CN101381817A - Method for directly recovering and producing electrowinning cobalt from waste and old lithium ionic cell - Google Patents
Method for directly recovering and producing electrowinning cobalt from waste and old lithium ionic cell Download PDFInfo
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- CN101381817A CN101381817A CNA2007100322912A CN200710032291A CN101381817A CN 101381817 A CN101381817 A CN 101381817A CN A2007100322912 A CNA2007100322912 A CN A2007100322912A CN 200710032291 A CN200710032291 A CN 200710032291A CN 101381817 A CN101381817 A CN 101381817A
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- hydrochloric acid
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
Abstract
The invention discloses a method for directly recovering and producing electro deposited cobalt from waste lithium ion cells. The method is mainly characterized in that: firstly, the waste lithium ion cells are disassembled and separated to obtain positive plates; secondly, the positive plates are immersed by an organic solvent N-methylformamide (NMP), and aluminum foils and anode materials of a current collector are separated; thirdly, the anode materials which contain lithium cobaltate are leached out by a hydrochloric acid and hydrogen peroxide system, and undissolved substances are filtered and separated; and fourthly, the electro deposited cobalt is obtained after electrodeposition of filtrate. By adoption of the method, the recovery rate of the cobalt in the waste lithium ion cells can be about 97.0 percent, and the purity of the electro deposited cobalt can be more than 99.8 percent.
Description
Technical field
The invention belongs to hydrometallurgy and metal electrodeposition field, more specifically relate to a kind ofly from waste and old lithium ion battery, directly to reclaim, the method for production electrodeposited cobalt.
Background technology
Lithium ion battery since realizing commercialization because its energy density height, in light weight, the life-span long and memoryless property is widely used.It is believed that breath Estate Division statistics, the cellphone subscriber of China increases very rapid, by 200,000,000 families in 2003,3.64 hundred million families in 2004 and 3.87 hundred million families in 2005, develop into 4.8 hundred million families in by the end of March, 2007, and surpass 6,000,000 the number development that Adds User with every month, become the maximum mobile communication big country in the whole world; Simultaneously along with the enhancing of china's overall national strength, the fast development of the level of consumption, China also becomes the production and one of consumption big country of the maximum digital products such as notebook computer in the whole world.Battery of mobile phone, MP3 rechargeable battery and laptop electric power etc. mainly are lithium ion batteries, and its mean lifetime was generally 2～3 years, and along with the lithium ion battery consumption increases rapidly, the lithium ion battery of scrapping also will increase considerably year by year.And contain a large amount of valuable metal elements in the waste and old lithium ion battery, wherein about 14%, the aluminium 4.7% of about 15%, the copper of cobalt, iron 2.5% and lithium 0.1% etc., to produce huge economic benefit if can reclaim, calculate with 2 batteries by every mobile phone, China at about about 1,000,000,000 with battery of mobile phone, scraps after 3 years at present fully, every lithium ion battery on average calculates by 20 grams, heavily about 20,000 tons, about 3000 tons of contained cobalt amount is worth about 1,500,000,000 yuan.Simultaneously, the recycling of old and useless battery can reduce its (as lithium hexafluoro phosphate etc.) pollution to environment that contains hazardous substance, economize on resources, cut down the consumption of energy, and can alleviate China's strategic resource cobalt metal shortage, long-term nervous situation according to anti-import promotes the Sustainable development of China's battery industry, realizes the industrial ecology circulation of battery industry.
At present, the recycling technical study of domestic old and useless battery still belongs to the starting stage, and the main technique of employing is dissolving, purifies, and then extracts cobalt salt with extraction process, chemical precipitation method etc. from solution.As Wu Fangzai " China YouSe Acta Metallurgica Sinica " Vol.54No.4,2004,697～701 introduce the employing alkali dissolution, and acidleach goes out, P204 extracting and purifying, P507 extracting and separating cobalt, lithium, back extraction reclaim(ed) sulfuric acid cobalt; Guo Liping etc. are at " battery " Vol.35No.4, adopt sulfuric acid and hydrogen peroxide system to leach useless cobalt acid lithium material in 2005,266～268, and employing sodium hydroxide is precipitation agent, with Co
2+Be converted into Co (OH)
2After, calcine recovery Co down at 300 ℃
2O
3Tan Haixiang etc. are at " power technology " Vol.31No.4, adopt acidleach in 2007,288～290, and bicarbonate of ammonia removes aluminium, and ammonium oxalate sinks cobalt, obtains the cobalt oxalate product.Foreign matter content height such as aluminium, magnesium, calcium in this class methods products obtained therefrom, technical process is long, the equipment requirements height, the cost height, added value of product is low, often needs deep processing, becomes electrolytic cobalt, high value added products such as cobalt powder.
