CN102544628B - Method for leaching positive electrode active material - Google Patents
Method for leaching positive electrode active material Download PDFInfo
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- CN102544628B CN102544628B CN201110250193.2A CN201110250193A CN102544628B CN 102544628 B CN102544628 B CN 102544628B CN 201110250193 A CN201110250193 A CN 201110250193A CN 102544628 B CN102544628 B CN 102544628B
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Abstract
Nickel, cobalt and lithium are efficiently leached from the positive electrode active material of lithium-ion secondary cell, obtaining solution suitable for isolating various metals. The invention relates to a method for leaching positive electrode active material which leaches valued metals from the positive electrode active materials of a lithium-ion formed by composite oxide having transition metals including at least manganese. The method comprises a first process which is to dissolve soluble parts of sulfuric acid solution in the positive electrode active material, and a second process which is no solid-liquid separation is conducted after the first process, and adding hydrogen peroxide in sulfuric acid leaching slurry solution, and leaching unleached parts in the left sulfuric acid leaching slurry.
Description
Technical field
The method that in the positive active material of the lithium ion battery that the composite oxides that the present invention relates to form from the transition metal by least containing manganese form, valuable metal is leached.
Background technology
Leaching method as positive active material, in Unexamined Patent 10-287864 communique (patent documentation 1), there is the leaching method that adopts inorganic acid and hydrogen peroxide, with respect to the metal in positive active material, with molar ratio computing, used respectively 1-5 inorganic acid, hydrogen peroxide doubly.In the method, due to inorganic acid, hydrogen peroxide surplus, acid, hydrogen peroxide a large amount of after therefore leaching are residual in leachate.Therefore,, the in the situation that of further the separation circuits such as solvent extraction being set in rear operation, for the acid to residual neutralizes, must add neutralization reagent.In addition, residual hydrogen peroxide, in solvent extraction, likely makes to extract solvent oxidation and deteriorated.Therefore, preferably before solvent extraction, remove in advance, but the reagent of hydrogen peroxide being removed from leachate becomes necessary.
In TOHKEMY 2007-122885 communique (patent documentation 2), recorded following technology: when the regeneration of lithium ion battery, by valuable metals such as lithium contained in positive active material etc., nickel, cobalts, use sulfuric acid leaching, and then utilize the fixed carbon such as carbon to contain thing leaching acceleration.
In Japanese kokai publication hei 11-167936 communique (patent documentation 3), as the concrete scheme that the problem of institute's phase is solved, recorded use hydrochloric acid, the method that positive active material is leached.
Following method is disclosed in TOHKEMY 2008-231522 communique (patent documentation 4): from useless lithium cell slag is used hydrochloric acid or sulfuric acid that manganese, cobalt, nickel are leached, from this leachate, carry out solvent extraction, by manganese, the separation of cobalt-nickel.
Patent documentation 1: Japanese kokai publication hei 10-287864 communique
Patent documentation 2: TOHKEMY 2007-122885 communique
Patent documentation 3: Japanese kokai publication hei 11-167936 communique
Patent documentation 4: TOHKEMY 2008-231522 communique
Summary of the invention
According to the method for recording in patent documentation 1, for positive active material is leached, there is following problem: not only need to make acid, hydrogen peroxide etc. excessive, and before the solution after leaching is processed, the processing of other employing nertralizer, reducing agent is also necessary.In addition, according to the method for recording in patent documentation 2, as adsorbent, must use fixed carbon to contain thing, the leaching facilitation effect that this contains deposits yields is not also suitable for all positive active materials, be limited to and can be adsorbed in fixed carbon and contain thing, therefore exist and become the problem that the positive active material of recycle object is restricted.In addition, as the concrete method of recording in patent documentation 3, if use hydrochloric acid when the leaching of positive active material, likely in Leaching reaction, produce chlorine, have undesirable problem.
In addition, as the method for recording in patent documentation 4, when after leaching, liquid donor solvent extracts, the manganese ion of high valence mumber is difficult for being extracted by counter, sometimes when anti-extraction, residue in organic phase, in this case under the residual state of manganese ion by organic phase repeatedly for extracting, from the viewpoint of the recovery of noble metal, not talkative good problem while having.
