CN103633393A - Recycling process for active material of waste cathode piece of lithium ion battery - Google Patents
Recycling process for active material of waste cathode piece of lithium ion battery Download PDFInfo
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- CN103633393A CN103633393A CN201310647489.7A CN201310647489A CN103633393A CN 103633393 A CN103633393 A CN 103633393A CN 201310647489 A CN201310647489 A CN 201310647489A CN 103633393 A CN103633393 A CN 103633393A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a recycling process for an active material of the waste cathode piece of a lithium ion battery. The key points of the technical scheme of the invention are as follows: (1) allowing a release agent to contact with the waste anode piece in the manner of spraying, drip washing, dipping or soaking, and keeping the contact state at the temperature of minus 10 to 120 DEG C for 0.1-36 hours; (2) screening or picking out aluminum foil, filtering or centrifuging the release agent mixture containing the active material, and washing to separate out the solid active material and the liquid release agent; (3) drying the solid active material at the temperature of 40-250 DEG C, adding a lithium source to the dried solid active material, and after thorough mixing, conducting three-step calcining; (4) after the three-step calcining, naturally reducing the furnace temperature, and then collecting the solid material which is the recycled cathode active material. The cathode active material recycled in the invention has the same structure, shape and composition as the material for preparing the cathode of the lithium ion battery, and the electrochemical properties of the cathode active material are stable.
Description
Technical field
The present invention relates to the recycling technical field of active material on the useless sheet of the positive pole that produces in anode of secondary battery preparation process, be specifically related to the regeneration technology of the useless sheet active material of a kind of lithium ion cell positive.
Background technology
Secondary cell is as the important device of this clean energy resource storage of electric energy, be directly connected to effective utilization and the action effect of electric energy, therefore, lifting to secondary cell performance is the focus of research, to the nineties in 20th century always, appearance along with lithium ion battery, the operating voltage that it is high, long cycle life, the good outstanding advantages such as fail safe are more and more subject to people's favor.At present, the positive electrode of commodity secondary cell is with LiCoO
2, LiMn
2o
4, LiNiO
2and LiCo
x ni
y mn
z o
2(
x+
y+
z=1) study more, because the metals resources such as Li, Ni, Co, Mn are limited, especially Co belongs to noble metal, and the content in its primary ore is very low, carries out the focus that the research of reclaiming useful metal resource or regenerating positive electrode from lithium ion old and useless battery becomes battery recycling technical research just gradually.
Along with the sustainable growth of secondary cell consumption, the anodal leftover bits that produce in secondary cell production process and relic are also more and more.It is estimated, positive electrode will have 1%-5% to be depleted in anodal useless sheet aborning, most enterprises only obtain cobalt salt or lithium salts etc. to process at a low price to relevant unit or to adopt soda acid to process to these anodal leftover pieces and relic, these modes of processing anodal useless sheet have been lost the positive electrode of a large amount of costlinesses, for secondary cell manufacturing enterprise, be not only subject to very large economic loss, but also can have caused a large amount of resource waste and pollution environment.
At present, people have wet method and dry process to the main method of the recycling of secondary battery positive electrode material.Dry process mainly comprises mechanical crushing, ball milling and ultrasonic disengaging etc., the technical study starting of wet treatment old and useless battery very early, mainly to pretreated electrode material, first with chemical reagent, metal ion in positive electrode is leached, then with electro-deposition, chemical precipitation, each metal ion of method separation such as extract, saltout.These techniques mainly comprise electrodeposition process, chemical precipitation method, solvent extraction, acidleach-salting out method, biological metallurgy technique etc.With regard to acidleach system, its object is mainly to pass through used acid and the reactive metal oxide of positive electrode, generates the metal cation salt of relative acid, then it is separated again metal ion to be purified, and precipitation granulation, then adds lithium calcining again.Meanwhile, before acidleach, often need fragmentation, in acidleach process, also need to add hydrogen peroxide assisted oxidation, make this technological process when reclaiming anodal useless sheet active component, seem that technological process is complicated, recycle cost higher and there is larger secondary pollution.
Summary of the invention
The technical problem that the present invention solves has been to provide the regeneration technology of the useless sheet active material of a kind of lithium ion cell positive, it is in the leftover pieces that produce from based lithium-ion battery positive plate preparation process or relic, to reclaim the technique of positive active material, is applicable to any regeneration of take the useless sheet active material of positive pole that aluminium foil is matrix and processes.