Summary of the invention
The object of the present invention is to provide a kind ofly from waste and old lithium ion battery, directly reclaim, the method for production electrodeposited cobalt, technology of the present invention is simple relatively, flow process is short, production cost is low, cobalt rate of recovery height is low in the pollution of the environment.Electrodeposited cobalt purity height of the present invention, purposes is wide, the added value of product height.
For achieving the above object, the present invention has adopted following technical scheme:
Fig. 4 is recovery process figure of the present invention.
As shown in Figure 4: the present invention adopt professional battery to disassemble machine (patent No.: ZL200620059829.X) disassemble waste and old lithium ion battery, the lithium ion cell positive scrap stock that artificial separation obtains containing cobalt positive plate or battery production producer are raw material; After N-methyl-2-pyrrolidone (NMP) immersion, separate aluminium foil and positive electrode active materials; After adopting hydrochloric acid and hydrogen peroxide to leach positive electrode active materials; The gained leach liquor behind the electrodeposition, obtains the electrowinning cobalt and realizes above purpose in Winning cell.
Among the present invention, the positive plate of the waste and old lithium ion battery of handling is that positive electrode material is applied on the about 20 μ m aluminum foil current collector of thickness uniformly, positive electrode material is by about 90% cobalt acid lithium active substance, and 7%～8% acetylene black conductive agent and 3%～4% organic binder bond polyvinylidene difluoride (PVDF) (PVDF) are formed.
Among the present invention, adopt organic solvent to soak when separating aluminium foil and positive active material, organic solvent N-methyl-2-pyrrolidone (NMP), N, N-N,N-DIMETHYLACETAMIDE (DMAC), N, N-dimethyl formamide equal solubilized binding agents of amine solvent such as (DMAC), reach isolating effect, but test-results shows N-methyl-2-pyrrolidone (NMP) separating effect the best.Use N-methyl-2-pyrrolidone (NMP) when cooking soak solution, temperature should be controlled to be 130 ± 5 ℃.Temperature is crossed when hanging down, and the binding agent dissolving is incomplete or dissolution rate is slow, and aluminium foil separates not thorough with active substance; Temperature is too high, and N-methyl-2-pyrrolidone (NMP) volatilization loss is big.Simultaneously, the solid-to-liquid ratio of positive plate and N-methyl-2-pyrrolidone (NMP) should be controlled between 195～205g/L, is about about 200g/L; At this moment, soltion viscosity is little, is easy to filtering separation.
Among the present invention, select to adopt hydrochloric acid and hydrogen peroxide that anodal active material is leached, this be since in hydrochloric acid the leaching effect of cobalt element best, leaching rate is fast, but easy generation Cl when using hydrochloric acid separately
2, working conditions is abominable; So add certain amount of H
2O
2Make reductive agent, reduce Cl
2Generation, and adopt hydrochloric acid system favourable to later stage electrodeposition operation.In this step reaction, hydrochloric acid starting point concentration, extraction temperature, extraction time, H
2O
2Consumptions etc. all directly influence the leaching yield of cobalt.Test-results shows: when concentration of hydrochloric acid is 6mol/L, and additive H
2O
2Occupation rate is 0.50mol/L in hydrochloric acid soln, and the solid-to-liquid ratio of positive active material and hydrochloric acid is 145～155g/L, and extraction temperature is 65～75 ℃, and extraction time is 38～42min, and when promptly being about 40min, the leaching yield of cobalt is the highest, reaches 99.5%.And find that the hydrochloric acid starting point concentration is the key factor that influences the cobalt leaching effect, and it is big that concentration becomes, and extraction time shortens, leaching yield rising (the hydrochloric acid starting point concentration is specifically seen accompanying drawing 1 to the influence of cobalt leaching yield).
