CN105322247A - Method for preparing lithium cobaltate by directly using spent lithium ion batteries - Google Patents
Method for preparing lithium cobaltate by directly using spent lithium ion batteries Download PDFInfo
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- CN105322247A CN105322247A CN201410343808.XA CN201410343808A CN105322247A CN 105322247 A CN105322247 A CN 105322247A CN 201410343808 A CN201410343808 A CN 201410343808A CN 105322247 A CN105322247 A CN 105322247A
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Abstract
A method for preparing lithium cobaltate by directly using spent lithium ion batteries comprises crushing spent lithium ion batteries or waste leftover materials generated during lithium cobaltate battery production by using a machinery crusher at normal temperature, adding one or more of water, acetic acid, sulfuric acid, hydrochloric acid and nitric acid, so as to prepare an aqueous solution of a mixture of the battery crushed materials and the acid, putting in an enclosed pressure reaction kettle, controlling the kettle internal temperature to be 50-150 DEG C, introducing or adding one of leaching additives sulfur dioxide and hydrogen, or adding hydrazine hydrate, stirring for leaching, then cooling and filtering, adding one of sodium carbonate, potassium carbonate and ammonium carbonate precipitating agents into the filtrate, or adding a composite precipitating agent composed of one of sodium carbonate, potassium carbonate and ammonium carbonate and one of sodium hydroxide and potassium hydroxide, so as to obtain a mixture of lithium carbonate, cobalt carbonate and cobalt hydroxide, and performing drying and high-temperature roasting, so as to obtain the lithium cobaltate product. The method is especially suitable for the processing scale of middle and small-sized enterprises, and is an effective method for direct material formation of cobalt-containing sources.
Description
Technical field
The present invention relates to a kind of method that direct disabled lithium ion cell prepares cobalt acid lithium, belong to nonferrous metal resource and recycle and battery material preparing technical field.Especially relating to cobalt acid lithium is the disabled lithium ion cell of positive electrode and the processing method of leftover bits, without the many pretreatment process being separated positive electrode, adopt special leaching means, make lithium, cobalt element enters solution, lithium, cobalt is precipitated again from solution, prepare cobalt acid lithium through roasting, a kind of method of disabled lithium ion cell direct material of not limit gauge mould is provided.
Background technology
Cobalt is the strategy metal resource of domestic shortage, is one of metal that external dependence degree is the highest, reaches more than 90%, needs a large amount of various containing cobalt raw material of import every year.Current China produces for secondary cell the cobalt amount of metal consumed and accounts for 50% of its aggregate consumption, and battery production consumes the maximum industry of metallic cobalt amount.Along with the development of economy, technology and the raising of people's living standard, various portable type electronic product, as mobile phone, notebook computer, digital camera and video camera etc. have become the everyday common items of people's work and life.Current most of lithium ion battery all uses lithium cobaltate cathode material.The lithium ion battery being positive electrode with cobalt acid lithium does not have the element of severe contamination to environment containing cadmium, lead, mercury etc., because operating voltage is high, volume is little, lightweight, specific energy is high, memory-less effect, pollution-free less, the advantage such as self discharge is little, have extended cycle life, the stable performance of simultaneously cobalt acid lithium, synthetic method are simple, it is the positive electrode of comparatively ideal lithium ion battery, become the maximum secondary portable battery of consumption with the lithium ion battery that cobalt acid lithium is positive electrode, especially sharply increased in field of mobile communication use amount.In recent years, for reducing the cost of manufacture of lithium ion battery, positive pole material of lithium cobalt acid (LiCoO is replaced divided by other metallic member
2) cobalt element outside, also developed LiMn2O4, lithium nickelate, LiFePO4 and lithium cobalt manganese nickel composite oxide lithium ion battery, but these lithium ion batteries be mainly used as electrokinetic cell.As the chargeable battery of portable type electronic product, with cobalt acid lithium (LiCoO
2) there is irreplaceable effect for the lithium ion battery of positive electrode, the update of annual a large amount of mobile phone and discarded, and the various waste materials of the inevitable output of lithium ion battery manufacturer, corresponding generation enormous amount containing the cobalt acid disabled lithium ion cell of lithium or waste material, become one of most important resource that cobalt regenerated metal reclaims and recycle.Disabled lithium ion cell containing cobalt acid lithium is worth high, and wherein main valuable metal is Li, Co, Cu, Al, and shell has plastics or aluminium packaging, alters a great deal, also adopt stainless steel if any some notebook computers casing of lithium ion battery used with purposes and brand.Lithium ion battery is made up of major parts such as positive pole, electrolyte, negative poles.The positive pole of battery by about 90% positive active material cobalt acid lithium (LiCoO
