CN101315996A - Method for selectively removing copper from waste lithium ion battery - Google Patents
Method for selectively removing copper from waste lithium ion battery Download PDFInfo
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- CN101315996A CN101315996A CNA2008101153494A CN200810115349A CN101315996A CN 101315996 A CN101315996 A CN 101315996A CN A2008101153494 A CNA2008101153494 A CN A2008101153494A CN 200810115349 A CN200810115349 A CN 200810115349A CN 101315996 A CN101315996 A CN 101315996A
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a method for selectively removing copper from a waste lithium ion battery, which comprises the following steps: the method comprises the steps of taking copper-containing waste lithium ion batteries as raw materials, taking an alkaline medium containing ammonia water as a leaching solution, leaching and separating copper from the crushed or roasted copper-containing waste lithium ion battery raw materials in the leaching solution, wherein the leaching rate of copper reaches 93-99.99%, the copper enters an ammoniacal aqueous solution, the leaching rates of lithium and cobalt are only 5-25% and 0.1-15%, the copper is favorably further recovered from the copper solution, and lithium and cobalt in leaching residues are enriched. The method has simple process, adopts ammoniacal leachate containing ammonia water, controls leaching conditions, preferentially leaches copper, mainly leaves lithium, cobalt and the like in leaching residues, and is beneficial to the efficient recovery of valuable metals in the waste lithium ion battery. The raw materials used in the invention have low price, mild treatment conditions and high decoppering efficiency, are suitable for decoppering requirements of large-scale waste lithium ion batteries, and have low production cost.
Description
Technical field
The present invention relates to a kind of processing of waste and old lithium ion battery and the recovery technology of valuable metal, relate in particular to a kind of method, belong to environmental protection and non-ferrous metallurgy technology field selective decoppering of waste lithium ion battery.
Background technology
In recent years, along with the development of economy, technology and the raising of people's living standard, various portable type electronic products have become the articles for daily use that people work and live as mobile phone, notebook computer, digital camera and video camera etc.Lithium ion battery because the operating voltage height, volume is little, in light weight, specific energy is high, memory-less effect, pollution-free less, advantage such as self discharge is little, have extended cycle life, rechargeable type power supply as portable type electronic product, its consumption has surpassed 90%, become the secondary portable battery of consumption maximum, especially sharply increase in the field of mobile communication use amount.Meanwhile, the also corresponding increase of the quantity of waste and old lithium ion battery.
Arbitrarily abandoning waste and old lithium ion battery is a kind of significant wastage of resource, and also corresponding meeting causes environmental pollution.Waste and old lithium ion battery mainly contains materials such as cobalt acid lithium, lithium hexafluoro phosphate, organic carbonate, carbon materials, copper, aluminium, nickel, manganese.Wherein cobalt, nickel metal are domestic nonferrous metal resources in short supply, and content is very high in applying waste lithium ionic, compare with other old and useless battery, and the recycling of waste and old lithium ion battery can obtain favorable economic benefit.
At present, many research work have been carried out in the processing of waste and old lithium ion battery and the recovery of valuable metal both at home and abroad, proposed many processing methods.In order fully to recycle the various materials in the waste and old lithium ion battery, usually carry out preliminary treatment with the method for physics or chemistry, earlier it is carried out discharge process, material with heterogeneity and composition separates or enrichment again, method with pyrometallurgy or hydrometallurgy reclaims valuable metal then, and comprehensively reclaims all the other materials or harmless treatment.As with waste and old lithium ion battery its after discharge process, pass through operations such as roasting, fragmentation, magnetic separation, classification again, obtain the enriched substance of valuable metal.Perhaps adopt specific organic solvent dissolving binding agent PVDF (Kynoar) that the collector (aluminium foil) on the electrode is separated with cobalt acid lithium, reclaim the cobalt lithium then from leach filter residue, the metal collector of anode (aluminium foil) can be directly as reclaiming product after cleaning.But great majority are only paid attention to the recovery of cobalt, lithium etc., do not note the Selective Separation of copper.
Equipment requirements height (1600 ℃) during the direct high melt waste and old lithium ion battery of pyrometallurgy, the rate of recovery of metal is lower.When from the enriched substance of waste and old lithium ion battery or its valuable metal, reclaiming metal with the method for hydrometallurgy, the most leaching agents that adopt are acid mediums, as sulfuric acid and hydrogen peroxide, nitric acid and hydrogen peroxide, nitric acid, hydrochloric acid, chloroazotic acid etc., be mainly the acid medium system, two kinds or multiple while are entered in the solution by leaching in the metal ions such as cobalt, nickel, copper and lithium; If during battery containing metal copper, can not obtain containing single metal ion solution, not reach the purpose of separating metal ion; And, then mainly contain the extraction or the precipitation method from when separating the different metal ion a kind of infusion solution, and each metal ion species is needed to handle respectively, long flow path is operated loaded down with trivial details; The extractant costliness, the separation costs height.External Sony company early adopts pyrometallurgy and hydrometallurgy process combined, burns waste and old lithium ion battery earlier under higher temperature, leaches alloy with wet method then and reclaims cobalt, and metal recovery rate is lower.
Publication number is the patent of CN1402376, and used discarded lithium ion battery in the high temperature kiln roasting, is decomposed and removes organic bath, pulverizes the back screening, and oversize is handled with magnetic separation and eddy current separation again, isolates iron-clad, Copper Foil and the aluminium foil etc. of size degradation; Screenings is then through corrosion, filtration, and by the control by pH value and electrolytic condition, respectively with diaphragm process electrolysis precipitating metal copper and cobalt.And after electrolysis, be rich in the solution of lithium ion, after adjusting pH-value precipitation metal impurities, then can add carbonate and form the high purity carbon hydrochlorate of lithium and lithium is reclaimed.The equipment and the technical process that relate in this invention are more, inconvenient operation, and the rate of recovery also is restricted.
Publication number is the patent of CN1617380, and in the high temperature kiln roasting, screening produces the fine powder body that contains metal and metal oxide with used discarded lithium ion, ni-mh, nickel-cadmium cell.With corrosion in two stages of fine powder body and filtration, cadmium sulfate is separated out in crystallization from the filtrate of phase I corrosion and filtration gained, and the pH value of filtrate of adjustment second stage corrosion and filtration gained reclaims iron, aluminium and rare earth metal with precipitation of hydroxide.The filtrate that stays can obtain containing two aqueous solution of cobalt and nickel again through extraction and back extraction program, and they are then separated out high-purity cobalt and nickel metal by electrolysis respectively.Electrolysis is separated out that residual water solution behind the nickel metal is added into a water soluble carbonate again and lithium ion is wherein gone out with carbonate deposition.If with this method Treatment of Copper material, when reclaiming valuable metal respectively from leachate, the phase mutual interference of each metal ion species is big.