Among the present invention, adopt Winning cell electrodeposition leach liquor to prepare electrodeposited cobalt.After hydrochloric acid and hydrogen peroxide leached gained solution and filter, use deionized water with solution dilution to Co
2+Concentration is about 40g/L, adds an amount of sodium hydroxide regulation system pH value then, as electrodeposition solution.Used Winning cell adopts polypropylene material to make, and anode material is a ruthenium titanium anode, is 250mm with interpole gap, and the cathode and anode area is than being 1.2:1, and the electrodeposition time is 10 hours.In this step operation, temperature control is very important: temperature is low excessively, and bath voltage is too high, and energy consumption is big; Temperature is too high, causes a large amount of evaporations of solvent, makes the high humidity of operating environment, and equipment is perishable, in the test card open channel temperature be about 48～52 ℃ optimum.Simultaneously, the pH value of electric effusion directly affects the quality of electrodeposited cobalt: when the pH value less than 0.6 the time, current efficiency is low, there is pin hole on the electrodeposited cobalt surface; PH value surpasses at 2.0 o'clock, and foreign matter content is too high in the electrodeposited cobalt, and the surface is jagged; So best pH value should be controlled at (pH value is seen accompanying drawing 2 to the influence of electrodeposited cobalt quality) between 1.0～1.2.Once more, current density also is the key factor that influences the electrodeposited cobalt quality: current density is crossed when hanging down, and the electrodeposition time is long, the energy consumption height; Current density is too high, foreign matter content height in the cobalt, and electrodeposited cobalt piece surface is jagged, and cathode hydrogen evolution is serious, and current efficiency is low; Optimum current density should be controlled to be 800A/m
2About (current density is seen accompanying drawing 3 to the influence of electrodeposited cobalt quality).
The electrodeposited cobalt of producing among the present invention is silvery white reguline metal, and thin and thick is even, and wherein cobalt contents is higher than 99.80%, and the cobalt metal rate of recovery is about 97.0%.
Compared with prior art, the present invention has following beneficial effect:
The present invention has realized directly becoming the end product electrodeposited cobalt by waste and old lithium ion battery, and reaction process is short, and cost of material is low, the added value of product height; Solved product foreign matter content height in the traditional technology, the problem that the cobalt metal rate of recovery is low, and a kind of new way of producing cobalt metal is provided.
Description of drawings
Fig. 1 is the influence figure of hydrochloric acid starting point concentration to the cobalt leaching yield;
Fig. 2 is the influence figure of pH value to the electrodeposited cobalt quality;
Fig. 3 is the influence figure of current density to the electrodeposited cobalt quality;
Fig. 4 is recovery process figure of the present invention.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment, but the present invention's scope required for protection is not limited to the scope that embodiment describes.
Embodiment 1
After adopting professional equipment to disassemble to waste and old lithium ion battery, carry out the sorting of positive and negative electrode waste material, obtaining active material is the positive plate of cobalt acid lithium.Get this waste material 800g, soak 60min with 4L N-methyl-2-pyrrolidone (NMP) at 130 ℃, use the ultra-sonic oscillation 10min of 28KHz then, active material cobalt acid lithium breaks away from from aluminium foil, remove aluminium foil, suction filtration separates N-methyl-2-pyrrolidone (NMP) and contains black solid powdered materials such as cobalt acid lithium, acetylene black.Organic solvent N-methyl-2-pyrrolidone (NMP) can be recycled after treatment, with this black powder washing back oven dry.Analytical results shows that the cobalt residual quantity accounts for 0.23% of total cobalt amount on the aluminium foil.
After adopting professional equipment to disassemble to waste and old lithium ion battery, carry out the sorting of positive and negative electrode waste material, obtaining active material is the positive plate of cobalt acid lithium.Get this waste material 800g, soak 60min with 4L N-methyl-2-pyrrolidone (NMP) at 100 ℃, use the ultra-sonic oscillation 10min of 28KHz then, active material cobalt acid lithium breaks away from from aluminium foil, remove aluminium foil, suction filtration separates N-methyl-2-pyrrolidone (NMP) and contains black solid powdered materials such as cobalt acid lithium, acetylene black.Organic solvent N-methyl-2-pyrrolidone (NMP) can be recycled after treatment, with this black powder washing back oven dry.Analytical results shows that the cobalt residual quantity accounts for 3.46% of total cobalt amount on the aluminium foil.