2), the acetylene black conductor of about 7% ~ 8%, about 3% ~ 4% organic bond Homogeneous phase mixing after, coat in the aluminum foil current collector of thick about 20 μm.The negative pole of battery by about 90% negative electrode active material carbon material, 4% ~ 5% acetylene black conductor, 6% ~ 7% adhesive Homogeneous phase mixing after, coat in the copper foil current collector of thick about 20 μm; The thickness of both positive and negative polarity is about 0.18 ~ 0.2mm, and the polyethylene film that centre thickness is about 10 μm separates, and fills the organic carbonate electrolyte with lithium hexafluoro phosphate.The comparison of ingredients of disabled lithium ion cell is complicated, cobalt acid lithium LiCoO
2also can change in charge and discharge process.To process and the recycling of disabled lithium ion cell, mainly contain chemical method and Mechanical Method.In chemical treatment method, more typical flow process is: fragmentation, electrolyte process, roasting, magnetic separation, fine grinding, classification and screening, again through melting, the high-grade cobalt alloy of output, then through wet treatment, output metallic cobalt or cobalt carbonate and lithium carbonate.Mechanical Method (physical method) more typical flow process is: fragmentation, electrolyte process, heat treatment, magnetic separation, fine grinding, sieve through classification again and be separated, output copper-bearing waste material and refining cobalt material, wherein refining cobalt material mainly comprises carbon material, cupric oxide, aluminium oxide, cobalt oxide, cobaltosic oxide and cobalt acid lithium etc., also may contain the oxide of a small amount of tin-lead solder, also will leach extraction process further.
Japan is one of country carrying out disabled lithium ion cell recovery at first, Sony and mine company of Sumitomo Metal Industries have developed the technology of the element such as Call Provision from disabled lithium ion cell cooperatively, propose Sony-Sumitomo technique (SonySumitomoprocess) in the world the earliest.Its technique is first burned by battery, to remove organic substance, then screen de-iron and copper, be dissolved in by the powder of remnants in the acid solution of heat, then cobalt is extracted in extraction.The method mainly comprises two parts: first in Sony subordinate factory by refuse battery through heat treatment, battery is opened, then subordinate factory of Sumitomo company extract cobalt.Battery can be made after 1000 DEG C of roasting heat process to open, and by combustible as electrolyte, diaphragm material burn removing, then by battery crushing, screening.Oversize mainly containing Fe, Cu and Al, is separated with magnetic selection method further; And screenings composition is mainly carbon, LiCoO
2or (with) LiCo
xni
(1-x)o
2, then extract cobalt through leaching, extracting.The binding agent (polyvinylidene fluoride, PVDF) of electrode material dissolves at experiment indoor 1-METHYLPYRROLIDONE (NMP) organic solvent by Rome, ITA university M.Contestabile etc., makes LiCoO
2, carbon dust is separated with collector, then with Leaching in Hydrochloric Acid process LiCoO
2with the mixture of carbon dust.But organic solvent is expensive, in use procedure, loss is large, and real value is little.Korea S develops the Wet-process metallurgy method-armorphous citrate precipitation regenerating cobalt acid lithium from disabled lithium ion cell.Technological process is: disabled lithium ion cell → Grape berry (battery dissociates, rigid plastics) → primary fragmentation → once screening → secondary heat treatment → regrading → high-temperature roasting → nitric acid medium reducing leaching (H
2o
2make reducing agent) → purification and impurity removal → citric acid precipitation → high-temperature roasting → cobalt acid lithium.Detailed process is that then use the mixed solution process of nitric acid and hydrogen peroxide, the leaching rate of cobalt, lithium reaches 95% by li-ion electrode materials isolated from collector after 700 ~ 900 DEG C of high temperature decarburizations.After obtaining nitrate solution, add citric acid, become Gel Precursor through concentrated, after 950 DEG C of calcining 24h, obtain the high LiCoO of degree of crystallinity
2product.Korea S develops the Wet-process metallurgy method-armorphous citrate precipitation regenerating cobalt acid lithium from disabled lithium ion cell.Technological process is: disabled lithium ion cell → Grape berry (battery dissociates, rigid plastics) → primary fragmentation → once screening → secondary heat treatment → regrading → high-temperature roasting → nitric acid medium reducing leaching (H
2o
2make reducing agent) → purification and impurity removal → citric acid precipitation → high-temperature roasting → cobalt acid lithium.Detailed process is that then use the mixed solution process of nitric acid and hydrogen peroxide, the leaching rate of cobalt, lithium reaches 95% by li-ion electrode materials isolated from collector after 700 ~ 900 DEG C of high temperature decarburizations.After obtaining nitrate solution, add citric acid, become Gel Precursor through concentrated, after 950 DEG C of calcining 24h, obtain the high LiCoO of degree of crystallinity