The present invention is in view of these problems, and object is to provide the method expeditiously valuable metal being leached from the positive active material of lithium ion 2 primary cells.In addition,, from other viewpoint, object is to provide and is being applicable to the method for not using reagent in the solution of the fluidity of each ion species separation and modulating.
The inventor finds, after positive active material being leached with sulfuric acid, use hydrogen peroxide, thereby can be by leaching required sulfuric acid, the amount of hydrogen peroxide is cut down compared with prior art, can realize high leaching efficiency simultaneously, also found by adding positive active material in the solution after leaching, thereby in the situation that not adding the reagent such as nertralizer, reducing agent, manganese ion in solution is reduced to divalent, make residual acid consumption etc., obtain the method for the solution of the preferred fluidity of separation method of solvent extraction method plasma kind.
The present invention is based on above-mentioned experience and complete, is the method that possesses the positive active material leaching that makes lithium ion battery of feature shown below.
(1) leaching method of positive active material, is the method for valuable metal leaching that makes in the positive active material of the lithium ion battery that forms from the composite oxides by least forming containing the transition metal of manganese, it is characterized in that comprising:
In having added sulphur aqueous acid, by the 1st operation that the soluble composition of sulfuric acid solution is dissolved in above-mentioned positive active material; With
After the 1st operation, do not carry out Separation of Solid and Liquid, in sulfuric acid leaching pulp solution, add hydrogen peroxide, further by the 2nd operation that does not leach composition leaching residual in sulfuric acid leaching slurry.
(2) method about recording in (1), is characterized in that, also comprises:
After the leaching that makes to obtain in the 2nd operation, the oxidation-reduction potential of liquid reduces, and improves the 3rd operation of pH; With
The reactant liquor obtaining in the 3rd operation is carried out after Separation of Solid and Liquid, adopt solvent extraction that manganese is extracted to organic phase, next with acidic aqueous solution, to organic phase is counter, extract, obtain the 4th operation of the manganese aqueous solution.
(3) method about recording in (2), is characterized in that, in above-mentioned the 3rd operation, after the leaching obtaining, in liquid, adds positive active material in above-mentioned the 2nd operation.
(4) method of recording about any one in (1)～(3), it is characterized in that, it is principal component that above-mentioned positive active material be take the oxide of contained nickel, cobalt, manganese and lithium in positive active material, and the amount of the sulfuric acid of interpolation is used to be less than the amount of total molal quantity of the molal quantity of nickel, cobalt, manganese, lithium.
(5) method about recording in (4), it is characterized in that, the amount of the hydrogen peroxide adding, with respect in positive active material in above-mentioned the 1st operation in sulfuric acid solution the total mole of the contained nickel of undissolved positive active material, cobalt, manganese, with 0.8～1.2 times of mole, use.
(6) method of recording about any one in (1)～(5), it is characterized in that, after the leaching that adopts sulfuric acid and hydrogen peroxide, in liquid, add positive active material, the value of oxidation-reduction potential is adjusted to below 700mV (vs.Ag/AgCl) to the anti-extraction of the manganese of the organic phase that promotion obtains from solvent extraction.
(7) method of recording about any one in (1)～(6), is characterized in that, after the leaching obtaining, in liquid, adds positive active material to stir in above-mentioned the 2nd operation, and the pH that leaches rear liquid is risen to more than 2.5.
According to the present invention, obtain following effect: in the leaching of the positive active material of lithium ion battery,
1) while leaching, use sulfuric acid, therefore do not produce chlorine etc.
2) first with sulfuric acid, the positive active material of the enough sulfuric acid dissolutions of energy is leached to the use amount that therefore can cut down hydrogen peroxide.
3) manganese ion in the solution after leaching is reduced to divalent, can be modulated to the solution of the separated fluidity that is applicable to solvent extraction plasma kind.
Can be from the positive active material of lithium ion battery leaching nickel, cobalt, manganese, lithium efficiently.
Accompanying drawing explanation
Fig. 1 means until the figure of the flow process of the extraction of manganese.
Fig. 2 means the figure of the leaching flow process of positive active material.