Embodiment 3:
Configuration contains H
2O
2Concentration is 0.5mol/L, HCl concentration is the mixing solutions 1L of 6mol/L, weighing embodiment 1 gained black powder 150g, it is transferred in the 2L glass beaker, slowly pours above-mentioned mixing solutions into, water-bath keeps 70 ℃ of solution constant temperature, and adopt the tetrafluoroethylene agitator to continue to stir, behind the extraction time 40min, filtered while hot is separated insoluble slag, repeatedly after the washing gained filtrate is settled to 2L.After testing, the cobalt residual quantity accounts for 0.34% of total cobalt amount in the filter residue; Each major metal content is as follows in the gained filtrate:
| Element | Co | Li | Al | Cu | Ni | Fe | Mn | Mg | Ca |
| Content (g/L) | 42.02 | 4.86 | 0.21 | 0.02 | 0.08 | 0.03 | 0.05 | 0.02 | 0.02 |
Embodiment 4:
Configuration contains H
2O
2Concentration is 0.5mol/L, HCl concentration is the mixing solutions 1L of 4mol/L, weighing embodiment 1 gained black powder 150g, it is transferred in the 2L glass beaker, slowly pours above-mentioned mixing solutions into, water-bath keeps 70 ℃ of solution constant temperature, and adopt the tetrafluoroethylene agitator to continue to stir, behind the extraction time 40min, filtered while hot is separated insoluble slag, repeatedly after the washing gained filtrate is settled to 2L.After testing, the cobalt residual quantity accounts for 4.23% of total cobalt amount in the filter residue; Each major metal content is as follows in the gained filtrate:
| Element | Co | Li | Al | Cu | Ni | Fe | Mn | Mg | Ca |
| Content (g/L) | 40.11 | 4.62 | 0.19 | 0.02 | 0.07 | 0.03 | 0.04 | 0.02 | 0.02 |
Embodiment 5:
Using the PH instrumentation to get embodiment 3 constant volume solution pH values is 0.61, this 2L solution is directly put into Winning cell (containing the long 200mm of liquid size * wide 150mm * high 100mm), use traffic is that the peristaltic pump of 250ml/min makes solution at the Winning cell internal recycle, adopt dc current stabilized power supply, ruthenium titanium anode, the cobalt sheet is that (size 60mm * 85mm), current density is 800A/m to negative electrode
2, electrodeposition 10 hours obtains electrodeposited cobalt 80.04g, and current efficiency is 96.2%, and there is pin hole on the electrodeposited cobalt surface.
Embodiment 6:
Gained constant volume solution adds an amount of sodium hydroxide in embodiment 3, adjustment system PH is 1.0, should directly put into Winning cell (containing the long 200mm of liquid size * wide 150mm * high 100mm) by about 2L solution, use traffic is that the peristaltic pump of 250ml/min makes solution at the Winning cell internal recycle, adopt dc current stabilized power supply, ruthenium titanium anode, the cobalt sheet is that (size 60mm * 85mm), current density is 800A/m to negative electrode
2, electrodeposition 10 hours obtains electrodeposited cobalt 82.11g, and current efficiency is 97.2%, the electrodeposited cobalt surfacing.As follows through its composition of ICP spectroscopic analysis:
| Element term | Cobalt | Copper | Nickel | Iron | Manganese | Other |
| Content (%) | 99.84 | 0.01 | 0.08 | 0.04 | 0.01 | 0.02 |
Embodiment 7:
Gained constant volume solution adds an amount of sodium hydroxide in embodiment 3, adjustment system PH is 1.0, should directly put into Winning cell (containing the long 200mm of liquid size * wide 150mm * high 100mm) by about 2L solution, use traffic is that the peristaltic pump of 250ml/min makes solution at the Winning cell internal recycle, adopt dc current stabilized power supply, ruthenium titanium anode, the cobalt sheet is that (size 60mm * 85mm), current density is 640A/m to negative electrode
2, electrodeposition 10 hours obtains electrodeposited cobalt 79.88g, and current efficiency is 95.9%, slightly descends.
The various embodiments described above have been carried out more detailed description to the present invention, this should be interpreted as that subject area of the present invention only limits to the foregoing description.All technology that realizes based on foregoing all belong to scope of the present invention.
Claims (4)
- One kind from waste and old lithium ion battery, directly reclaim, the method for production electrodeposited cobalt, it is characterized in that: comprise following technological step:(1) employing is disassembled machine and is disassembled waste and old lithium ion battery, obtains containing the cobalt positive plate after the sorting;(2) adopt N-methyl-2-pyrrolidone to soak the waste lithium ion cell anode sheet, the positive electrode material that contains cobalt acid lithium, acetylene black is separated with aluminium foil;(3) employing hydrochloric acid and hydrogen peroxide leach cobalt, the lithium ion in the positive electrode material;(4) adopt insoluble petal anode electrodeposition to prepare electrodeposited cobalt.
- According to claim 1 describedly a kind ofly from waste and old lithium ion battery, directly reclaim, the method for production electrodeposited cobalt, it is characterized in that: when using N-methyl-2-pyrrolidone to soak in (2) step, temperature should be controlled at 125～135 ℃, and soak time is 60min; The solid-to-liquid ratio of positive plate and N-methyl-2-pyrrolidone is 195～205g/L.