2product.Australia's Ao Simote (AUSMELT) technical finesse disabled lithium ion cell realizes by adding vulcanizing agent, through high melt, the valuables in battery is enriched in matte.The element of low value and the composition without the need to reclaiming oxidized enter slag, plastics are burned in stove top, can be stove and provide part heat supply.There is sulphur in the rapid cooling of flue gas and flue gas, be conducive to the generation preventing dioxin, furans.But this technique must combine with existing large-scale metallurgical equipment and process.Umicore Company of Belgium (Umicore) is one of Metal Production the biggest in the world and resource circulation utilization enterprise, adopt the process of high melt method containing cobalt battery, output alloy, cobalt compound product is produced again by wet process, adopt special process, control the generation of dioxin in flue gas.Technique is advanced, and treatment scale is large, and reach European environmental protection standard, the rate of recovery is high.But equipment investment is huge in whole flow process, be suitable for the countries and regions that resoures recycling based industry chain is complete, need certain treatment scale.In disabled lithium ion cell, polyethylene diagrams toughness is strong, and wrapped up by electrode material, positive electrode then firmly sticks on aluminium collector by polyvinylidene fluoride binding agent, more difficultly peels off, and the leaching hindering metallic element is extracted.Adopt the solvent used during organic solvent dissolution binding agent expensive, also have certain difficulty independent being separated with other material in battery by electrode material in addition.Adopt roasting pretreatment method organics removal then simpler, decrease separation circuit and the equipment of electrode material, obtain metallic product of roasting, but roasting is by gases such as the hydrogen fluoride of generation serious toxicity, dioxin and furans, contaminated environment, also create new for cobalt thing phase in a large number, as cobaltosic oxide etc., leach, extract difficulty, be extremely unfavorable for the recovery of cobalt, also make tin-lead solder etc. become during roasting and be easy to leach, subsequent solution impurity content is increased.
The different process method of current domestic existence, the chemical agent kind used during Footwall drift is many, long flow path, and refuse generation is large, and cost is higher.In addition, due to the more difficult collection of domestic disabled lithium ion cell, be difficult to reach the requirement focused on a large scale, the scale of general process enterprise is general all less.Because the structure comparison of lithium ion battery is special, main valuable material-cobalt acid lithium and aluminum foil current collector bond closely, not only not easily disintegrate and fragmentation, and when screening and magnetic separation, the mechanical entrapment loss of cobalt acid lithium is serious, the rate of recovery is very low, and this causes cobalt in whole technique, copper, main cause that lithium comprehensive recovery is low, and general processing method efficiency is also low at present.For armorphous citrate precipitation, the comprehensive recovery of its valuable metal cobalt, copper, lithium only has an appointment 50%, and due to treatment process more, costly, processing cost is higher for various reagents ratios used.The present invention is directed to the material characteristics of disabled lithium ion cell, the scale recycling enterprise and technical merit, disclose a kind of method that direct disabled lithium ion cell prepares cobalt acid lithium, adopt special reagent, carry out direct weighting leaching, the method technique is simple, and device therefor is few.
Summary of the invention
The object of the invention is: provide a kind of direct disabled lithium ion cell to prepare the straightforward procedure of cobalt acid lithium, the cobalt acid lithium direct material in disabled lithium ion cell can be made; Be applicable to enterprise and the treating capacity of different scales and technical merit, significantly reduce treatment process, improve treatment effeciency, reduce costs, reduce the generation of pollutant, and lithium, the cobalt element direct material in disabled lithium ion cell is made when processing, produce cobalt acid lithium, for the preparation of lithium ion battery.Its technique comprises: with the disabled lithium ion cell containing cobalt acid lithium for raw material, through fragmentation, pressure leaching, precipitation, precipitation calcining process, directly prepares cobalt acid lithium; The method does not need to peel off or roasting battery material, and also do not need to be separated positive electrode etc., make with medicament single, treatment effeciency is high, and middle refuse, waste liquid output are few, and flow process is short, processing cost is low.The method also can be applicable to process and the direct material of LiMn2O4, nickle cobalt lithium manganate, lithium nickel cobalt dioxide and other polynary positive pole material of lithium ion cell.