Publication number is the patent of CN1953269, and battery is emitted electric weight fully, the positive pole of split cell, negative pole and barrier film.Again isolated positive pole is cut into fragment, places N-methyl pyrrolidone solution, stir under 50～100 ℃ of temperature, isolate aluminium foil, filter out positive electrode active materials, vacuumize obtains the thick product of positive electrode active materials; Then with Li
2CO
3Mechanical ball milling mixes, and cooling is ground after the high-temperature calcination, obtains LiCoO
2It is purer that this method reclaims the product that obtains, but following positive pole, negative pole and the barrier film in the waste and old lithium ion battery will be separated separately, thereby reclaim different material separately, is difficult to accomplish in the large-scale production operating process.
Patent or achievement in research that many waste and old lithium ion batteries are handled are disclosed at present both at home and abroad, adopt acid medium to leach multiple valuable metal element in the waste and old lithium ion battery simultaneously, obtain a kind ofly containing multiple metal ion solution simultaneously, and then separation and Extraction, technological process is longer.Plus plate current-collecting body aluminium foil in the waste and old lithium ion battery is less to the recycling influence of other valuable metal in the battery, can control preferably; But negative current collector mainly is a metallic copper, and effective recovery of lithium, cobalt is produced a very large impact.If in leaching process, select suitable technology, the different metal ion was leached in the different stages, obtain the purer multiple leachate that contains the different metal ion respectively, no longer need from the same a kind of leachate that contains multiple metal ion, to extract metal with the method for extraction or fractional precipitation, can simplify production process greatly, and reduce cost and invest.
Lithium ion battery is the just extensive in recent years secondary cell that uses, and the waste and old lithium ion battery recovery method also has many asking to need to be resolved hurrily at present.Because the roasting meeting produces the harm of dioxin, the recovery processing technique requirements of process of pollution-free full wet method is further developed.The solubility behavior of the valuable metal of cupric waste and old lithium ion battery yet there are no research and report in the ammonia solution of ammonia and ammonium salt.Therefore, the inventor finds, waste and old lithium ion battery with the ammonia solution Treatment of Copper, can in leaching process, optionally copper be leached, separate with lithium, cobalt in the battery, copper-containing solution can directly reclaim the high copper products of purity, and can save too much pretreatment process in the present waste and old lithium ion battery recovery method, helps suitability for industrialized production.
Summary of the invention
Embodiment of the present invention provides a kind of method of selective decoppering of waste lithium ion battery, obtains the few copper solution of impurity content by leaching, and copper-containing solution can be directly used in recovery copper.This method is simple, and the recovery of favourable copper makes metallic elements such as lithium and cobalt obtain enrichment, and has eliminated in subsequent recovery operation copper to the influence that metallic elements such as lithium, cobalt extract, and is convenient to the recycling of waste and old lithium ion battery valuable metal.
The objective of the invention is to be achieved through the following technical solutions:
Embodiment of the present invention provides a kind of method of selective decoppering of waste lithium ion battery, this method comprises: with the cupric waste and old lithium ion battery is raw material, the alkaline medium that employing contains ammoniacal liquor is an infusion solution, described cupric waste and old lithium ion battery raw material broken after fragmentation or the roasting leached copper in described infusion solution separate, the leaching rate that obtains copper is 93～99.99%, the leaching rate of lithium is 5～25%, the leaching rate of cobalt is 0.1～15% the ammonia aqueous solution.
Described infusion solution comprises:
Leaching agent A: with a kind of in ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, carbonic hydroammonium, the ammonium chloride or two kinds of ammonium salts and ammoniacal liquor is raw material, and being made into ammonium salt-containing concentration is that 40～280g/L, ammonia concn are the aqueous solution of 5～85g/L; Wherein, when using two kinds of ammonium salts to be ammonium sulfate and ammonium hydrogen sulfate, or in ammonium carbonate and the carbonic hydroammonium combination any;
Perhaps,
Leaching agent B: with pure ammoniacal liquor is raw material, is made into the aqueous solution that ammonia concn is 5～60g/L.
Described described cupric waste and old lithium ion battery raw material with fragmentation after fragmentation or the roasting leaches separation with copper and comprises in described infusion solution: cupric waste and old lithium ion battery raw material is broken into less than 5mm
2Particle.
The liquid-solid ratio of described infusion solution and described cupric waste and old lithium ion battery raw material is 4～25: 1; Extraction time 0.5～6 hour, 15～95 ℃ of extraction temperatures.
Perhaps, with broken after the roasting of cupric waste and old lithium ion battery raw material, its sintering temperature is that 350～900 ℃, roasting time are 3～8 hours.
With described leaching agent A is infusion solution, and cupric waste and old lithium ion battery raw material is broken into less than 5mm
2Particle, with described leaching agent A by liquid-solid ratio 4～25: 1 batching, described particle is added in the described leaching agent A leaching;
Bubbling air or oxygen during leaching, per hour air capacity of Tong Ruing or amount of oxygen and used leaching agent A volume ratio are 100～800: 1, extraction time 1.5～4 hours, 15～50 ℃ of extraction temperatures;
Perhaps,
Adding ammonium persulfate during leaching as oxidant, is 5～50g/L by leachate stereometer addition, extraction time 0.5～4 hour, 20～95 ℃ of extraction temperatures.
With described leaching agent A is infusion solution, and with the roasting of cupric waste and old lithium ion battery raw material, sintering temperature is that 350～900 ℃, roasting time are 3～8 hours, will be broken into less than 5mm after the described raw material cooling after the roasting
2Particle, with described leaching agent A by liquid-solid ratio 4～25: 1 batching, particle is added in the described leaching agent A leaching;
Bubbling air or oxygen during leaching, per hour the volume ratio of air capacity of Tong Ruing or amount of oxygen and used leaching agent A is 100～800: 1, extraction time 1～4 hour, 15～50 ℃ of extraction temperatures;
Perhaps,
Adding ammonium persulfate during leaching as oxidant, is 5～50g/L by leachate stereometer addition, extraction time 0.5～4 hour, 20～95 ℃ of extraction temperatures;
Perhaps,
Directly leach extraction time 2～8 hours, 30～95 ℃ of extraction temperatures.
Described method also comprises: the enriched substance of the cupric that will produce in the time of will handling waste and old lithium ion battery, lithium, cobalt is broken into less than 5mm
2Particle, described particle and described leaching agent A by liquid-solid ratio 4～25: 1 batching, are added described enriched substance particle in the described leaching agent A solution leaching;
Bubbling air or oxygen during leaching, per hour air capacity of Tong Ruing or amount of oxygen are 100～800: 1 with the liquor capacity ratio of used leaching agent A, extraction time 1～4 hour, 15～50 ℃ of extraction temperatures;
Perhaps,
Add ammonium persulfate as oxidant, addition is counted 5～50g/L by the liquor capacity of used leaching agent A, extraction time 0.5～4 hour, 20～95 ℃ of extraction temperatures.
