CN101831548B - Method for recovering valuable metals from waste lithium manganese oxide battery - Google Patents
Method for recovering valuable metals from waste lithium manganese oxide battery Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000002699 waste material Substances 0.000 title claims abstract description 25
- 229910002102 lithium manganese oxide Inorganic materials 0.000 title claims abstract description 23
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 150000002739 metals Chemical class 0.000 title abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- -1 iron ions Chemical class 0.000 claims abstract description 10
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 108010064245 urinary gonadotropin fragment Proteins 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 150000002978 peroxides Chemical class 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 238000000247 postprecipitation Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 abstract description 12
- 238000011084 recovery Methods 0.000 abstract description 8
- 238000000151 deposition Methods 0.000 abstract description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 229910000570 Cupronickel Inorganic materials 0.000 abstract 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 abstract 1
- 229910001431 copper ion Inorganic materials 0.000 abstract 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 abstract 1
- 238000010304 firing Methods 0.000 abstract 1
- 239000011888 foil Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 206010014357 Electric shock Diseases 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- DDXROPFGVVLFNZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) tricarbonate Chemical compound [Mn+2].[Co+2].C([O-])([O-])=O.[Ni+2].C([O-])([O-])=O.C([O-])([O-])=O DDXROPFGVVLFNZ-UHFFFAOYSA-H 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a method for recovering valuable metals from a waste lithium manganese oxide battery with simple process, low cost and high purification purity to comprehensively metals such as manganese, lithium, aluminum, copper nickel and the like. The method comprises the following steps of: soaking and peeling off active substances of the battery in organic solvent to directly obtain clean aluminum, copper, nickel foils and diaphragms; reacting acid solution with LiMn2O4 in a battery electrical core to generate soluble salts of the lithium and the manganese; regulating a pH value to 5-7 by using NaOH solution or ammonia water to enable iron ions, aluminum ions and copper ions in the solution to be wholly deposited, filtering and separating; regulating the pH value to 10-12 by using the NaOH solution or the ammonia water, and depositing and filtering to obtain manganous hydroxide solids and lithium containing filtrate; and finally, firing the manganous hydroxide solids to obtain MnO2, reacting the lithium containing filtrate with sodium carbonate to generate lithium carbonate, and filtering, washing and drying the lithium carbonate to obtain pure lithium carbonate. Through the steps, the recovery rate of the lithium in the battery is higher than 85 percent.
Description
Technical field
The invention belongs to waste and old power cell recovery technology field, particularly relate to a kind of method that in waste lithium manganese oxide battery, reclaims valuable metal.
Background technology
Along with 3C electronic product, various power tools etc. present the explosive type development, people sharply increase the demand of secondary cell.And characteristics such as that lithium-ions battery has is environmentally friendly, specific energy is high (140Wh/kg), voltage platform is high, have extended cycle life, good rate capability, self-discharge are little, memory-less effect; Be far superior to plumbic acid, Ni-Cd, Ni-MH battery, obtained broader applications at military, civil area.With respect to other power lithium-ion batteries; Characteristics such as lithium manganate power lithium-ion battery cost is lower, cycle performance is better, energy density is higher, security is good, be easy to synthesize, processibility is good have begun to obtain to use preferably in fields such as electric bicycle, electromobile, power tools.Correspondingly, the recycling of waste lithium manganese oxide battery also more and more obtains people's attention.
Patent CN200910116656.9 discloses a kind of MnO that in anode material of wasted lithium manganate battery, reclaims
2Method and application thereof.Promptly in autoclave, with the mineral acid of 0.25～10mol/L, in 100～200 ℃, under 0.1～10MPa, period 1-24h prepares λ-MnO
2Or α-/β-/γ-MnO, what obtained has various crystal form M nO than large specific surface and vesicular structure
2Can be directly as the catalyzer of synthetic fat compounds, or as the positive electrode material of Li/MnO2 primary cell, or as the electrode materials of ultracapacitor.Though the MnO that this patent reclaims
2Obtain good applied research, but take electric core to disassemble classification separately, can not realize mass disposal; Be employed in that HTHP carries out acidleach in the reaction kettle, complex process, facility investment are high; And this method does not reclaim lithium resource.