The object of the invention is to be realized by following scheme: 1, treatment process process comprises: under normal temperature first with mechanical crusher by disabled lithium ion cell or produce cobalt acid lithium battery time leftover bits be crushed to and be less than 3 ~ 10mm
2particle, secondary is washed with dilute sulfuric acid aqueous solution, then add containing acetic acid, sulfuric acid, hydrochloric acid or nitre aqueous acid, obtained battery particle and sour mixture aqueous solution, load airtight pressure reaction still, raise temperature in the kettle, controlling temperature in the kettle is 50 ~ 150 DEG C, pass into or add additive to extraction, leaching, then mixture aqueous solution is cooled, filter, sodium carbonate is added in filtrate, one in potash and ammonium carbonate precipitation reagent, or add sodium carbonate, one in potash and ammonium carbonate and NaOH, one in potassium hydroxide forms compound precipitants, obtain lithium carbonate and cobalt carbonate, cobalt hydroxide, the mixture precipitation of basic cobaltous carbonate, drying, high-temperature roasting, output cobalt acid lithium, 2, disabled lithium ion cell raw material comprises the various inefficacy rechargeable type secondary lithium battery containing cobalt acid lithium, and leftover bits during production cobalt acid lithium battery, 3, with mechanical crusher disabled lithium ion cell is crushed under normal temperature and is less than 3 ~ 10mm
2particle, do not need particle sorting, screening, with the dilute sulfuric acid water washing secondary of 2 ~ 5g/L, water is filtered dry after washing, and then one or more adding in water and acetic acid, sulfuric acid, hydrochloric acid or nitric acid, be deployed into battery particle and sour mixture aqueous solution, acid concentration is 0.2 ~ 3.5mol/L, liquid-solid ratio 3 ~ 20: 1, 4, load in airtight pressure reaction still by battery particle and the mixture aqueous solution of acid, raise temperature in the kettle, control temperature is 50 ~ 150 DEG C, 5, stress reaction temperature in the kettle reaches a timing, and pass into the one in sulfur dioxide or hydrogen, the dividing potential drop of sulfur dioxide or hydrogen is 0.005 ~ 0.8MPa, or the one added in hydrazine hydrate, sodium sulfite, glucose, hydrazine hydrate, sodium sulfite, glucose concentration is in aqueous 3 ~ 20g/L, in pressure reaction still, the mixture aqueous solution Leaching reaction time is 0.5 ~ 2.5h, 6, after Leaching reaction, at battery particle in pressure reaction still and the mixture aqueous solution of acid are cooled to 85 DEG C, and still internal pressure is reduced to normal pressure, release mixture aqueous solution, after filtration, obtain the filtrate containing lithium, cobalt, washing filter residue once, wash water mixes with filtrate, obtains the filtrate containing lithium, cobalt, 7, containing lithium, the sodium carbonate that concentration is 1 ~ 5mol/L is added in the filtrate of cobalt, potash and the ammonium carbonate precipitation reagent aqueous solution, or add concentration 1 ~ 5mol/L sodium carbonate, a kind of in potash and ammonium carbonate is the NaOH of 0.5 ~ 4mol/L with concentration, the one composition compound precipitants aqueous solution in potassium hydroxide, to pH value to 6.5 ~ 13 of filtrate, lithium carbonate containing and cobalt carbonate is obtained after filtering, cobalt hydroxide, the sediment of basic cobaltous carbonate, wash secondary with water, through 80 ~ 110 DEG C of oven dry, with a small amount of lithium carbonate or cobalt carbonate or cobaltosic oxide adjustment lithium cobalt ratio, 600 ~ 950 DEG C of high-temperature roastings, output cobalt acid lithium.
The present invention compares the advantage that has with existing known technology and good effect is: disabled lithium ion cell without disassembling, roasting, the preliminary treatment such as screening, save a large amount of labour cost, the hydrogen fluoride of the serious toxicity produced without roasting, dioxin and furans gas, do not need first to be separated positive electrode and to extract cobalt acid lithium enriched substance, decrease the possibility that cobalt acid lithium is dispersed in different material, significantly decrease treatment process, reduce processing cost; In airtight pressure reaction still, adopt special leaching reagent to leach, reaction speed is fast, leaching efficiency is high, infusion solution purity is high, can be directly used in and prepare cobalt acid lithium, added value of product is high, is adapted to medium-sized and small enterprises treatment scale especially, be a kind of disabled lithium ion cell and produce cobalt acid lithium battery time the effective ways of the direct material such as leftover bits.
Embodiment
To embodiments of the present invention, particularly preparation method is illustrated.But when implementing of the present invention, be not limited to the concrete numerical value of the various raw materials, reagent, solution etc. listed in following explanation, those skilled in the art can according to claims scope of disclosure in addition appropriate change.
A kind of direct disabled lithium ion cell that the present invention relates to prepares the straightforward procedure of cobalt acid lithium, disabled lithium ion cell is soaked 3 ~ 8 hours in the sodium chloride solution of 3 ~ 10%, put except dump energy, be crushed to the leftover bits of mechanical crusher by disabled lithium ion cell or when producing cobalt acid lithium battery at normal temperatures and be less than 3 ~ 10mm
2particle, with 2 ~ 5g/L dilute sulfuric acid aqueous solution washing secondary, then water and acetic acid is added, sulfuric acid, one or more in hydrochloric acid or nitric acid, preparation acetic acid, sulfuric acid, hydrochloric acid or nitre aqueous acid, obtained battery particle and sour mixture aqueous solution, load airtight pressure reaction still, raise temperature in the kettle, controlling temperature in the kettle is 50 ~ 150 DEG C, pass into or add additive to extraction sulfur dioxide, one in hydrogen, or add hydrazine hydrate, sodium sulfite, glucose, leaching 0.5 ~ 2.5h, then mixture aqueous solution is cooled, filter, sodium carbonate is added in filtrate, one in potash and ammonium carbonate precipitation reagent, or add sodium carbonate, one in potash and ammonium carbonate and NaOH, the compound precipitants of a kind of composition in potassium hydroxide, obtain lithium carbonate and cobalt carbonate, cobalt hydroxide, the mixture precipitation of basic cobaltous carbonate, drying, high-temperature roasting, output cobalt acid lithium product.
