as follows：
Obtained ultra-fine alumina monitoring data are as follows：
| Main content | Na | Co | Ni | Mn | Ca |
| 99.51% | 25ppm | 2.1ppm | 1.8ppm | 5.1ppm | 5.8ppm |
| D50 | D100 | Primary particle size | BET | Sulfate radical | Tap density |
| 0.8 micron | 2.1 micron | 22nm | 123m2/g | 65ppm | 0.4g/mL |
The rate of recovery 99.2% of final lithium synthesis, the rate of recovery 97.8% of aluminium, the rate of recovery of nickel cobalt manganese is respectively 99.3%,
99.5% and 99.2%.
Embodiment 3
A kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material, is following steps：
(1) pre-process, waste and old nickle cobalt lithium manganate battery is disassembled, by positive plate be put into liquid nitrogen frozen crusher into
Row is broken, is then sieved, and 170 mesh sieve is crossed, and oversize, which returns, continues freezing crushing, and screenings is spare；
(2) screenings that step (1) obtains is put into reduction furnace, is passed through hydrogen and is restored, screenings is in reduction furnace
The interior residence time is 9.5 hours, and charging thickness of the screenings in saggar is 4.5cm, flowing speed of the hydrogen in reduction furnace
Degree is 4.2m/s, restores hydrogen content in furnace atmosphere and is more than 99.5%, reduction temperature is 440 DEG C, then in reduction furnace
Cooling section comes out of the stove to obtain reducing material after being cooled to 40 DEG C of temperature ＜；
(3) it step (2) is obtained reducing material is put into the Storage Box full of nitrogen to preserve, hot pure water is then added and is washed
It washs, solid-to-liquid ratio 1：11, by three-level countercurrent washing, cleaning solution and washed-residue are obtained, cleaning solution is passed through carbon dioxide, then
Filtering, obtains lithia water and aluminum hydroxide precipitation, by aluminum hydroxide precipitation after the washing of 3 stage countercurrents, by calcining,
Ultra-fine alumina is obtained, obtained lithium bicarbonate obtains battery-level lithium carbonate by pyrolytic；
(4) hydrazine hydrate solution is added in the washed-residue for obtaining step (3), and the pH that sodium hydrate regulator solution is then added exists
13.8, it is subsequently poured into stirring grinding jar, it is 82 DEG C to be warming up to temperature, is stirred to react 1.6 hours, mistake after then pouring out material
Filter, obtains the second filtrate and the second filter residue, and hydrazine hydrate solution, which is added, in the second filter residue carries out 3 stage countercurrent washings, is then placed in true
It is dried in vacuo in empty drying box, the material after drying mixes after sieving magnetic separation with the cobalt powder of outsourcing, nickel powder and manganese powder
Dispensing obtain nickel-cobalt-manganese ternary alloy powder or be directly added into acid dissolving obtain nickel-cobalt-manganese ternary mixed solution.
Saggar uses stainless steel saggar in the step (2).
The temperature of hot pure water washing reducing material process hot pure water is 79 DEG C in the step (3), is being passed through carbon dioxide
When precipitation of aluminium process, pH meter is inserted into cleaning solution, starts to be passed through carbon dioxide process, pH value continuously decreases, and process generates
Aluminium hydroxide and lithium carbonate precipitation are obtained, then is continuing to be passed through carbon dioxide, then the pH value of cleaning solution gradually rises, then directly
Stop being passed through carbon dioxide after to pH meter no longer changing, then be filtered, aluminum hydroxide precipitation obtains after the washing of 3 stage countercurrents
The washings arrived are mixed with lithia water, and the mass ratio of washing process aluminum hydroxide precipitation and washings is 1:4, washings
Temperature be 42 DEG C, aluminum hydroxide precipitation calcination temperature after washing is 820 DEG C, and calcination time is 3.8 hours, and lithium bicarbonate is molten
Temperature of the liquid in pyrolytic is 98 DEG C, speed of agitator 185r/min, and the resolving time is 2.5 hours, the filtrate after decomposition
Washing reducing material is returned to, obtained lithium carbonate is packaged to be battery-level lithium carbonate by drying sieving.
The mass ratio of a concentration of 0.5mol/L of hydrazine hydrate solution in step (4), washed-residue and hydrazine hydrate solution is 1:3,
The stirring of Ball-stirring mill is 30r/min, and the abrading-ball of addition is zirconium oxide material, and a diameter of 0.2-1cm of abrading-ball is passed through carbon dioxide
Gas make aluminum precipitation be aluminium hydroxide, aluminium hydroxide washing after with the aluminum hydroxide precipitation in step (3) it is admixed together into
Row calcining, a concentration of 0.06mol/L for the hydrazine hydrate solution that the second residue washing uses, the second filter residue process of vacuum drying are done
Dry temperature is 68 DEG C, and vacuum degree is -0.083Mpa.
Nickel-cobalt-manganese ternary mixed solution return prepares nickel-cobalt lithium manganate cathode material in the step (4).
Finally obtained lithium carbonate meets the requirement of professional standard YS/T 582-2013.Obtained nickel-cobalt-manganese ternary alloy
Powder monitoring data are as follows：
| Ni+Co+Mn | Fe | Al | Zn | Li |
| 99.31% | 28ppm | 29ppm | 6ppm | 31ppm |
| Na | Ca | Mg | S | O |
| 29ppm | 21ppm | 18ppm | 28ppm | 0.11% |
Obtained ultra-fine alumina monitoring data are as follows：
| Main content | Na | Co | Ni | Mn | Ca |
| 99.48% | 25ppm | 2.1ppm | 3.5ppm | 5.1ppm | 6.7ppm |
| D50 | D100 | Primary particle size | BET | Sulfate radical | Tap density |
| 0.7 micron | 2.0 micron | 21nm | 128m2/g | 61ppm | 0.4g/mL |
The rate of recovery 99.3% of final lithium synthesis, the rate of recovery 97.9% of aluminium, the rate of recovery of nickel cobalt manganese is respectively 99.4%,
99.5% and 99.3%.