- 3. according to claim 1ly a kind ofly from waste and old lithium ion battery, directly reclaim, the method for production electrodeposited cobalt, it is characterized in that: when leaching in (3) step, the concentration of hydrochloric acid is 6mol/L; Remove that the solid-to-liquid ratio of gained pressed powder and hydrochloric acid is 145～155g/L behind the aluminium foil; Additive H 2O 2Occupation rate is 0.48～0.52mol/L in hydrochloric acid soln, and temperature should be controlled at 65～75 ℃, and extraction time is 38～42min.
- 4. according to claim 1ly a kind ofly from waste and old lithium ion battery, directly reclaim, the method for production electrodeposited cobalt, it is characterized in that: in (4) step, the concentration of cobalt is 38～42g/L in the electrodeposition solution, and the pH value should be controlled between 1.0～1.2, and cathode current density is 800A/m 2, temperature is 48～52 ℃, the electrodeposition time is 10h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101603126B (en) * | 2009-07-08 | 2010-11-10 | 中南大学 | Process for efficiently leaching anode active material of waste lithium battery |
| CN102347521A (en) * | 2011-10-08 | 2012-02-08 | 佛山市邦普循环科技有限公司 | Method for recycling manganese and lithium from power type lithium manganate battery for electric automobile |
| CN102650063A (en) * | 2012-05-17 | 2012-08-29 | 大连理工大学 | Method for recovering elementary-substance cobalt from lithium cobaltate in one step by utilizing microbial electrolysis cell |
| CN103261455A (en) * | 2010-12-14 | 2013-08-21 | 住友金属矿山株式会社 | Method for separating positive-ole active substance and method for recovering valuable metals from lithium ion battery |
| CN103641175A (en) * | 2013-12-02 | 2014-03-19 | 河南师范大学 | Method for dissolving positive material of waste/used lithium-ion batteries |
| CN106841364A (en) * | 2015-12-03 | 2017-06-13 | 有研半导体材料有限公司 | A kind of VPD metal recovery liquid and its compound method |
| CN110257631A (en) * | 2019-06-14 | 2019-09-20 | 广西师范大学 | A kind of method of lithium and other metals in separating waste, worn lithium ion cell positive |
| CN111763956A (en) * | 2020-07-03 | 2020-10-13 | 陕西科技大学 | Method for separating and recovering valuable metals in waste lithium batteries by electrochemical technology |
| CN113802000A (en) * | 2021-08-13 | 2021-12-17 | 恩施市致纯电子材料有限公司 | Lithium ion battery positive electrode material recovery process |
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2007
- 2007-12-07 CN CNA2007100322912A patent/CN101381817A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101603126B (en) * | 2009-07-08 | 2010-11-10 | 中南大学 | Process for efficiently leaching anode active material of waste lithium battery |
| CN103261455A (en) * | 2010-12-14 | 2013-08-21 | 住友金属矿山株式会社 | Method for separating positive-ole active substance and method for recovering valuable metals from lithium ion battery |
| CN103261455B (en) * | 2010-12-14 | 2015-08-26 | 住友金属矿山株式会社 | The separation method of positive active material and reclaim the method for valuable metal from lithium ion battery |
| CN102347521A (en) * | 2011-10-08 | 2012-02-08 | 佛山市邦普循环科技有限公司 | Method for recycling manganese and lithium from power type lithium manganate battery for electric automobile |
| CN102650063A (en) * | 2012-05-17 | 2012-08-29 | 大连理工大学 | Method for recovering elementary-substance cobalt from lithium cobaltate in one step by utilizing microbial electrolysis cell |
| CN102650063B (en) * | 2012-05-17 | 2014-07-23 | 大连理工大学 | Method for recovering elementary-substance cobalt from lithium cobaltate in one step by utilizing microbial electrolysis cell |
| CN103641175A (en) * | 2013-12-02 | 2014-03-19 | 河南师范大学 | Method for dissolving positive material of waste/used lithium-ion batteries |
| CN106841364A (en) * | 2015-12-03 | 2017-06-13 | 有研半导体材料有限公司 | A kind of VPD metal recovery liquid and its compound method |
| CN110257631A (en) * | 2019-06-14 | 2019-09-20 | 广西师范大学 | A kind of method of lithium and other metals in separating waste, worn lithium ion cell positive |
| CN111763956A (en) * | 2020-07-03 | 2020-10-13 | 陕西科技大学 | Method for separating and recovering valuable metals in waste lithium batteries by electrochemical technology |
| CN111763956B (en) * | 2020-07-03 | 2022-10-18 | 陕西科技大学 | Method for separating and recovering valuable metals in waste lithium batteries by electrochemical technology |
| CN113802000A (en) * | 2021-08-13 | 2021-12-17 | 恩施市致纯电子材料有限公司 | Lithium ion battery positive electrode material recovery process |
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