Carry out according to the following steps during enforcement.
Step 1, discharge process
Disabled lithium ion cell is soaked 3 ~ 8 hours in the sodium chloride solution of 3 ~ 10%, puts except dump energy; During leftover bits when process for producing cobalt acid lithium battery, do not need to carry out discharge process.
Step 2, broken washing
With mechanical crusher disabled lithium ion cell or leftover bits be crushed under normal temperature and be less than 3 ~ 10mm
2particle, does not need particle sorting, screening, with the dilute sulfuric acid water washing secondary of 2 ~ 5g/L, is filtered dry water after washing; When process cobalt acid lithium battery time leftover bits time, do not need to carry out dilute sulfuric acid aqueous solution washing.
Step 3, solution preparation
Add in water and acetic acid, sulfuric acid, hydrochloric acid or nitric acid in battery particle after fragmentation one or more, be 0.2 ~ 3.5mol/L by acid concentration, liquid-solid ratio 3 ~ 20: 1, is deployed into the mixture aqueous solution of battery particle and acid;
Wherein preferred acid concentration is 0.6 ~ 2mol/L.
Step 4, leaching
Battery particle and the mixture aqueous solution of acid are loaded in airtight pressure reaction still, raise temperature in the kettle, when stress reaction temperature in the kettle reaches 50 ~ 150 DEG C, pass into the one in sulfur dioxide or hydrogen, the dividing potential drop of sulfur dioxide or hydrogen is 0.005 ~ 0.8MPa; Or adding the one in hydrazine hydrate, sodium sulfite, glucose by charge of intermediation tank, hydrazine hydrate, sodium sulfite, glucose concentration is in aqueous 3 ~ 20g/L; In pressure reaction still, the mixture aqueous solution Leaching reaction time is 0.5 ~ 2.5h; Wherein the dividing potential drop of preferred sulfur dioxide or hydrogen is 0.02 ~ 0.5MPa.
Step 5, discharging and filtration
After Leaching reaction, at battery particle in pressure reaction still and the mixture aqueous solution of acid are cooled to 85 DEG C, and still internal pressure is reduced to normal pressure, release mixture aqueous solution, after filtration, obtain the filtrate containing lithium, cobalt, washing filter residue once, wash water mixes with filtrate, obtains the filtrate containing lithium, cobalt.
Step 6, precipitation
The one in sodium carbonate, potash and the ammonium carbonate precipitation reagent aqueous solution that concentration is 1 ~ 5mol/L is added in the filtrate containing lithium, cobalt; or a kind of and concentration added in concentration 1 ~ 5mol/L sodium carbonate, potash and ammonium carbonate be the NaOH of 0.5 ~ 4mol/L, one in potassium hydroxide forms the compound precipitants aqueous solution; to pH value to 6.5 ~ 13 of filtrate; obtain the sediment of lithium carbonate containing and cobalt carbonate, cobalt hydroxide, basic cobaltous carbonate after filtering, wash secondary with water; Wherein in the preferred precipitation reagent aqueous solution, sodium carbonate, potash and ammonium carbonate concentration are 2.5 ~ 3.5mol/L, or a kind of and concentration in the sodium carbonate of concentration 2 ~ 3mol/L, potash and ammonium carbonate be the NaOH of 1 ~ 2mol/L, one in potassium hydroxide forms the compound precipitants aqueous solution; When to add in hydrazine hydrate, sodium sulfite, glucose additive a kind of, the one in the NaOH that preferred precipitation reagent is the sodium carbonate of concentration 2 ~ 3mol/L, a kind of and concentration in potash and ammonium carbonate is 1 ~ 2mol/L, potassium hydroxide forms the compound precipitants aqueous solution.
Step 7, cobalt acid lithium synthesis step
The sediment of lithium carbonate and cobalt carbonate, cobalt hydroxide, basic cobaltous carbonate dries 4 ~ 12h at 80 ~ 110 DEG C, analytical chemistry composition, the mol ratio of adjustment lithium and cobalt is 1.03 ~ 1.07: 1, when departing from this mol ratio, by a small amount of lithium carbonate or cobalt carbonate or cobaltosic oxide adjustment lithium cobalt mol ratio, mix, then at 600 ~ 950 DEG C of high-temperature roasting 4 ~ 12h, output cobalt acid lithium.