Technical scheme of the present invention is: the regeneration technology of the useless sheet active material of a kind of lithium ion cell positive, it is characterized in that mainly comprising the following steps: (1) mode with spray, drip washing, dipping or immersion contacts with anodal useless sheet by remover, and-10-120 ℃ maintenance 0.1-36h, wherein remover is that mass concentration is the ethylene glycol solution of the sulfuric acid solution of 30%-90% or the ethanolic solution of sulfuric acid or sulfuric acid or the mixed solution of sulfuric acid and ethanol and ethylene glycol; (2) sieve or sort out aluminium foil, by the remover mixture filtration that contains active material or centrifugal, washing, isolates solid active agents and liquid remover; (3) solid active agents step (2) being obtained in 40-250 ℃ dry, in dried solid active agents, add lithium source, three steps calcinings after mixing; (4) after calcining, make the naturally cooling collection solid matter of furnace temperature be the positive active material of regeneration.
The ethanolic solution of sulfuric acid in step of the present invention (1), in the mixed solution of the ethylene glycol solution of sulfuric acid and sulfuric acid and ethanol and ethylene glycol the mass concentration of sulfuric acid be 10%-90%; In described step (2) washing agent of washing be water, absolute ethyl alcohol, acetone or N-first class pyrrolidones one or more, described liquid remover can recycle; Lithium source in described step (3) is one or more in lithium carbonate, lithium hydroxide or lithium acetate, and actual temp and the time of three step calcinings are respectively: first step 250-500 ℃, 0.5-5h, second step 400-750 ℃, 1-10h, the 3rd step 600-1200 ℃, 3-24h.
Beneficial effect of the present invention is: (1) whole production process technology is simple, and production cost is low, remarkable in economical benefits; (2) positive electrode of the method reclaiming has identical structure, pattern and composition, stable electrochemical property with the anodal material therefor of manufacturing lithium ion battery; (3) the method can make the active material in anodal leftover pieces and relic at utmost be reused; (4) make battery producer avoid unnecessary economic loss; (5) can not cause secondary pollution to environment; (6) aluminium foil of getting rid of can effectively reclaim.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the positive electrode of the embodiment of the present invention 1 regeneration, and Fig. 2 is the XRD collection of illustrative plates of the positive electrode of the embodiment of the present invention 1 regeneration.
Embodiment
By the following examples foregoing of the present invention is described in further details, but this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology realizing based on foregoing of the present invention all belong to scope of the present invention.
The useless sheet of positive pole the present invention relates to refers to anodal leftover pieces and the relic producing in secondary cell production process, and it mainly comprises: the medicine face adhering on aluminium foil matrix (collector) and matrix, medicine face mainly contains active material LiCoO
2, LiMn
2o
4, LiNiO
2and LiCo
x ni
y mn
z o
2(
x+
y+
z=1) etc. form with adhesive and conductive agent (carbon black, petroleum coke, acetylene black) and roll or cohere at aluminium foil surface.
Principle of the present invention is: employing organic solvent is carrier, the gas tension that utilizes sulfuric acid to produce with the aluminium foil surface generation passivation reaction initial stage in organic solvent, make containing the medicine face of positive active material, from aluminium foil, to peel off in flakes on anodal useless sheet, calcine in the lithium source that adds subsequently, can supplement on the one hand the lithium loss when peeling off and calcining, can make on the other hand the crystal formation acquisition of positive active material perfect, thereby this technological process is effectively simplified.Due to when peeling off, positive active material is included in adhesive, and the sulfuric acid in organic solvent reacts with positive active material hardly, has reduced as much as possible the active principle loss in positive active material, has also kept its original pattern.In calcination process, because final calcining heat is higher, so the carbon-containing impurities comprising in anodal useless sheet, the sulfate that may form while peeling off can be removed completely.Because the present invention is that passivation principle based on aluminium foil is carried out, therefore, if adopt immersion way that remover is contacted with anode waste, should be according to medicine face and the timely separated aluminium foil of separation case, the remover of aluminium foil and the medicine face that contains positive active material, otherwise, along with the prolongation of soak time, anodal active component can be lost gradually, finally makes positive active material regenerate by this technique.Compare and can find out with the positive electrode recoverying and utilizing method of current proposition: technique of the present invention is simple, and manufacturing cost is low, can make the active material in anodal leftover pieces and relic farthest be recycled, economize on resources, environment is not produced and polluted.The positive electrode theoretical recovery of regeneration reaches as high as 80% of anode waste total weight, the general rate of recovery is between the 55%-75% of anode waste total weight, the battery capacity of salvage material can reach the 80%-98% of original positive electrode capacity, and part keeps original spherical morphology.