The coordinate diagram that ORP, the pH of leachate when Fig. 3 means the leaching of positive active material changes.
Fig. 4 is the figure that schematically represents that liquid carries out the tone comparison of the organic phase after solvent extraction, anti-extraction from leaching.
Embodiment
A scheme of the present invention is shown in to Fig. 1.As leach processing positive active material that material that object uses is lithium ion battery or the positive active material, the extraction check processing product in quality management, the residue being obtained by method of the present invention etc. of (substandard) outside the specification of the generations such as manufacture process of positive active material.So-called positive active material is the composite oxides that contain lithium nickelate, cobalt acid lithium, LiMn2O4 and nickel, cobalt, manganese, lithium with various ratios.
The composition that contains the enough sulfuric acid leachings of energy in positive active material, therefore, first, is used sulfuric acid to leach for these compositions, obtains sulfuric acid leaching pulp solution (the 1st operation).The amount of the sulfuric acid now adding, from made the viewpoint of its leaching completely in the past, be at least the total equivalent with the molal quantity of each valuable metal, if considering efficiency, for more amount is general knowledge, in the present invention, be preferably less than the total of the molal quantity of nickel in positive active material, cobalt, manganese, lithium, from the viewpoint of the efficient activity that dissolves, preferably nickel, more than [(total of the molal quantity of cobalt, manganese, lithium)-(molal quantity * 0.5 of lithium)].For example, in positive active material, contain respectively nickel, cobalt, manganese separately 0.3 mole of 0.1 mole and lithium in the situation that, the sulfuric acid amount that leaching is used in processing is generally and is less than 0.1+0.1+0.1+0.3=0.6 mole, if consider the efficiency leaching, preferably more than 0.1+0.1+0.1+0.3 * 0.5=0.45 mole.As use the reason of sulfuric acid with this amount, even if be, because be not, do not use superfluous sulfuric acid that valuable metal is leached completely, but used sulfuric acid still less, by the leaching in the 2nd operation, process and also can make roughly total amount leach, by controlling sour use amount, reduce costs, and do not need the neutralisation treatment after leaching, or needn't under strict condition, carry out.Should illustrate, even if liquid temperature is reacted also and carried out at normal temperatures.
Secondly, after the 1st operation, do not carry out Separation of Solid and Liquid, in sulfuric acid leaching pulp solution, add hydrogen peroxide (the 2nd operation).Now, the interpolation of hydrogen peroxide is carried out after can adding at sulfuric acid, stirring continuously, also can change the time or also changes place and carry out.By first with sulfuric acid, positive active material being leached, the use amount of hydrogen peroxide less.This is the reason of first using sulfuric acid leaching.Amount that can enough sulfuric acid leachings, because of the composition of positive active material different.Therefore,, if side by side pack hydrogen peroxide into sulfuric acid, produce the profit and loss of hydrogen peroxide.If first use sulfuric acid leaching, for not dissolving part, add hydrogen peroxide, for the composition that can dissolve, can not use hydrogen peroxide, the use amount that can cut down hydrogen peroxide in sulfuric acid.
In the positive active material of crossing with sulfuric acid leaching, the nickel, cobalt, manganese, the lithium that do not leach are completely residual.For they are leached, add hydrogen peroxide.About the addition of hydrogen peroxide, add for the total amount left and right with the undissolved nickel of sulfuric acid, cobalt, manganese equimolar amounts, for example, for the total mole of nickel, cobalt, manganese, add 0.8～1.2 times of mole.For example, in the positive active material of crossing with sulfuric acid leaching, contain respectively in the situation of 0.06 mole, nickel, 0.06 mole of cobalt, 0.06 mole, manganese, leaching the amount of hydrogen peroxide of using in processing is 0.06+0.06+0.06=0.18 mole of left and right, for example 0.144 (0.18 * 0.8)～0.216 (0.18 * 1.2) mole.The interpolation of the hydrogen peroxide that it is above is disadvantageous on cost.In addition,, when residual hydrogen peroxide adopts solvent extraction to carry out ion species separated in rear operation, sometimes to extracting solvent, produce harmful effect.By the interpolation of hydrogen peroxide, the leaching of the nickel of failing to leach the in the situation that of sulfuric acid just, cobalt, manganese, lithium gets along with, while adopting the leaching of sulfuric acid, add and in solution residual sulfuric acid be consumed.