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment one
Get the mobile phone disabled lithium ion cell 8 pieces of every block heavily about 54g, put into 1000ml glass beaker, add the sodium-chloride water solution 400ml of 5%, soak 5 hours, put except dump energy, when bubble-free is emerged in sodium-chloride water solution, take out battery, rinse with a small amount of water; With mechanical crusher disabled lithium ion cell is crushed at normal temperatures and is less than 3 ~ 6mm
2particle, with 3g/L dilute sulfuric acid aqueous solution washing secondary.
Battery particle is put into 5000ml glass beaker, then adds water and hydrochloric acid, be made into the aqueous solution of 2500ml concentration of hydrochloric acid 1.8mol/L, form battery particle and the mixture aqueous solution of acid, load in airtight pressure reaction still, raise temperature in the kettle, controlling temperature in the kettle is 95 DEG C, pass into sulfur dioxide gas, dividing potential drop is 0.03MPa, leaching 1.5h, then mixture aqueous solution is cooled to 75 DEG C, and still internal pressure is reduced to normal pressure, release mixture aqueous solution, after filtration, battery particle is separated with the mixture aqueous solution of acid, obtain containing lithium, the filtrate of cobalt, washing filter residue once, wash water mixes with filtrate, obtain containing lithium, the filtrate of cobalt, the aqueous sodium carbonate that concentration is 2.5mol/L is added in filtrate, to the pH value to 10 of filtrate, lithium carbonate and cobalt carbonate is obtained after filtering, cobalt hydroxide, the mixture of basic cobaltous carbonate, wash secondary with water, 100 DEG C of oven dry, the mol ratio of adjustment lithium and cobalt is in 1.03 ~ 1.07: 1 scope, add 0.27g lithium carbonate, ground and mixed is even, load alumina crucible, roasting 6h at 800 DEG C, measure through x-ray diffractometer, for cobalt acid lithium phase structure, without other impurity diffraction maximum, product is pure cobalt acid lithium.
With one or more in acetic acid, sulfuric acid, hydrochloric acid or nitric acid, preparation battery particle and the mixture aqueous solution of acid, replace sulfur dioxide gas with hydrogen, adopt above-mentioned process, equally can handling failure lithium ion battery, obtains pure cobalt acid lithium.
The one in sodium carbonate, potash and ammonium carbonate precipitation reagent is added in the filtrate containing lithium, cobalt, or add a kind of and NaOH in sodium carbonate, potash, ammonium carbonate, the one in potassium hydroxide forms compound precipitants, replace sodium carbonate precipitation reagent, the preparation precipitation reagent aqueous solution, adopt above-mentioned process, equally can handling failure lithium ion battery, obtain pure cobalt acid lithium.
Embodiment two
Get leftover bits 300g when producing cobalt acid lithium battery, mainly consist of aluminium foil, binding agent, LiCoO
2and carbon dust, with mechanical crusher leftover bits are crushed at normal temperatures and are less than 5 ~ 10mm
2particle.
Particle is put into 5000ml glass beaker, then water and hydrochloric acid, nitric acid two kinds of acid are added, be made into the mixed acid aqueous solution of 3000ml concentration of hydrochloric acid 0.8mol/L, concentration of nitric acid 1.0mol/L, form battery particle and the mixture aqueous solution of acid, load in airtight pressure reaction still, raise temperature in the kettle, controlling temperature in the kettle is 110 DEG C, pass into hydrogen, dividing potential drop is 0.3MPa, leaching 2h, then mixture aqueous solution is cooled to 75 DEG C, and still internal pressure is reduced to normal pressure, release mixture aqueous solution, after filtration, battery particle is separated with the mixture aqueous solution of acid, obtain containing lithium, the filtrate of cobalt, washing filter residue once, wash water mixes with filtrate, obtain containing lithium, the filtrate of cobalt, the mixed aqueous solution that ammonium carbonate that concentration is 2.5mol/L and concentration are the NaOH of 1.2mol/L is added in filtrate, to the pH value to 11.5 of filtrate, lithium carbonate and cobalt carbonate is obtained after filtering, cobalt hydroxide, the mixture of basic cobaltous carbonate, wash secondary with water, after 105 DEG C of oven dry, ground and mixed is even, record the mol ratio of lithium and cobalt in 1.03 ~ 1.07: 1 scope, load alumina crucible, roasting 6h at 750 DEG C, measure through x-ray diffractometer, for cobalt acid lithium phase structure, without other impurity diffraction maximum, product is pure cobalt acid lithium.