With described leaching agent B is infusion solution, and the waste and old lithium ion battery raw material of cupric is broken into less than 5mm
2Particle, prepare burden by liquid-solid ratio 4～25: 1 with described leaching agent B, described particle is added in the described leaching agent B solution, bubbling air and carbon dioxide, or aerating oxygen and carbon dioxide, leaching, per hour the gas flow of air capacity of Tong Ruing and carbon dioxide is 100～800: 1 with the liquor capacity ratio of described leaching agent B, or the liquor capacity ratio of the gas flow of aerating oxygen amount and carbon dioxide and described leaching agent B is 50～300: 1, extraction time 1.5～5 hours, 15～50 ℃ of extraction temperatures.
With described leaching agent B is infusion solution, and with the roasting of cupric waste and old lithium ion battery raw material, sintering temperature is that 350～900 ℃, roasting time are 3～8 hours, will be broken into less than 5mm after the described raw material cooling after the roasting
2Particle, prepare burden by liquid-solid ratio 4～25: 1 with the pure ammonia spirit of leaching agent B, described particle is added in the solution of described leaching agent B, while bubbling air or oxygen and carbon dioxide, leaching, per hour the air capacity of Tong Ruing and the carbon dioxide gas scale of construction are respectively 100～800: 1 with the liquor capacity ratio of used leaching agent B, perhaps the amount of oxygen of Tong Ruing and the carbon dioxide gas scale of construction are 50～300: 1 with the liquor capacity ratio of used leaching agent B, extraction time 2～6 hours, 15～50 ℃ of extraction temperatures.
Described method also comprises: the enriched substance of the cupric that will produce in the time of will handling waste and old lithium ion battery, lithium, cobalt is broken into less than 5mm
2Particle, the solution of described particle and described leaching agent B is prepared burden by liquid-solid ratio 4～25: 1, described particle is added in the solution of leaching agent B, while bubbling air and carbon dioxide, or aerating oxygen and carbon dioxide, leaching, per hour the air capacity of Tong Ruing and the carbon dioxide gas scale of construction are 100～800: 1 with the liquor capacity ratio of described leaching agent B, or the liquor capacity ratio of the amount of oxygen that feeds and the carbon dioxide gas scale of construction and described leaching agent B is 50～300: 1, extraction time 2～6 hours, 15～50 ℃ of extraction temperatures.
The technical scheme that is provided by the invention described above execution mode as can be seen, it is infusion solution that embodiment of the present invention adopts the alkaline medium that contains ammoniacal liquor, cupric waste and old lithium ion battery broken after the fragmentation or after the roasting is leached in infusion solution, obtain impure less copper solution, help from copper solution, reclaiming copper.This method is simple, the leaching agent raw material sources are extensive, can select for use according to the actual conditions of different location, do not need during processing waste and old lithium ion battery is carried out numerous and diverse preliminary treatment, only need unfired waste and old lithium ion battery discharge, chopping, after perhaps the waste and old lithium ion battery of large volume being peeled off, discharge, shredded, can leach selective decoppering and handle; The enriched substance selective decoppering requirement of the cupric that produces when also being suitable for the waste and old lithium ion battery after the calcination process and handling waste and old lithium ion battery, lithium, cobalt.This method applicability is strong, flow process short, helps extensive chemical industry operation, and production cost is low.Particularly having eliminated copper lithium, cobalt are extracted the influence of reclaiming, is further to simplify the waste and old lithium ion battery handling process, reduces treatment process link and consumption of raw materials, reduces production costs, for high efficiente callback valuable metal or direct materialization provide the foundation.
Embodiment
Embodiment of the present invention provides a kind of method of selective decoppering of waste lithium ion battery, the waste and old lithium ion battery that is mainly used in cupric carries out selective decoppering, thereby finish the recovery of copper, this method specifically comprises: with the cupric waste and old lithium ion battery is raw material, the alkaline medium that employing contains ammoniacal liquor is an infusion solution, described cupric waste and old lithium ion battery raw material broken after fragmentation or the roasting is leached separation with copper in described infusion solution, the leaching rate that obtains copper is 93～99.99%, lithium, the leaching rate of cobalt then has only 5～25% respectively, 0.1～15% the ammonia aqueous solution reclaims copper from the described ammonia aqueous solution.Mainly be to adopt a kind of in the ammonium salts such as ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, carbonic hydroammonium, ammonium chloride or two kinds to mix mutually as leaching agent with ammoniacal liquor, be made into the aqueous solution, waste and old lithium ion battery after adding fragmentation or the roasting fragmentation leaches wherein metallic copper or cupric oxide; Perhaps the aqueous solution with leaching agent mixes with unfired waste and old lithium ion battery particle, leaches metallic copper wherein under the situation that adds oxidant or bubbling air (or oxygen).Leaching agent also can adopt weak aqua ammonia, and bubbling air (or oxygen) and carbon dioxide leach the copper in the waste and old lithium ion battery simultaneously.Adopt above-mentioned different leaching agent, the raw material of selecting to handle can be unfired waste and old lithium ion battery, it also can be waste and old lithium ion battery through high-temperature roasting, and the enriched substance of the cupric that produces when handling waste and old lithium ion battery, lithium, cobalt, in conjunction with different leaching conditions, form different method for decoppering.This method helps further reclaiming copper from the copper solution that obtains, and lithium and cobalt are enriched in the leached mud.
For ease of understanding, embodiment of the present invention is described further below in conjunction with specific embodiment.
Embodiment one
Present embodiment provides a kind of method of selective decoppering of waste lithium ion battery, this method comprises: with the cupric waste and old lithium ion battery is raw material, the alkaline medium that employing contains ammoniacal liquor is an infusion solution, described cupric waste and old lithium ion battery raw material broken after fragmentation or the roasting is leached separation with copper in described infusion solution, obtain containing lithium, cobalt respectively less than the copper solution of 0.6g/L, 0.25g/L, help further reclaiming copper from copper solution, lithium, cobalt obtain enrichment in the leached mud.
Wherein, described infusion solution comprises following two kinds:
(1) leaching agent A: with a kind of in ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, carbonic hydroammonium, the ammonium chloride or two kinds of ammonium salts and ammoniacal liquor is raw material, and being made into ammonium salt-containing concentration is that 40～280g/L, ammonia concn are the aqueous solution of 5～85g/L; Wherein, when using two kinds of ammonium salts to be ammonium sulfate and ammonium hydrogen sulfate, or in ammonium carbonate and the carbonic hydroammonium combination any;
Perhaps,
(2) leaching agent B: with pure ammoniacal liquor is raw material, is made into the aqueous solution that ammonia concn is 5～60g/L.