Conventionally, the solution after leaching is used for to the separating treatment of ensuing metal ion, but can reduces the oxidation-reduction potential of the rear liquid of this leaching with sulfuric acid, hydrogen peroxide, improve pH.Thus, think and the ion species that becomes high oxidation state is reduced to the ion of divalent.After leaching now, the oxidation-reduction potential of liquid is below 700mV (vs.Ag/AgCl).Thus, can promote from the anti-extraction of the manganese of the organic phase of solvent extraction.Even also carry out in the lower reaction of normal temperature (20～30 ℃).
The method reducing as the oxidation-reduction potential that makes to leach rear liquid, can enumerate for example interpolation of positive active material.As the positive active material adding, even if use the leaching residue shown in Fig. 2, also can obtain same effect.Or, can add the positive active material not leaching, also can add the positive active material of not leaching and the positive active material after leaching.
As from solution by the method for separation of metal ions, can use following solvent extraction method: for liquid after liquid after leaching or oxidation-reduction potential and the leaching of pH after regulating, carry out after Separation of Solid and Liquid, under the existence of the extractant of the extraction of auxiliary regulation metal ion with an organic solvent.Organic phase before metal ion is extracted is colourless, but the organic phase after colored metal ion in solution is extracted is painted, with anti-extraction of the aqueous solution of suitable acid concentration, to extract in the aqueous solution the metal ion of organic phase is counter, the organic phase after anti-extraction is returned to colourless again.Thus, can confirm the alternate movement of metal ion.
As such extractant, can enumerate phosphoric acid is that extractant, phosphonic acids are extractant etc., more specifically, can enumerate di-(2-ethylhexyl)phosphoric acid etc.
In the process leaching, the valence mumber of manganese etc. becomes higher than divalent sometimes.Even metal of the same race, the different multiple metal ion of valence mumber mixes the phenomenon existing like this, when the method for each ion species separation being carried out to solvent extraction method after leaching, becomes problem.If under the state that the manganese ion kind that in liquid, valence mumber is high after leaching exists, carry out solvent extraction, sometimes after anti-extraction, be extracted a part of manganese ion that agent controls and still remain in organic phase.Its result, sees the painted of purple in the solvent after anti-extraction sometimes.Think that this is the color of the manganese ion that valence mumber is higher than divalent.
Residual manganese amount in organic solvent, a small amount of for every 1L organic solvent tens mg manganese, in solvent extraction, generally turns back to extraction by the organic solvent after instead extracting again, extracts continuously, so in organic solvent, has the thoroughly anti-manganese extracting accumulate.In addition, the manganese ion that valence mumber is high has oxidizing force, therefore in solvent extraction likely by oxidation in organic solvent.Due to these reasons, by anti-extraction, from organic phase, by the metal ion of whole amounts, to extract be desirable, and the metal ion that can not instead extract is removed in advance or regulated valence mumber etc. to become the ion species that can instead extract and becomes important.
As its method, if add positive active material in liquid after leaching, the valence mumber of manganese ion reduces, and becomes and easily by counter, is extracted, and therefore in the organic phase after anti-extraction, the residual quantity of manganese reduces.Organic phase after anti-extraction is colourless.
By adding positive active material, consume residual sulfuric acid and hydrogen peroxide.Thus, the pH that leaches rear liquid rises.In the situation that liquid from leaching adopts solvent extraction etc. by nickel, cobalt, manganese, lithium separation, faintly acid is to middle sexual compatibility.Reason is, the extraction pH that extracts the solvent of nickel, cobalt, manganese, lithium is that faintly acid is to neutral region.Therefore, if the acid concentration height of liquid after leaching is improper.But if improve the pH after leaching with nertralizers such as alkaline agents, reagent cost additionally necessitates, if add the positive active material as raw material, does not need neutralization reagent.