With one or more in acetic acid, sulfuric acid, hydrochloric acid or nitric acid, preparation battery particle and the mixture aqueous solution of acid, replace hydrogen gas with sulfur dioxide, adopt above-mentioned process, equally can process for producing cobalt acid lithium battery time leftover bits, obtain pure cobalt acid lithium.
The one in sodium carbonate, potash and ammonium carbonate precipitation reagent is added in the filtrate containing lithium, cobalt, or add a kind of and NaOH in sodium carbonate, potash and ammonium carbonate, the one in potassium hydroxide forms compound precipitants, replace the compound precipitants that ammonium carbonate and NaOH form, the preparation precipitation reagent aqueous solution, adopt above-mentioned process, equally can process for producing cobalt acid lithium battery time leftover bits, obtain pure cobalt acid lithium.
Embodiment three
Get the mobile phone disabled lithium ion cell 10 pieces of every block heavily about 35g, put into 1000ml glass beaker, add the sodium-chloride water solution 400ml of 5%, soak 4 hours, put except dump energy, in sodium-chloride water solution, bubble-free is emerged, take out battery, rinse with a small amount of water; With mechanical crusher disabled lithium ion cell is crushed at normal temperatures and is less than 5 ~ 8mm
2particle, with 3g/L dilute sulfuric acid aqueous solution washing secondary; Get leftover bits 50g when producing cobalt acid lithium battery again, mainly containing binding agent, LiCoO
2and carbon dust, with mechanical crusher leftover bits are crushed at normal temperatures and are less than 4 ~ 6mm
2particle; By two kinds of battery particle mixing.
5000ml glass beaker put into by battery particle, then water and sulfuric acid, acetic acid two kinds of acid are added, be made into the mixed acid aqueous solution of 3500ml sulfuric acid concentration 1.2mol/L, acetate concentration 1.5mol/L, form battery particle and the mixture aqueous solution of acid, load in airtight pressure reaction still, raise temperature in the kettle, controlling temperature in the kettle is 120 DEG C, and add hydrazine hydrate by charge of intermediation tank, concentration of hydrazine hydrate is in aqueous 14g/L, leaching 2h, then mixture aqueous solution is cooled to 75 DEG C, and still internal pressure is reduced to normal pressure, release mixture aqueous solution, after filtration, battery particle is separated with the mixture aqueous solution of acid, obtain containing lithium, the filtrate of cobalt, washing filter residue once, wash water mixes with filtrate, obtain containing lithium, the filtrate of cobalt, the mixed aqueous solution that potash that concentration is 2.2mol/L and concentration are the potassium hydroxide of 1.5mol/L is added in filtrate, to the pH value to 12 of filtrate, lithium carbonate and cobalt carbonate is obtained after filtering, cobalt hydroxide, the mixture of basic cobaltous carbonate, wash secondary with water, 100 DEG C of oven dry, the mol ratio of adjustment lithium and cobalt is in 1.03 ~ 1.07: 1 scope, add 0.18g lithium carbonate, ground and mixed is even, load alumina crucible, roasting 8h at 700 DEG C, measure through x-ray diffractometer, for cobalt acid lithium phase structure, without other impurity diffraction maximum, product is pure cobalt acid lithium.
With one or more in acetic acid, sulfuric acid, hydrochloric acid or nitric acid, preparation battery particle and sour mixture aqueous solution, hydrazine hydrate is replaced with sodium sulfite or glucose, adopt above-mentioned process, equally can handling failure lithium ion battery form with leftover bits when producing cobalt acid lithium battery mix particle, obtain the sour lithium of pure cobalt.
In the filtrate containing lithium, cobalt, add a kind of and NaOH in sodium carbonate, potash, ammonium carbonate, the one in potassium hydroxide forms compound precipitants, replace the mixed precipitant that potash and potassium hydroxide form, the preparation precipitation reagent aqueous solution, adopt above-mentioned process, equally can handling failure lithium ion battery form with leftover bits when producing cobalt acid lithium battery mix particle, obtain the sour lithium of pure cobalt.