Often handle one ton of discarded nickel-cobalt lithium manganate material, the wastewater flow rate that the embodiment of the present invention 1,2 and 3 generates less than
15 tons, and use conventional sulfuric acid solution, precipitation except aluminium, extraction and separation nickel cobalt manganese, carbonizatin method prepare the work of battery-level lithium carbonate
The wastewater flow rate of skill, generation is more than 30 tons, and the rate of recovery of lithium is low, is usually no more than 99%, and technological process is long.
Finally illustrate, the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to compared with
Good embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the right of invention.
Claims (5)
1. a kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material, which is characterized in that be following steps：
(1) it pre-processes, waste and old nickle cobalt lithium manganate battery is disassembled, positive plate is put into liquid nitrogen frozen crusher and is broken
It is broken, it is then sieved, crosses 100-200 mesh sieve, oversize, which returns, continues freezing crushing, and screenings is spare；
(2) screenings that step (1) obtains is put into reduction furnace, is passed through hydrogen and is restored, screenings is in reduction furnace
Residence time is 8-12 hours, and charging thickness of the screenings in saggar is 3-5cm, and flowing velocity of the hydrogen in reduction furnace is
3-5m/s restores hydrogen content in furnace atmosphere and is more than 99.5%, and reduction temperature is 400-450 DEG C, then in reduction furnace
Cooling section comes out of the stove to obtain reducing material after being cooled to 40 DEG C of temperature ＜；
(3) it step (2) is obtained reducing material is put into the Storage Box full of nitrogen to preserve, hot pure water is then added and is washed,
Solid-to-liquid ratio is 1：10-15 obtains cleaning solution and washed-residue by three-level countercurrent washing, cleaning solution is passed through carbon dioxide, then
Filtering, obtains lithia water and aluminum hydroxide precipitation, by aluminum hydroxide precipitation after the washing of 3 stage countercurrents, by calcining,
Ultra-fine alumina is obtained, obtained lithium bicarbonate obtains battery-level lithium carbonate by pyrolytic；
(4) hydrazine hydrate solution is added in the washed-residue for obtaining step (3), and the pH of sodium hydrate regulator solution is then added in 13-
14, it is subsequently poured into stirring grinding jar, it is 75-85 DEG C to be warming up to temperature, is stirred to react 1-2 hours, mistake after then pouring out material
Filter, obtains the second filtrate and the second filter residue, and hydrazine hydrate solution, which is added, in the second filter residue carries out 3 stage countercurrent washings, is then placed in true
It is dried in vacuo in empty drying box, the material after drying mixes after sieving magnetic separation with the cobalt powder of outsourcing, nickel powder and manganese powder
Dispensing obtain nickel-cobalt-manganese ternary alloy powder or be directly added into acid dissolving obtain nickel-cobalt-manganese ternary mixed solution.
2. a kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material according to claim 1, it is characterised in that：It is described
Saggar uses corundum, mullite or stainless steel saggar in step (2).
3. a kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material according to claim 1, it is characterised in that：It is described
The temperature of hot pure water washing reducing material process hot pure water is 75-90 DEG C in step (3), carrys out precipitation of aluminium process being passed through carbon dioxide
When, pH meter is inserted into cleaning solution, starts to be passed through carbon dioxide process, pH value continuously decreases, and process generates to obtain hydroxide
Aluminium and lithium carbonate precipitation, then continuing to be passed through carbon dioxide, then the pH value of cleaning solution gradually rises, then until pH meter no longer
Stop being passed through carbon dioxide after variation, then be filtered, the washings that aluminum hydroxide precipitation obtains after the washing of 3 stage countercurrents
It is mixed with lithia water, the mass ratio of washing process aluminum hydroxide precipitation and washings is 1:4, the temperature of washings is
35-45 DEG C, the aluminum hydroxide precipitation calcination temperature after washing is 750-850 DEG C, and calcination time is 2-4 hours, and lithium bicarbonate is molten
Temperature of the liquid in pyrolytic is 95-99 DEG C, speed of agitator 150-200r/min, and the resolving time is 2.5 hours, after decomposition
Filtrate return to washing reducing material, obtained lithium carbonate is packaged to be battery-level lithium carbonate by drying sieving.
4. a kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material according to claim 1, it is characterised in that：Step
(4) mass ratio of a concentration of 0.5mol/L of hydrazine hydrate solution in, washed-residue and hydrazine hydrate solution is 1:3, the stirring of Ball-stirring mill
Abrading-ball for 30r/min, addition is zirconium oxide material, and a diameter of 0.2-1cm of abrading-ball is passed through carbon dioxide gas and so that aluminium is heavy
It is aluminium hydroxide to form sediment, after aluminium hydroxide washing with the aluminum hydroxide precipitation in step (3) is admixed together is calcined, the second filter
A concentration of 0.06mol/L of the hydrazine hydrate solution of use is washed in wash heat, and the drying temperature of the second filter residue process of vacuum drying is 60-70
DEG C, vacuum degree is -0.09~-0.08Mpa.
5. a kind of recovery method of waste and old nickel-cobalt lithium manganate cathode material according to claim 1, it is characterised in that：It is described
Nickel-cobalt-manganese ternary mixed solution return prepares nickel-cobalt lithium manganate cathode material in step (4).
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