If liquid from leaching, using phosphoric acid is that extractant, phosphonic acids are the solvent extraction that extractant carries out manganese, obtain the extracted amount of certain degree, and it is necessary extracting balance pH and be and be more than 2.5.Therefore, before preferably extracting, the pH of liquid also approaches this pH or for more than it, and the pH that preferably makes to leach rear liquid is more than 2.5.Reason is, if extracted than liquid before extracting the extraction that balance pH is low with pH, in order to maintain, extract balance pH, must carry out and the neutralization of extracting liquid the neutralization of the proton emit from extractant together and extraction simultaneously, therefore must add a large amount of pH adjusting agents during abstraction reaction, extract pH and control the difficulty that becomes.
At this, the extraction of manganese is specifically illustrated, other valuable metals are that cobalt, nickel, lithium can adopt existing known method to extract respectively.
The positive active material adding, its major part becomes leaching residue, if but this residue is added after repeatedly leaching or leaching, can not become the loss entering outside operation.
Embodiment
(embodiment 1: for the effect with adding hydrogen peroxide after sulfuric acid leaching)
As shown in Figure 2, in the sulfuric acid solution 0.5L of 1 mole/L (0.5 mole, sulfuric acid), add positive active material 1 (31.3 be dried-g), in the situation that not heating, with 600rpm, stir.The sulfuric acid amount of adding for positive active material in nickel, cobalt, manganese equimolar amounts sulfuric acid with respect to lithium, take the total amount of the sulfuric acid that molar ratio computing is 0.5.The composition of the positive active material of interpolation is shown in to table 1.Liquid temperature is 20～30 ℃.In addition,, according to the table 2 that represents the composition of sulfuric acid leaching residue 2, by only adopting the leaching of sulfuric acid, by leaching respectively 37wt% in nickel contained in the positive active material before leaching, cobalt, manganese, lithium is leached to 66wt%.
After the leaching that only adopts sulfuric acid of preceding paragraph, do not carry out Separation of Solid and Liquid, in the pulp solution of sulfuric acid leaching, add hydrogen peroxide.Add the 35wt% aquae hydrogenii dioxidi containing the hydrogen peroxide of the total amount that in the positive active material with respect to vitriolization not, contained nickel, cobalt, manganese is equimolar amounts, in the situation that not heating, with 600rpm, stir.The positive active material of vitriolization does not consist of the composition shown in table 2.Its result, according to the table 3 of the composition of liquid 3 after represent leaching, after first leaching with sulfuric acid, adds hydrogen peroxide and leaches, and makes respectively nickel more than 96wt%, cobalt, manganese, lithium in the positive active material before leaching leach.
Table 1
Table 2
Table 3
(embodiment 2: adopt the interpolation of positive active material and the manganese solvent extraction of the leachate after interpolation)
In solution 0.5L after the leaching that adopts sulfuric acid and hydrogen peroxide, add positive active material (10 be dried-g), while stirring under normal temperature (20～30 ℃) with 600rpm, the oxidation-reduction potential ORP of solution drops to below 700mV (vs.Ag/AgCl).In addition, the pH of solution rises to more than 3.The results are shown in Fig. 3.The composition of the positive active material adding is identical with the positive active material shown in table 1.The time of having added positive active material is while being the 6.5 hours reaction time in figure.Then, continue to stir, find the decline of oxidation-reduction potential ORP and the rising of pH.Add after positive active material, after 8.5 hours, (from leaching, start 15 hours), after leaching, the ORP of liquid is below 700mV.PH rises to 3.8.