embodiment 1
(1) to the ternary material (LiCo collecting
xni
ymn
zo
2, x+y+z=1) the useless sheet of anode of secondary battery sorts, the sordid positive pole of effects on surface useless sheet for ethanol, acetone or 1-METHYLPYRROLIDONE clean, make to enter step (2) after surperficial cleaning, the clean positive pole sheet that gives up can directly enter step (2);
(2) the remover drip washing repeatedly of the sulfuric acid solution that is 35% with 200ml containing mass concentration by the useless sheet 50g of clean positive pole, makes the medicine face on anodal useless sheet effectively contact with remover, and ambient temperature is the lower 1h that keeps in 30 ℃;
(3) take out the useless sheet of positive pole of step (2), shake gently, the medicine face nature that (ultrasonic, all can to stir) contains active material comes off from aluminium foil, removes aluminium foil;
(4) with 50ml absolute ethanol washing, filter the solid 3 times of coming off, the absolute ethyl alcohol after washing can enter step (2) and use;
(5) by the solid active agents after step (4) washing in 150 ℃ of dry 1h, reclaiming solid gross mass is 29.5g;
(6) analyze dry after lithium ion content in solid active agents be 5.0%, using lithium carbonate as lithium source, by lithium ion content, be 8.5% to add the amount of lithium carbonate to be about 5.43g;
(7) after adding solid active agents behind lithium source to mix, put into Muffle furnace, first temperature is raised to 350 ℃, insulation 2h, subsequently, is elevated to 450 ℃ by temperature, and insulation 5h is last, and temperature is elevated to 730 ℃, insulation 14h;
(8) with the naturally cooling rear collection solid matter of furnace temperature, be the positive active material of regeneration.
Fig. 1 is the scanning electron microscope (SEM) photograph of the positive electrode of regeneration, and the positive electrode of regeneration is still spherical morphology as seen from the figure, and the active material of regeneration is as shown in Figure 2 ternary material (LiCo
xni
ymn
zo
2, x+y+z=1).
embodiment 2
(1) to the LiMn collecting
2o
4the useless sheet of anode of secondary battery sorts, the sordid positive pole of effects on surface useless sheet for ethanol, acetone or 1-METHYLPYRROLIDONE clean, make to enter step (2) after surperficial cleaning, the clean positive pole sheet that gives up can directly enter step (2);
(2) the useless sheet 50g of clean positive pole is immersed in the remover of the sulfuric acid solution that 1L is 10% containing mass concentration, the medicine face on anodal useless sheet is effectively contacted with remover, ambient temperature is the lower 36h that keeps in-10 ℃;
(3) take out the useless sheet of positive pole of step (2), shake gently, the medicine face nature that (ultrasonic, all can to stir) contains active material comes off from aluminium foil, removes aluminium foil;
(4) with 50ml absolute ethanol washing, cross filter solid 3 times, the absolute ethyl alcohol after washing can enter step (2) and use; If (take acetone or 1-METHYLPYRROLIDONE as washing agent, step that No Entry (2) is used, otherwise there will be danger.)
(5) by the solid active agents after step (4) washing in 40 ℃ of dry 12h, reclaiming solid gross mass is 33.5g;
(6) lithium ion content of analyzing in dry rear solid active agents is 5.7%, usings lithium carbonate as lithium source, by lithium ion content, is that 11% calculating adds the amount of lithium carbonate to be about 9.34g;
(7) after adding solid active agents behind lithium source to mix, put into Muffle furnace, first temperature is raised to 250 ℃, insulation 5h, is elevated to temperature 650 ℃ subsequently, and temperature retention time 1h, is finally elevated to temperature 1200 ℃, insulation 24h;
(8) with the naturally cooling rear collection solid matter of furnace temperature, be the positive active material of regeneration.
embodiment 3
(1) to the LiMn collecting
2o
4the useless sheet of anode of secondary battery sorts, the sordid positive pole of effects on surface useless sheet for ethanol, acetone or 1-METHYLPYRROLIDONE clean, make to enter step (2) after surperficial cleaning, the clean positive pole sheet that gives up can directly enter step (2);
(2) the useless sheet 50g of clean positive pole is immersed in the remover of the sulfuric acid solution that 1L is 90% containing mass concentration, the medicine face on anodal useless sheet is effectively contacted with remover, ambient temperature is the lower 0.1h that keeps in 120 ℃;
(3) take out the useless sheet of positive pole of step (2), shake gently, the medicine face nature that (ultrasonic, all can to stir) contains active material comes off from aluminium foil, removes aluminium foil;
(4) with 50ml absolute ethanol washing, cross filter solid 3 times, the absolute ethyl alcohol after washing can enter step (2) and use; If (take acetone or 1-METHYLPYRROLIDONE as washing agent, step that No Entry (2) is used, otherwise there will be danger.)