Wherein, described cupric waste and old lithium ion battery raw material being carried out fragmentation, is that cupric waste and old lithium ion battery raw material is broken into less than 5mm
2Particle, or with cupric waste and old lithium ion battery raw material 350～900 ℃ of following roastings of temperature 3～8 hours, the product after the roasting is fractured into less than 5mm
2Particle;
Wherein, when in described infusion solution copper leach being separated, be 4～25 with the liquid-solid ratio of described infusion solution and described cupric waste and old lithium ion battery raw material: 1 prepares burden; Extraction time 0.5～6 hour, 15～95 ℃ of extraction temperatures.
The method of utilizing above-mentioned leaching agent A and leaching agent B to carry out the waste and old lithium ion battery decopper(ing) specifically comprises following several:
(1). it is specific as follows to be with described leaching agent A that infusion solution carries out the method for decopper(ing):
(1) method for decoppering one: unfired waste and old lithium ion battery is cut into less than 5mm
2Particle, prepare burden by liquid-solid ratio 4～25: 1 with leaching agent A, particle is added in the solution of leaching agent A, leaching, and bubbling air (or oxygen), per hour the air capacity of Tong Ruing (or amount of oxygen) is 100～800: 1 with leaching agent A liquor capacity ratio, extraction time 1.5～4 hours, 15～50 ℃ of extraction temperatures.
(2) method for decoppering two: unfired waste and old lithium ion battery is cut into less than 5mm
2Particle, with leaching agent A by liquid-solid ratio 4～25: 1 batching, particle is added in the solution of leaching agent A leaching; Bubbling air (or oxygen) not during leaching, but add the oxidant ammonium persulfate, addition is counted 5～50g/L by leaching agent A liquor capacity, extraction time 0.5～4 hour, 20～95 ℃ of extraction temperatures.
(3) method for decoppering three: with the waste and old lithium ion battery roasting, sintering temperature, roasting time were respectively 350～900 ℃, 3～8 hours, and make less than 5mm with the method for shredding or grind the cooling back
2Particle, prepare burden by liquid-solid ratio 4～25: 1 with leaching agent A, particle is added in the leaching agent A solution, leaching, and bubbling air (or oxygen), per hour the air capacity of Tong Ruing (or amount of oxygen) is 100～800: 1 with leaching agent liquor capacity ratio, extraction time 1～4 hour, 15～50 ℃ of extraction temperatures.
(4) method for decoppering four: with the waste and old lithium ion battery roasting, sintering temperature, roasting time were respectively 350～900 ℃, 3～8 hours, and make less than 5mm with the method for shredding or grind the cooling back
2Particle.Prepare burden by liquid-solid ratio 4～25: 1 with leaching agent A, particle is added in the leaching agent A solution leaching; Bubbling air (or oxygen) not during leaching, but add the oxidant ammonium persulfate, addition is counted 5～50g/L by the leaching agent liquor capacity, extraction time 0.5～4 hour, 20～95 ℃ of extraction temperatures.
(5) method for decoppering five: with the waste and old lithium ion battery roasting, sintering temperature, roasting time were respectively 350～900 ℃, 3～8 hours, and make less than 5mm with the method for shredding or grind the cooling back
2Particle.Prepare burden by liquid-solid ratio 4～25: 1 with leaching agent A, particle is added in the leaching agent A solution leaching; Bubbling air (or oxygen) not during leaching does not add the oxidant ammonium persulfate, extraction time 2～8 hours, 20～95 ℃ of extraction temperatures yet.
(6) method for decoppering six: the enriched substance of the cupric that will produce in the time of will handling waste and old lithium ion battery, lithium, cobalt and leaching agent A are by liquid-solid ratio 4～25: 1 batching, the enriched substance particle is added in the leaching agent A solution, leaching, and bubbling air (or oxygen), per hour the air capacity of Tong Ruing (or amount of oxygen) is 100～800: 1 with leaching agent liquor capacity ratio, extraction time 1～4 hour, 15～50 ℃ of extraction temperatures.
(7) method for decoppering seven: the enriched substance of the cupric that produces when handling waste and old lithium ion battery, lithium, cobalt and leaching agent A are by liquid-solid ratio 4～25: 1 batching, and in enriched substance particle adding leaching agent A solution, leaching; Bubbling air (or oxygen) not during leaching, but add the oxidant ammonium persulfate, addition is counted 5～50g/L by the leaching agent liquor capacity, extraction time 0.5～4 hour, 20～95 ℃ of extraction temperatures.
(2). be the method that infusion solution carries out decopper(ing) with described leaching agent B, specific as follows:
(1) method for decoppering one: unfired waste and old lithium ion battery is cut into less than 5mm
2Particle, prepare burden by liquid-solid ratio 4～25: 1 with the pure ammonia spirit of leaching agent B, particle is added in the dilute ammonia solution of leaching agent B, while bubbling air (or oxygen) and carbon dioxide, leaching, per hour the air capacity of Tong Ruing (or amount of oxygen) and the carbon dioxide gas scale of construction are respectively 100～800: 1 and 50～300 with leaching agent B liquor capacity ratio: 1, and extraction time 1.5～5 hours, 15～50 ℃ of extraction temperatures.
(2) method for decoppering two: with the waste and old lithium ion battery roasting, sintering temperature, roasting time were respectively 350～900 ℃, 3～8 hours, and make less than 5mm with the method for shredding or grind the cooling back
2Particle.Prepare burden by liquid-solid ratio 4～25: 1 with the pure ammonia spirit of leaching agent B, particle is added in the dilute ammonia solution of leaching agent B, while bubbling air (or oxygen) and carbon dioxide, leaching, per hour the air capacity of Tong Ruing (or amount of oxygen) and the carbon dioxide gas scale of construction are respectively 100～800: 1 and 50～300 with leaching agent B liquor capacity ratio: 1, extraction time 2～6 hours, 15～50 ℃ of extraction temperatures.
(3) method for decoppering three: the enriched substance of the cupric that produces when handling waste and old lithium ion battery, lithium, cobalt and the pure ammonia spirit of leaching agent B are by liquid-solid ratio 4～25: 1 prepares burden, particle is added in the dilute ammonia solution of leaching agent B, while bubbling air (or oxygen) and carbon dioxide, leaching, per hour the air capacity of Tong Ruing (or amount of oxygen) and the carbon dioxide gas scale of construction are respectively 100～800: 1 and 50～300 with leaching agent B liquor capacity ratio: 1, extraction time 2～6 hours, 15～50 ℃ of extraction temperatures.