It is the method for feedstock production nickle cobalt lithium manganate with the waste and old lithium ion battery that patent CN200810198972.0 discloses a kind of.After soon pole piece crushed and screened, high temperature removed sticker and acetylene black, adopted NaOH removal of impurity aluminium; And go out with acidleach, the P204 abstraction impurity removal is added composition at last; Obtain nickel cobalt manganese carbonate ternary presoma, allocate the Quilonum Retard of suitable proportion into, can prepare nickle cobalt lithium manganate by high temperature sintering.The very difficult batch consistence that guarantees to reclaim the preparation material of this patented process all need be carried out the constituent content test of complicacy, costliness at every turn, and technical difficulty is big.
Summary of the invention
The objective of the invention is to propose the method that in waste lithium manganese oxide battery, reclaims valuable metal that a kind of technology is simple, cost is low, purification purity is high, to realize comprehensive recovery to metals such as manganese, lithium, aluminium, copper, nickel.
The method key that in waste lithium manganese oxide battery, reclaims valuable metal of the present invention is to comprise the steps:
A: take out the electric core of battery, and electric core is ground into electric core fragment;
B: electric core fragment is soaked with organic solvent and stirs;
C: with the electric core fragment after the immersion treatment through filter with separated from solvent after, wash again, filter, carry out drying and vibrosieve then, obtain clean aluminium, copper, nickel foil and barrier film on the sieve, reclaim through melting; Obtain mixed powder under the sieve;
D: mixed powder was soaked 0.5～2 hour with acid fluid dissolves, and intermittently stir, last filtering to the acid filtrate that contains manganese, lithium, said acid solution is the mixing solutions of ydrogen peroxide 50 of the 30wt% of 1～2M mineral acid and 0.5～1M;
E: the acid filtrate that will contain manganese, lithium is with NaOH solution or ammoniacal liquor adjustment pH value to 5～7, and fully stirring, makes iron ion, aluminum ion, cupric ion and NaOH solution or ammoniacal liquor reaction postprecipitation, filtering separation then in the solution;
F: the filtrating that obtains after the filtration of E step with NaOH or ammonia soln adjustment pH value to 10～12, is obtained the manganous hydroxide solid and contains lithium filtrating through deposition, filtration again;
G: behind the fast manganous hydroxide solid drying of institute, calcination obtained MnO in 2～12 hours in 400～800 degree air or oxygen atmosphere
2The said heating of lithium filtrating, the concentrated back adding sodium carbonate solution of containing, reaction generates Quilonum Retard, and warp filters again, washs, is drying to obtain purified Quilonum Retard.
Aforesaid method adopts organic solvent that the active substance of battery is soaked and peels off; Can dissolve most sticker, directly obtain clean aluminium, copper, nickel foil and barrier film, and promote the direct contact reacts of follow-up pickling liquor and lithium manganate; Can not cause tiny aluminium, copper scale too much; Reduce the workload of back removal of impurities, organic solvent can multistagely use, and distillation is at last reclaimed; Utilize the LiMn in acidic solution and the battery battery core
2O
4React, generate the solubility salt of lithium and manganese, the effect of ydrogen peroxide 50 mainly is that reduction high price mn ion is the low price mn ion, helps the carrying out of accelerate dissolution reaction.Ydrogen peroxide 50 ability and LiMn
2O
4In the Mn-O-Mn effect, weaken the Mn-O key, promote its decomposition; Simultaneously, LiMn in acidic solution
2O
4Structure deteriorate, the Mn of generation
3+With Mn
4+Very easily from H
2O
2Negative monovalence oxygen in electron gain be reduced to Mn
2+, Mn
2+Be dissolved in the mineral acid rapidly, thus the leaching yield of raising Mn.With NaOH solution or ammoniacal liquor adjustment pH value to 5～7, can make that foreign metals such as iron ion in the solution, aluminum ion, cupric ion can all precipitate, filtering separation under solutions of weak acidity, can not influence the sedimentary purity of manganese of subsequent recovery.After the above-mentioned steps processing, the recovery of lithium is greater than 85% in the battery.
In the said steps A: before the electric core that takes out battery, with discharge equipment waste lithium manganese oxide battery is discharged earlier, in order to avoid remaining electric weight causes Danger Electric shock risk to operator in the waste lithium manganese oxide battery.