Add this positive active material, liquid after the leaching of oxidation-reduction potential ORP and pH having been carried out regulate in addition after Separation of Solid and Liquid, is carried out to manganese solvent extraction from filtrate, the manganese of leachate is extracted to organic phase.Secondly, in organic phase, add aqueous sulfuric acid, from organic phase, extract the aqueous solution manganese is counter.It is the mixed solvent of di-(2-ethylhexyl)phosphoric acid (D2EHPA processed of LANXESS company) 25 volume % and diluent shell sol D70 (Shell Chemicals Co., Ltd.) that manganese used herein extracts solvent.Extraction conditions, anti-extraction conditions are shown in table 4.Its result, the color of the organic phase after anti-extraction is colourless, and the manganese in the organic phase after anti-extraction is analyzed, the manganese concentration of result organic phase 1L seldom, is 30mg/L, the manganese extracting roughly instead can be extracted.(table 5)
Table 4
| Extract balance pH | 3.0 |
| PH adjusting agent | 25wt% caustic soda |
| O/A is than (organic phase/leachate) | 50ml/50ml |
| O/A is than (organic phase/anti-extract) | 50ml/50ml |
| Anti-extract | 200g/L aqueous sulfuric acid |
| Liquid temperature (℃) | 20-30 |
| Reaction time (dividing) | 15 |
| Time of repose (dividing) | 15 |
Table 5
| Mn extracted amount (mg/ organic phase L) | 9500 |
| Organic phase residual quantity (mg/ organic phase L) | 30 |
(about having or not the comparison of the anti-extracted amount that adds the manganese that positive active material causes in liquid after leaching)
The condition of embodiment 2 is designated as to " condition A ".Condition except embodiment 1, after leaching, in liquid, do not add beyond positive active material, after making positive active material leach, for the filtrate of Separation of Solid and Liquid, under the identical condition of the table 4 with embodiment 2, carry out solvent extraction and anti-extraction of manganese under the condition identical with embodiment 2.Be designated as " condition B ".Color to the organic phase after anti-extraction in condition A and condition B compares, after leaching, added under the condition (condition A) of positive active material, organic phase is colourless, and is not adding under the condition (condition B) of positive active material, and organic phase is coloured to purple.The results are shown in Fig. 4 (a), (b).As shown in table 6, for residual manganese concentration in the organic phase after anti-extraction, with leach after do not add the condition (condition B) of positive active material to compare, condition (condition A) side who has added positive active material after leaching is lower, by add positive active material after leaching, can extract more manganese.
Table 6
Claims (4)
1. a leaching method for positive active material, is the method that makes the positive active material leaching of the lithium ion battery that valuable metal forms from the composite oxides by least forming containing the transition metal of manganese, it is characterized in that, comprising:
In having added sulphur aqueous acid, by the 1st operation that the soluble composition of sulfuric acid solution is dissolved in described positive active material; With
After the 1st operation, do not carry out Separation of Solid and Liquid, in sulfuric acid leaching pulp solution, add hydrogen peroxide, further by the 2nd operation that does not leach composition leaching residual in sulfuric acid leaching slurry,
Also comprise the oxidation-reduction potential that is reduced in liquid after the leaching obtaining in the 2nd operation, improve the 3rd operation of pH, wherein, in the 2nd operation, adopt after the leaching that sulfuric acid and hydrogen peroxide obtain and add positive active material in liquid, the value of oxidation-reduction potential is adjusted to below 700mV, and the pH that leaches rear liquid is risen to more than 2.5, reference electrode is Ag/AgCl.
2. the method for claim 1, is characterized in that, also comprises:
The reactant liquor obtaining in the 3rd operation is carried out after Separation of Solid and Liquid, adopt solvent extraction that manganese is extracted to organic phase, next organic phase is obtained the 4th operation of the manganese aqueous solution with anti-extraction of acidic aqueous solution.
3. method as claimed in claim 1 or 2, it is characterized in that, it is principal component that described positive active material be take the oxide of the nickel, cobalt, manganese and the lithium that contain in positive active material, and the amount of the sulfuric acid of interpolation is used to be less than the amount of total molal quantity of the molal quantity of nickel, cobalt, manganese, lithium.
4. method as claimed in claim 3, it is characterized in that, the amount of the hydrogen peroxide adding, the total mole of the nickel contained with respect to the positive active material that is not dissolved in sulfuric acid solution in positive active material in described the 1st operation, cobalt, manganese, is used with 0.8～1.2 times of mole.
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| JP2010206087 | 2010-08-30 | ||
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| JP2011-164477 | 2011-07-27 | ||
| JP2011164477A JP5254407B2 (en) | 2010-08-30 | 2011-07-27 | Cathode active material leaching method |
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| CN102544628B true CN102544628B (en) | 2014-09-10 |
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| CN1949584A (en) * | 2006-10-25 | 2007-04-18 | 丁四宜 | Environment protection using method for waste Ni-Cd battery |
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| CN102544628A (en) | 2012-07-04 |
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