After above method decopper(ing) processing, the contained copper of waste and old lithium ion battery leaches removal efficiency and reaches 93～99.99%, enters in the ammonia aqueous solution, and the leaching rate of lithium, cobalt then has only 5～25%, 0.1～15% respectively, and lithium, cobalt are mainly stayed in the leached mud.Wherein handle best through waste and old lithium ion battery and product effect thereof after the roasting.According to different waste and old lithium ion batteries, select suitable leaching condition, the leaching rate of copper, lithium, cobalt can stablize respectively be controlled to be＞99.5%,＜10%,＜0.5%, realize the selectively removing of copper, particularly with the separating of cobalt.
Embodiment two
Present embodiment provides a kind of method of selective decoppering of waste lithium ion battery, cooperate as leaching agent with ammonium salt with ammoniacal liquor, bubbling air leaches unfired waste and old lithium ion battery, specifically comprise: the heavy 18.6g of certain brand mobile phone waste and old lithium ion battery, its major metal composition is lithium Li2.74%, cobalt Co22.31%, copper Cu 7.47%, nickel 0.40%, manganese Mn 0.08%, aluminium A19.78%, get 10 of this waste and old lithium ion batteries, without roasting, discharge, peel off the aluminium shell earlier, waste and old lithium ion battery is cut into less than 5mm
2Particle, join contain ammonium carbonate, ammonia concn is respectively in the leaching tanks of the aqueous solution as leaching agent of 80g/L, 30g/L, the liquor capacity of leaching agent is 2100ml, leaching agent and refuse battery particle are fully stirred, particle is suspended in the leaching agent solution, after 5 minutes, can sees the copper of many lights chips float being arranged in mixed solution, from leaching tanks bottoms bubbling air, air feeding amount is 1.2m per hour
3, and even air is overflowed in mixed solution; Extraction temperature is 23 ℃ of room temperatures, and extraction time 2 hours can see in the leaching process that solution colour constantly becomes blue, and the copper fragment fades away; After reaching desired extraction time, will leach mixed solution and filter, washing and filtering slag 2 times obtains blue cupric infusion solution.Analyze copper, lithium, the cobalt composition of infusion solution, the leaching rate of calculating copper reaches 99.1%, and the leaching rate of lithium, cobalt then is respectively 10.6%, 12.1%, and aluminium is not leached.When the ammonia aqueous solution leached, the separating effect of copper and lithium, cobalt was better.
A kind of with in the ammonium salts such as ammonium sulfate, ammonium hydrogen sulfate, carbonic hydroammonium, ammonium chloride, or a kind of replacement ammonium carbonate in ammonium sulfate and ammonium hydrogen sulfate, ammonium carbonate and the carbonic hydroammonium combination, by above-mentioned steps, the leaching rate of copper all can reach more than 96%, the leaching rate of lithium, cobalt then is respectively 9～18%, 0.1～13%, can realize that the selectivity of copper leaches; And replace air with oxygen, can reach same leaching effect.
Embodiment three
Present embodiment provides a kind of method of selective decoppering of waste lithium ion battery, cooperate as leaching agent with ammonium salt with ammoniacal liquor, add oxidant and leach unfired waste and old lithium ion battery, specifically comprise: get 10 of waste and old lithium ion batteries, without roasting, discharge, peel off the aluminium shell earlier, waste and old lithium ion battery is cut into less than 5mm
2Particle, join the sulfur acid ammonium, ammonia concn is respectively in the leaching tanks of the aqueous solution as leaching agent of 50g/L, 20g/L, the liquor capacity of leaching agent is 3000ml, add oxidant ammonium persulfate 50g again, leaching agent solution and refuse battery particle are fully stirred, particle is suspended in the leaching agent solution.After heating in 30 minutes, the temperature that leaches mixed liquor reaches 85 ℃, and it is blue that solution colour also becomes, and insulation extraction time 1 hour can see in the leaching process that solution colour deepens, and the copper fragment of light fades away.After reaching extraction time, will mix infusion solution and filter, washing and filtering slag 3 times obtains blue cupric infusion solution.Analyze copper, lithium, the cobalt composition of infusion solution, the leaching rate of calculating copper reaches 99.5%, and the leaching rate of lithium, cobalt then is respectively 15.7%, 14.3%; The leaching rate of cobalt is lower, has realized that copper separates with the selectivity leaching of lithium, cobalt.
A kind of with in the ammonium salts such as ammonium hydrogen sulfate, ammonium carbonate, carbonic hydroammonium, ammonium chloride, or a kind of replacement ammonium sulfate in ammonium sulfate and ammonium hydrogen sulfate, ammonium carbonate and the carbonic hydroammonium combination, by scheme of the present invention and above-mentioned steps, the leaching rate of copper all can reach more than 94%, the leaching rate of lithium, cobalt then is respectively 15～20%, 10.5～14.5%, can realize that the selectivity of copper leaches.
Embodiment four
Present embodiment provides a kind of method of selective decoppering of waste lithium ion battery, with ammoniacal liquor as leaching agent, aerating oxygen and carbon dioxide leach unfired waste and old lithium ion battery, specifically comprise: get 10 of waste and old lithium ion batteries, without roasting, discharge, peel off the aluminium shell earlier, waste and old lithium ion battery is cut into less than 5mm
2Particle, mix ammonia concn 40g/L with dilute ammonia solution in the leaching tanks, the volume of infusion solution is 2500ml, and ultrasonic probe is put into the mixed solution of leaching agent solution and refuse battery particle, vibrates 5 minutes, fully stir then, particle is suspended in the leaching agent solution.Feed gas from the leaching tanks bottom, the feeding amount of oxygen and carbon dioxide is respectively per hour 1.3m
3, 0.5m
3Extraction temperature is 25 ℃ of room temperatures, extraction time 3.5 hours, and the copper fragment of light is constantly dissolved in the leaching process, and the blue color of solution deepens gradually.After reaching extraction time, will leach mixed liquor and filter, washing and filtering slag 2 times obtains blue cupric infusion solution.The copper of infusion solution, lithium, cobalt composition by analysis, the leaching rate of calculating copper reaches 99.5%, and the leaching rate of lithium, cobalt then is respectively 13.5%, 12.3%.
Replace oxygen by air, press the treatment step in the scheme described in the present embodiment, the leaching rate of copper can cross 99.3%, and the leaching rate of lithium, cobalt then is respectively 14.6%, 12.5%, and copper is leached by selectivity.