Organic solvent among the said step B is N, one or more mixed solvents in dinethylformamide, N-Methyl pyrrolidone, the THF.
Among the said step B, when stirring, carry out ultra-sonic oscillation and handle, to quicken, to improve the dissolving of sticker in the electric core fragment.
The organic solvent filtrating that obtains after electric core fragment filters for the first time among the said step C is through the distillation recycling, to practice thrift cost.
Mineral acid among the said step D is one or more mixing solutionss in the sulfuric acid of nitric acid, 98wt% of hydrochloric acid, the 68wt% of 36wt%.
In the said step e: before F step adjustment pH, add a spot of ydrogen peroxide 50 again.Purpose is the micro Fe that oxidation maybe be residual
2+Be Fe
3+, because Fe
3+Oxyhydroxide o'clock can precipitate fully in pH＜3, just can Ex-all during removal of impurities; Fe
2+Then will under alkaline condition, could precipitate fully, this can be doped in the deposition regenerant of manganese.The manganous hydroxide that subsequent step is reclaimed through above-mentioned processing is purer.
Among the said step G: saidly contain lithium filtrating and be heated to more than 95 ℃, be concentrated into 300～400g/L, add 300～400g/L sodium carbonate solution again and react.Because Quilonum Retard has also reached 0.72g when solubleness is minimum in boiling water; Not the material of indissoluble, so before the deposition Quilonum Retard, must concentrate to solution; If but concentrate excessively; Can cause solute sodium salt or ammonium salt to be separated out, produce impurity, therefore will calculate contained and the total amount soluble substance that adds in the solution.The strict concentration that contains lithium filtrating and sodium carbonate solution that limits of the present invention can make the sedimentary Quilonum Retard of institute purer.
The metal purity height that the method technology of recovery valuable metal is simple in waste lithium manganese oxide battery, cost is low, reclaimed of the present invention has also been realized the comprehensive recovery of metals such as manganese, lithium, aluminium, copper, nickel is well suited for being used to handle waste lithium manganese oxide battery.
Description of drawings
Fig. 1 is the process flow sheet that in waste lithium manganese oxide battery, reclaims the method for valuable metal of the present invention.
Embodiment
Specify the present invention below in conjunction with specific embodiment and accompanying drawing.
Embodiment 1:
As shown in Figure 1, the method that in waste lithium manganese oxide battery, reclaims valuable metal of present embodiment comprises the steps:
A: waste lithium manganese oxide battery is discharged earlier, removes the outer packaging and the shell of battery, take out electric core by shears or cutting machine with special-purpose discharge equipment, and with kibbler with the concentrated 0.5～5cm that is crushed to of the electric core of waste lithium manganese oxide battery
2The fragment of size;
B: electric core fragment is used N, and the dinethylformamide organic solvent soaks, and the solid-to-liquid ratio of electric core fragment and solvent is 0.05～1kg/L, carries out mechanical stirring and intermittently sonic oscillation processing, soak time 5 hours simultaneously;
C: with the electric core fragment after the immersion treatment through filter with separated from solvent after, wash again, filter, carry out drying and vibrosieve then, obtain clean aluminium, copper, nickel foil and barrier film on the sieve, reclaim through melting; Sieve obtains containing the mixed powder of lithium manganate and graphite down;
D: mixed powder was soaked 2 hours with acid fluid dissolves, and intermittently stir, filter out undissolvable graphite at last; Obtain containing the acid filtrate of manganese, lithium; Said acid solution is the mixing solutions of ydrogen peroxide 50 of 30wt% of sulfuric acid and 1M of the 98wt% of 2M, the solid-to-liquid ratio 60g/L of acid solution and mixed powder, and wherein sulfuric acid and lithium manganate react; Generate the solubility salt of manganese, lithium, the low price mn ion that ydrogen peroxide 50 can the oxidation the inside be a mn ion at high price;
E: the acid filtrate that will contain manganese, lithium mixes with certain density NaOH solution and fully stirring, and adjustment pH value to 5～7 make iron ion, aluminum ion, cupric ion and NaOH solution reaction postprecipitation, filtering separation then in the solution; Slowly add ydrogen peroxide 50 in the solution after filtering separation, generate up to no longer including new throw out, and then carry out filtering separation, so that the manganous hydroxide that subsequent step reclaimed is purer.Its reaction principle is following:
Fe
3++3OH
-→Fe(OH)
3↓；
Al
3++3OH
-→Al(OH)
3↓；
Cu
2++2OH
-→Cu(OH)
2↓；
F: the filtrating that obtains after the filtration of E step with NaOH or ammonia soln adjustment pH value to 10～12, is obtained the manganous hydroxide solid and contains lithium filtrating through deposition, filtration again, and its reaction principle is following:
Mn
2++2OH
-→Mn(OH)
2↓；
G: behind the said manganous hydroxide solid drying, calcination obtained MnO in 8 hours in 600 degree air or oxygen atmosphere
2Saidly contain lithium filtrating and be heated to more than 95 ℃, be concentrated into 300～400g/L, add 300～400g/L sodium carbonate solution again and react, reaction generates Quilonum Retard, through filtering, washs, is drying to obtain purified Quilonum Retard again, and its reaction principle is following:
Mn(OH)
2+O
2→MnO
2+H
2O；
2Li
++CO
3 2-→Li
2CO
3↓。
After the above-mentioned steps processing, the recovery of lithium is greater than 85% in the battery.