Claims (7)
1. a direct disabled lithium ion cell prepares the method for cobalt acid lithium, leftover bits by disabled lithium ion cell or when producing cobalt acid lithium battery are broken into battery particle, wash with dilute sulfuric acid aqueous solution, add containing acetic acid, sulfuric acid, hydrochloric acid or nitre aqueous acid, obtained battery particle and sour mixture aqueous solution, load airtight pressure reaction still, raise temperature in the kettle, pass into or add additive to extraction, or in mixture aqueous solution, adding a kind of additive in hydrazine hydrate, sodium sulfite, glucose; Leaching, after leaching, mixture aqueous solution cooled, filter, the one in sodium carbonate, potash and ammonium carbonate precipitation reagent is added in filtrate, or add a kind of and NaOH in sodium carbonate, potash and ammonium carbonate, the one in potassium hydroxide forms compound precipitants, obtain the mixture of lithium carbonate and cobalt carbonate, cobalt hydroxide, basic cobaltous carbonate, drying, high temperature sintering, output cobalt acid lithium; It is characterized in that comprising the following steps: under normal temperature, first with mechanical crusher, leftover bits when disabled lithium ion cell or production cobalt acid lithium battery are broken into battery particle, secondary is washed with dilute sulfuric acid aqueous solution, then add containing acetic acid, sulfuric acid, hydrochloric acid or nitre aqueous acid, obtained battery particle and sour mixture aqueous solution, load airtight pressure reaction still, raise temperature in the kettle, controlling temperature in the kettle is 50 ~ 150 DEG C, pass into or add additive to extraction, the dividing potential drop of additive sulfur dioxide or hydrogen is 0.005 ~ 0.8MPa; Or a kind of additive added in mixture aqueous solution in hydrazine hydrate, sodium sulfite, glucose; Leaching, then mixture aqueous solution cooled, filter, the one in sodium carbonate, potash and ammonium carbonate precipitation reagent is added in filtrate, or add a kind of and NaOH in sodium carbonate, potash and ammonium carbonate, the one in potassium hydroxide forms compound precipitants, obtain the mixture of lithium carbonate and cobalt carbonate, cobalt hydroxide, basic cobaltous carbonate, drying, high temperature sintering, output cobalt acid lithium.
2. the method for cobalt acid lithium is prepared by a kind of direct disabled lithium ion cell according to claim 1, it is characterized in that disabled lithium ion cell raw material comprises the various inefficacy rechargeable type secondary lithium battery containing cobalt acid lithium, and leftover bits during production cobalt acid lithium battery.
3. prepared the method for cobalt acid lithium by a kind of direct disabled lithium ion cell described in claim 1,2, it is characterized in that with mechanical crusher disabled lithium ion cell being crushed under normal temperature being less than 3 ~ 10mm
2particle, do not need particle sorting, screening, with the dilute sulfuric acid water washing secondary of 2 ~ 5g/L, water is filtered dry after washing, and then one or more adding in water and acetic acid, sulfuric acid, hydrochloric acid or nitric acid, be deployed into battery particle and sour mixture aqueous solution, acid concentration is 0.2 ~ 3.5mol/L, liquid-solid ratio 3 ~ 20: 1.
4. prepared the method for cobalt acid lithium by a kind of direct disabled lithium ion cell described in claim 1,3, it is characterized in that battery particle and the mixture aqueous solution of acid to load in airtight pressure reaction still, raise temperature in the kettle, control temperature is 50 ~ 150 DEG C.
5. the method for cobalt acid lithium is prepared by a kind of direct disabled lithium ion cell described in claim 1,4, it is characterized in that stress reaction temperature in the kettle reaches a timing, pass into the one in sulfur dioxide or hydrogen, the dividing potential drop of sulfur dioxide or hydrogen is 0.005 ~ 0.8MPa; Or the one added in hydrazine hydrate, sodium sulfite, glucose, hydrazine hydrate, sodium sulfite, the glucose concentration in mixture aqueous solution is 3 ~ 20g/L; In pressure reaction still, the mixture aqueous solution Leaching reaction time is 0.5 ~ 2.5h.
6. the method for cobalt acid lithium is prepared by a kind of direct disabled lithium ion cell described in claim 1,5, after it is characterized in that Leaching reaction, at battery particle in pressure reaction still and the mixture aqueous solution of acid are cooled to 85 DEG C, and still internal pressure is reduced to normal pressure, release mixture aqueous solution, after filtration, obtain the filtrate containing lithium, cobalt, once, wash water mixes with filtrate washing filter residue, obtains the filtrate containing lithium, cobalt.
7. by claim 1, a kind of direct disabled lithium ion cell described in 6 prepares the method for cobalt acid lithium, it is characterized in that containing lithium, the sodium carbonate that concentration is 1 ~ 5mol/L is added in the filtrate of cobalt, potash and the ammonium carbonate precipitation reagent aqueous solution, or add concentration 1 ~ 5mol/L sodium carbonate, a kind of in potash and ammonium carbonate is the NaOH of 0.5 ~ 4mol/L with concentration, the one composition compound precipitants aqueous solution in potassium hydroxide, to pH value to 6.5 ~ 13 of filtrate, lithium carbonate containing and cobalt carbonate is obtained after filtering, cobalt hydroxide, the sediment of basic cobaltous carbonate, wash secondary with water, through 80 ~ 110 DEG C of oven dry, with a small amount of lithium carbonate or cobalt carbonate or cobaltosic oxide adjustment lithium cobalt ratio, 600 ~ 950 DEG C of high-temperature roastings, output cobalt acid lithium.
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Application publication date: 20160210 |