Embodiment five
Present embodiment provides a kind of method of selective decoppering of waste lithium ion battery, cooperate as leaching agent with ammonium salt with ammoniacal liquor, aerating oxygen leaches the waste and old lithium ion battery after roasting, specifically comprise: for accelerating roasting process, after the waste and old lithium ion battery discharge of the same kind that 10 embodiment 1 are used, peel off the metallic aluminium shell, in Muffle furnace,, be chopped into less than 5mm after the cooling in 600 ℃ roasting temperature 5 hours
2Particle, join contain ammonium chloride, ammonia concn is respectively in the leaching tanks of the aqueous solution as leaching agent of 150g/L, 25g/L, the liquor capacity of leaching agent is 3000ml, and leaching agent and refuse battery particle are fully stirred, and particle is suspended in the leaching agent solution.Stir after 10 minutes, from leaching tanks bottoms aerating oxygen, oxygen feeding amount is 0.5m per hour
3, and oxygen is evenly distributed in the mixed solution of leaching tanks.Extraction temperature is 35 ℃ of room temperatures, and extraction time 1.5 hours after reaching the time of leaching requirement, will leach mixed solution and filter, and washing and filtering slag 2 times obtains blue cupric infusion solution.Analyze copper, lithium, the cobalt composition of infusion solution, the leaching rate of calculating copper reaches 98.9%, and the leaching rate of lithium, cobalt then is respectively 14.8%, 1.3%, and aluminium is not leached.
A kind of with in the ammonium salts such as ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, carbonic hydroammonium, or a kind of replacement ammonium chloride in ammonium sulfate and ammonium hydrogen sulfate, ammonium carbonate and the carbonic hydroammonium combination, by above-mentioned steps, the leaching rate of copper all can reach more than 97%, the leaching rate of lithium, cobalt then is respectively 10～20%, 0.1～1.5%, can realize that the selectivity of copper leaches; And replace oxygen with air, can reach same leaching effect.
Embodiment six
Present embodiment provides a kind of method of selective decoppering of waste lithium ion battery, cooperate as leaching agent with ammonium salt with ammoniacal liquor, add the waste and old lithium ion battery of oxidant leaching through roasting, specifically comprise: the heavy 40.5g of the supporting waste and old lithium ion battery of certain brand notebook computer, after peelling off shell, its internal material tenor is respectively Co17.48, Cu9.19, Ni0.28, Fe14.61, Al3.88, Li2.60.6 internal materials of peelling off such battery of shell are put into Muffle furnace together in 700 ℃ roasting temperature 6 hours, be chopped into less than 5mm after the cooling
2Particle.Particle is joined sulfur acid ammonium, ammonium hydrogen sulfate, ammonia concn be respectively in the leaching tanks of the aqueous solution as leaching agent of 35g/L, 80g/L, 30g/L, the liquor capacity of leaching agent is 4800ml, adds oxidant ammonium persulfate 40g again.Leaching agent solution and refuse battery particle are fully stirred, particle is suspended in the leaching agent solution.After heating in 40 minutes, the temperature that leaches mixed liquor reaches 80 ℃, and it is blue that solution colour also becomes, insulation extraction time 1.5 hours.After reaching extraction time, will mix infusion solution and filter, washing and filtering slag 3 times obtains blue cupric infusion solution.Behind copper in the analysis infusion solution, lithium, the cobalt content, the leaching rate of calculating copper reaches 99.2%, and the leaching rate of lithium, cobalt then is respectively 16.9%, 0.2%.
A kind of with in the ammonium salts such as ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, carbonic hydroammonium, ammonium chloride, or the replacement ammonium sulfate and the ammonium hydrogen sulfate of ammonium carbonate and carbonic hydroammonium combination, by scheme of the present invention and above-mentioned steps, the leaching rate of copper all can reach more than 98%, the leaching rate of lithium, cobalt then is respectively 12～23%, 0.1～0.3%, realizes that the selectivity of copper leaches.
Embodiment seven
Present embodiment provides a kind of method of selective decoppering of waste lithium ion battery, cooperate as leaching agent with ammonium salt with ammoniacal liquor, bubbling air (or oxygen) not, do not add the waste and old lithium ion battery of oxidant leaching through roasting yet, specifically comprise: with 6 of the old and useless batterys of model of the same race among the embodiment five as leaching raw material, peel off shell and take out internal material, put into Muffle furnace, grind less than 3mm after the cooling in 750 ℃ of roasting temperatures 6 hours
2Particle, particle joined contain ammonium carbonate, carbonic hydroammonium, ammonia concn and be respectively in the leaching tanks of the aqueous solution of 50g/L, 40g/L, 40/L as leaching agent, the liquor capacity of leaching agent is 4500ml, leaching agent solution and refuse battery particle are fully stirred, particle is suspended in the leaching agent solution.After heating in 45 minutes, the temperature that leaches mixed liquor reaches 90 ℃, insulation extraction time 3 hours.Steam that wherein overflows and ammonia are back in the leaching tanks after the water composite cooling pipe cooling, after reaching extraction time, will mix infusion solution and filter, and washing and filtering slag 2 times obtains blue cupric infusion solution.Behind copper in the analysis infusion solution, lithium, the cobalt content, the leaching rate of calculating copper is 95.3%, and the leaching rate of lithium, cobalt then is respectively 16.7%, 1.1%.
A kind of with in the ammonium salts such as ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, carbonic hydroammonium, ammonium chloride, or the replacement ammonium carbonate and the carbonic hydroammonium of ammonium sulfate and ammonium hydrogen sulfate combination, by scheme of the present invention and above-mentioned steps, the leaching rate of copper all can reach more than 94%, the leaching rate of lithium, cobalt then is respectively 11～24%, 0.9～1.6%, and copper is leached by selectivity.
Embodiment eight
Present embodiment provides a kind of method of selective decoppering of waste lithium ion battery, with the weak aqua ammonia is infusion solution, bubbling air and carbon dioxide leach the waste and old lithium ion battery through roasting, specifically comprise: with 6 of the old and useless batterys of embodiment five models of the same race as leaching raw material, peel off shell and take out internal material, put into Muffle furnace in 750 ℃ of roasting temperatures 6 hours, grind less than 3mm after the cooling
2Particle.Particle is mixed with dilute ammonia solution in the leaching tanks, and ammonia concn 50g/L, the volume of infusion solution are 4500ml, ultrasonic probe is put into the mixed solution of leaching agent solution and refuse battery particle, vibrate 5 minutes, fully stir then, particle is suspended in the leaching agent solution.Feed gas from the leaching tanks bottom, the feeding amount of air and carbon dioxide is respectively per hour 2.0m
3, 0.5m
3In 35 ℃ of leachings of room temperature, temperature retention time 3 hours, the blue color of solution deepens gradually in the leaching process, after reaching extraction time, will leach mixed liquor and filter, and washing and filtering slag 2 times obtains blue cupric infusion solution.The copper of infusion solution, lithium, cobalt composition by analysis, the leaching rate of calculating copper reaches 99.3%, and the leaching rate of lithium, cobalt then is respectively 9.4%, 1.9%.
Replace air by oxygen, by scheme of the present invention and above-mentioned steps, the leaching rate of copper is more than 99.2%, and the leaching rate of lithium, cobalt then is respectively 9.7%, 2.1%, and copper is leached by selectivity, and lithium, cobalt are then mainly stayed in the leached mud.