Claims (7)
1. a method that in waste lithium manganese oxide battery, reclaims valuable metal is characterized in that comprising the steps:
A: take out the electric core of battery, and electric core is ground into electric core fragment;
B: electric core fragment is soaked with organic solvent and stirs;
C: with the electric core fragment after the immersion treatment through filter with separated from solvent after, wash again, filter, carry out drying and vibrosieve then, obtain clean aluminium, copper, nickel foil and barrier film on the sieve, reclaim through melting; Obtain mixed powder under the sieve;
D: mixed powder was soaked 0.5～2 hour with acid fluid dissolves, and intermittently stir, filter the acid filtrate that obtains containing manganese, lithium at last, said acid solution is the mixing solutions of ydrogen peroxide 50 of the 30wt% of 1～2M mineral acid and 0.5～1M; E: the acid filtrate that will contain manganese, lithium mixes with NaOH solution or ammoniacal liquor and fully stirring, and adjustment pH value to 5～7 make iron ion, aluminum ion, cupric ion and NaOH solution or ammoniacal liquor reaction postprecipitation, filtering separation then in the solution;
F: the filtrating that obtains after the filtration of E step with NaOH or ammonia soln adjustment pH value to 10～12, is obtained the manganous hydroxide solid and contains lithium filtrating through deposition, filtration again;
G: behind the said manganous hydroxide solid drying, calcination obtained MnO in 2～12 hours in 400～800 degree air or oxygen atmosphere
2Saidly contain lithium filtrating and be heated to more than 95 ℃, be concentrated into 300～400g/L, add 300～400g/L sodium carbonate solution again and react, reaction generates Quilonum Retard, through filtering, washs, is drying to obtain purified Quilonum Retard again.
2. the method that in waste lithium manganese oxide battery, reclaims valuable metal according to claim 1 is characterized in that in the said steps A: before the electric core that takes out battery, with discharge equipment waste lithium manganese oxide battery is discharged earlier.
3. the method that in waste lithium manganese oxide battery, reclaims valuable metal according to claim 1 is characterized in that the organic solvent among the said step B is N, one or more mixed solvents in dinethylformamide, N-Methyl pyrrolidone, the THF.
4. the method that in waste lithium manganese oxide battery, reclaims valuable metal according to claim 1 is characterized in that among the said step B, when stirring, carries out ultra-sonic oscillation and handles.
5. the method that in waste lithium manganese oxide battery, reclaims valuable metal according to claim 1, the organic solvent filtrating that it is characterized in that obtaining after electric core fragment filters for the first time among the said step C is through the distillation recycling.
6. the method that in waste lithium manganese oxide battery, reclaims valuable metal according to claim 1 is characterized in that mineral acid among the said step D is one or more mixing solutionss in the sulfuric acid of nitric acid, 98wt% of hydrochloric acid, the 68wt% of 36wt%.
7. the method that in waste lithium manganese oxide battery, reclaims valuable metal according to claim 1; It is characterized in that in the said step e: slowly add ydrogen peroxide 50 in the solution after final filtering separation; Generate up to no longer including new throw out, and then carry out filtering separation.
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