Embodiment nine
Present embodiment provides a kind of method of selective decoppering of waste lithium ion battery, cooperate as leaching agent with ammonium salt with ammoniacal liquor, logical oxygen leaches handles cupric, lithium, the cobalt enriched substance that produces behind the waste and old lithium ion battery, specifically comprise: after waste and old lithium ion battery was carried out processing such as decompress(ion), discharge, roasting, fragmentation, magnetic separation, classification through perforation, the cupric of output, lithium, cobalt enriched substance major metal composition were Li4.75%, Co58.84%, Cu0.58%, Ni0.04%, Al6.10%.Get this refuse battery enriched substance particle 230g, join the sulfur acid ammonium, ammonia concn is respectively in the leaching tanks of the aqueous solution as leaching agent of 150g/L, 20g/L, the liquor capacity of leaching agent is 3000ml.Leaching agent and enriched substance particle are fully stirred, particle is suspended in the leaching agent solution.After 10 minutes, from leaching tanks bottoms bubbling air, air feeding amount is 1.1m per hour
3, and even air is overflowed in mixed solution.Extraction temperature is 30 ℃ of room temperatures, extraction time 1.5 hours.After reaching the leaching requirement, will leach mixed solution and filter, washing and filtering slag 3 times obtains blue cupric infusion solution.Analyze copper, lithium, the cobalt composition of infusion solution, the leaching rate of calculating copper reaches 98.6%, and the leaching rate of lithium, cobalt then is respectively 11.6%, 0.3%.When the ammonia aqueous solution leached, the separating effect of copper and lithium, cobalt was better.
A kind of with in the ammonium salts such as ammonium hydrogen sulfate, carbonic hydroammonium, ammonium carbonate, ammonium chloride, or a kind of replacement ammonium sulfate in ammonium sulfate and ammonium hydrogen sulfate, ammonium carbonate and the carbonic hydroammonium combination, by above-mentioned steps, the leaching rate of copper all can reach more than 97%, the leaching rate of lithium, cobalt then is respectively 9.1～18.5%, 0.1～0.4%, can realize that the selectivity of copper leaches; And replace oxygen with air, can reach same leaching effect.
Embodiment ten
Present embodiment provides a kind of method of selective decoppering of waste lithium ion battery, cooperate as leaching agent with ammonium salt with ammoniacal liquor, add oxidant and leach the cupric that produces behind the processing waste and old lithium ion battery, lithium, the cobalt enriched substance, specifically comprise: after treatment waste and old lithium ion battery, the output cupric, lithium, the enriched substance of cobalt, its major metal composition is Li2.55%, Co2.26%, Cu3.09%, Ni0.04%, get this refuse battery enriched substance particle 260g, join and contain ammonium chloride, ammonia concn is respectively 90g/L, in the leaching tanks of the aqueous solution of 35g/L as leaching agent, the liquor capacity of leaching agent is 2000ml, add oxidant ammonium persulfate 30g again, leaching agent solution and refuse battery particle are fully stirred, particle is suspended in the leaching agent solution.After heating in 18 minutes, the temperature that leaches mixed liquor reaches 60 ℃, and insulation extraction time 1 hour after reaching extraction time, will mix infusion solution and filter, and washing and filtering slag 3 times obtains blue cupric infusion solution.Analyze copper, lithium, the cobalt composition of infusion solution, the leaching rate of calculating copper reaches 96.2%, and the leaching rate of lithium, cobalt then is respectively 16.6%, 0.3%.
With ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, carbonic hydroammonium, etc. a kind of in the ammonium salt, or a kind of replacement ammonium chloride in ammonium sulfate and ammonium hydrogen sulfate, ammonium carbonate and the carbonic hydroammonium combination, by scheme of the present invention and above-mentioned steps, the leaching rate of copper all can reach more than 94%, the leaching rate of lithium, cobalt then is respectively 14～20%, 0.1～0.5%, can realize that the selectivity of copper leaches.
Embodiment 11
Present embodiment provides a kind of method of selective decoppering of waste lithium ion battery, with the weak aqua ammonia is infusion solution, the enriched substance of the cupric that is produced behind bubbling air and the carbon dioxide leaching processing waste and old lithium ion battery, lithium, cobalt, this enriched substance major metal composition is Li4.32%, Co2.95%, Cu3.47%, Ni20.14%, Al7.03%, get this refuse battery enriched substance particle 260g, mix with the dilute ammonia solution in the leaching tanks, ammonia concn 50g/L, the volume of infusion solution are 2000ml.Fully stir, particle is suspended in the leaching agent solution.Feed gas from the leaching tanks bottom, the feeding amount of oxygen and carbon dioxide is respectively per hour 1.4m
3, 0.4m
3Extraction temperature is 25 ℃ of room temperatures, extraction time 5 hours.After reaching extraction time, will leach mixed liquor and filter washing and filtering slag 2 times.Analyze copper, lithium, cobalt composition in the blue cupric infusion solution, the leaching rate of calculating copper reaches 96.7%, and the leaching rate of lithium, cobalt then is respectively 10.3%, 1.1%, and the leaching rate of nickel is 65.9%.
Replace air by oxygen, by scheme of the present invention and above-mentioned steps, the leaching rate of copper is 98.9%, and the leaching rate of lithium, cobalt then is respectively 8.6%, 1.6%, and the leaching rate of nickel is 70.1%, and cobalt is separated by selectivity with copper.
In sum, the alkaline medium that contains ammoniacal liquor and ammonium salt by employing in the embodiment of the invention is a leaching agent, leaches decopper(ing) in advance, obtains the higher copper solution of purity; Utilize some oxides of cobalt acid lithium and cobalt to be insoluble to the character of ammonia solution, control cobalt and lithium etc. are not leached, obtain the leached mud of enriching lithium and cobalt etc., help reducing the treatment process process, overcome the phase mutual interference when containing multiple metal ion solution separating valuable metals element, the high efficiency extraction of valuable metal element in the favourable waste and old lithium ion battery reduces treatment process link and consumption of raw materials, reduces production costs.This method technology is simple, can directly handle the small-sized waste and old lithium ion battery after overdischarge; To bigger waste and old lithium ion battery, metal or plastic casing are removed in the discharge back, also can handle easily, will save disposal cost like this, the increase treating capacity.
Above-mentioned have among some embodiment, and used waste and old lithium ion battery has been peelled off aluminium shell etc. when preliminary treatment, just in order to reclaim aluminium better; If do not divest the aluminium shell, and it is shredded, other material in waste and old lithium ion battery carries out decopper(ing) to be handled, and also can not influence the decopper(ing) effect.
The above; only be specific embodiments of the invention; succession between each embodiment does not cause any restriction to the present invention; protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claim.
Claims (10)
1, a kind of method of selective decoppering of waste lithium ion battery, it is characterized in that, this method comprises: with the cupric waste and old lithium ion battery is raw material, the alkaline medium that employing contains ammoniacal liquor is an infusion solution, described cupric waste and old lithium ion battery raw material broken after fragmentation or the roasting leached copper in described infusion solution separate, the leaching rate that obtains copper is 93～99.99%, the leaching rate of lithium is 5～25%, the leaching rate of cobalt is 0.1～15% the ammonia aqueous solution.
2, method according to claim 1 is characterized in that, described infusion solution comprises:
Leaching agent A: with a kind of in ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, carbonic hydroammonium, the ammonium chloride or two kinds of ammonium salts and ammoniacal liquor is raw material, and being made into ammonium salt-containing concentration is that 40～280g/L, ammonia concn are the aqueous solution of 5～85g/L; Wherein, when using two kinds of ammonium salts to be ammonium sulfate and ammonium hydrogen sulfate, or in ammonium carbonate and the carbonic hydroammonium combination any;
Perhaps,
Leaching agent B: with pure ammoniacal liquor is raw material, is made into the aqueous solution that ammonia concn is 5～60g/L.
3, method according to claim 1 is characterized in that, described described cupric waste and old lithium ion battery raw material with fragmentation after fragmentation or the roasting leaches separation with copper and comprises in described infusion solution: cupric waste and old lithium ion battery raw material is broken into less than 5mm
2Particle.
According to claim 1 or 2 or 3 described methods, it is characterized in that 4, the liquid-solid ratio of described infusion solution and described cupric waste and old lithium ion battery raw material is 4～25: 1; Extraction time 0.5～6 hour, 15～95 ℃ of extraction temperatures.
Perhaps, with broken after the roasting of cupric waste and old lithium ion battery raw material, its sintering temperature is that 350～900 ℃, roasting time are 3～8 hours.
5, method according to claim 2 is characterized in that, is infusion solution with described leaching agent A, and cupric waste and old lithium ion battery raw material is broken into less than 5mm
2Particle, with described leaching agent A by liquid-solid ratio 4～25: 1 batching, described particle is added in the described leaching agent A leaching;
Bubbling air or oxygen during leaching, per hour air capacity of Tong Ruing or amount of oxygen and used leaching agent A volume ratio are 100～800: 1, extraction time 1.5～4 hours, 15～50 ℃ of extraction temperatures;
Perhaps,
Adding ammonium persulfate during leaching as oxidant, is 5～50g/L by leachate stereometer addition, extraction time 0.5～4 hour, 20～95 ℃ of extraction temperatures.
6, method according to claim 2, it is characterized in that, be infusion solution with described leaching agent A, with the roasting of cupric waste and old lithium ion battery raw material, sintering temperature is that 350～900 ℃, roasting time are 3～8 hours, will be broken into less than 5mm after the described raw material cooling after the roasting
2Particle, with described leaching agent A by liquid-solid ratio 4～25: 1 batching, particle is added in the described leaching agent A leaching;
Bubbling air or oxygen during leaching, per hour the volume ratio of air capacity of Tong Ruing or amount of oxygen and used leaching agent A is 100～800: 1, extraction time 1～4 hour, 15～50 ℃ of extraction temperatures;
Perhaps,
Adding ammonium persulfate during leaching as oxidant, is 5～50g/L by leachate stereometer addition, extraction time 0.5～4 hour, 20～95 ℃ of extraction temperatures;
Perhaps,
Directly leach extraction time 2～8 hours, 30～95 ℃ of extraction temperatures.
7, method according to claim 2 is characterized in that, described method also comprises: the enriched substance of the cupric that will produce in the time of will handling waste and old lithium ion battery, lithium, cobalt is broken into less than 5mm
2Particle, described particle and described leaching agent A by liquid-solid ratio 4～25: 1 batching, are added described enriched substance particle in the described leaching agent A solution leaching;
Bubbling air or oxygen during leaching, per hour air capacity of Tong Ruing or amount of oxygen are 100～800: 1 with the liquor capacity ratio of used leaching agent A, extraction time 1～4 hour, 15～50 ℃ of extraction temperatures;
Perhaps,
Add ammonium persulfate as oxidant, addition is counted 5～50g/L by the liquor capacity of used leaching agent A, extraction time 0.5～4 hour, 20～95 ℃ of extraction temperatures.
8, method according to claim 2 is characterized in that, is infusion solution with described leaching agent B, and the waste and old lithium ion battery raw material of cupric is broken into less than 5mm
2Particle, prepare burden by liquid-solid ratio 4～25: 1 with described leaching agent B, described particle is added in the described leaching agent B solution, bubbling air and carbon dioxide, or aerating oxygen and carbon dioxide, leaching, per hour the gas flow of air capacity of Tong Ruing and carbon dioxide is 100～800: 1 with the liquor capacity ratio of described leaching agent B, or the liquor capacity ratio of the gas flow of aerating oxygen amount and carbon dioxide and described leaching agent B is 50～300: 1, extraction time 1.5～5 hours, 15～50 ℃ of extraction temperatures.
9, method according to claim 2, it is characterized in that, be infusion solution with described leaching agent B, with the roasting of cupric waste and old lithium ion battery raw material, sintering temperature is that 350～900 ℃, roasting time are 3～8 hours, will be broken into less than 5mm after the described raw material cooling after the roasting
2Particle, prepare burden by liquid-solid ratio 4～25: 1 with the pure ammonia spirit of leaching agent B, described particle is added in the solution of described leaching agent B, while bubbling air or oxygen and carbon dioxide, leaching, per hour the air capacity of Tong Ruing and the carbon dioxide gas scale of construction are respectively 100～800: 1 with the liquor capacity ratio of used leaching agent B, perhaps the amount of oxygen of Tong Ruing and the carbon dioxide gas scale of construction are 50～300: 1 with the liquor capacity ratio of used leaching agent B, extraction time 2～6 hours, 15～50 ℃ of extraction temperatures.
10, method according to claim 2 is characterized in that, described method also comprises: the enriched substance of the cupric that will produce in the time of will handling waste and old lithium ion battery, lithium, cobalt is broken into less than 5mm
2Particle, the solution of described particle and described leaching agent B is prepared burden by liquid-solid ratio 4～25: 1, described particle is added in the solution of leaching agent B, while bubbling air and carbon dioxide, or aerating oxygen and carbon dioxide, leaching, per hour the air capacity of Tong Ruing and the carbon dioxide gas scale of construction are 100～800: 1 with the liquor capacity ratio of described leaching agent B, or the liquor capacity ratio of the amount of oxygen that feeds and the carbon dioxide gas scale of construction and described leaching agent B is 50～300: 1, extraction time 2～6 hours, 15～50 ℃ of extraction temperatures.
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