(5) by the solid active agents after step (4) washing in 40 ℃ of dry 12h, reclaiming solid gross mass is 33.5g;
(6) lithium ion content of analyzing in dry rear solid active agents is 5.7%, usings lithium carbonate as lithium source, by lithium ion content, is that 11% calculating adds the amount of lithium carbonate to be about 9.34g;
(7) after adding solid active agents behind lithium source to mix, put into Muffle furnace, first temperature is raised to 250 ℃, insulation 5h is elevated to temperature 650 ℃ subsequently, and temperature retention time 1h, is finally elevated to temperature 1200 ℃, insulation 24h;
(8) with the naturally cooling rear collection solid matter of furnace temperature, be the positive active material of regeneration.
embodiment 4
(1) to the LiMn collecting
2o
4the useless sheet of anode of secondary battery sorts, the sordid positive pole of effects on surface useless sheet for ethanol, acetone or 1-METHYLPYRROLIDONE clean, make to enter step (2) after surperficial cleaning, the clean positive pole sheet that gives up can directly enter step (2);
(2) the useless sheet 50g of clean positive pole is immersed in the remover of ethanolic solution of the sulfuric acid that 1L is 10% containing mass concentration, the medicine face on anodal useless sheet is effectively contacted with remover, ambient temperature is lower maintenance 36h in-10 ℃;
(3) take out the useless sheet of positive pole of step (2), shake gently, the medicine face nature that (ultrasonic, all can to stir) contains active material comes off from aluminium foil, removes aluminium foil;
(4) with 50ml absolute ethanol washing, cross filter solid 3 times, the absolute ethyl alcohol after washing can enter step (2) and use; If (take acetone or 1-METHYLPYRROLIDONE as washing agent, step that No Entry (2) is used, otherwise there will be danger.)
(5) by the solid active agents after step (4) washing in 40 ℃ of dry 12h, reclaiming solid gross mass is 33.5g;
(6) lithium ion content of analyzing in dry rear solid active agents is 5.7%, usings lithium carbonate as lithium source, by lithium ion content, is that 11% calculating adds the amount of lithium carbonate to be about 9.34g;
(7) after adding solid active agents behind lithium source to mix, put into Muffle furnace, first temperature is raised to 250 ℃, insulation 5h is elevated to temperature 650 ℃ subsequently, and temperature retention time 1h, is finally elevated to temperature 1200 ℃, insulation 24h;
(8) with the naturally cooling rear collection solid matter of furnace temperature, be the positive active material of regeneration.
embodiment 5
(1) to the ternary material (LiCo collecting
xni
ymn
zo
2, x+y+z=1) the useless sheet of anode of secondary battery sorts, the sordid positive pole of effects on surface useless sheet for ethanol, acetone or 1-METHYLPYRROLIDONE clean, make to enter step (2) after surperficial cleaning, the clean positive pole sheet that gives up can directly enter step (2);
(2) in the remover of the ethylene glycol solution of the sulfuric acid that is 90% at 12ml containing mass concentration by the useless sheet 50g spray of clean positive pole, the medicine face on anodal useless sheet is effectively contacted with remover, ambient temperature is the lower 0.1h that keeps in 20 ℃;
(3) take out the useless sheet of positive pole of step (2), shake gently, the medicine face nature that (ultrasonic, all can to stir) contains active material comes off from aluminium foil, removes aluminium foil;
(4) with come off solid 3 times of 50ml absolute ethanol washing, the absolute ethyl alcohol after washing can enter step (2) and use;
(5) by the 250 ℃ of dry 1h of solid active agents after step (4) washing, reclaiming solid gross mass is 30.1g;
(6) analyze dry after lithium ion content in solid active agents be 5.3%, using lithium hydroxide as lithium source, by lithium ion content, be 8% to add the amount of lithium hydroxide to be about 2.79g;
(7) after adding solid active agents behind lithium source to mix, put into Muffle furnace, first temperature is raised to 350 ℃, insulation 2h is elevated to temperature 400 ℃ subsequently, and temperature retention time 10h, is finally elevated to temperature 600 ℃, insulation 14h;
(8) with the naturally cooling rear collection solid matter of furnace temperature, be the positive active material of regeneration.
embodiment 6
(1) to the LiCoO collecting
2the useless sheet of anode of secondary battery sorts, the sordid positive pole of effects on surface useless sheet for ethanol, acetone or 1-METHYLPYRROLIDONE clean, make to enter step (2) after surperficial cleaning, the clean positive pole sheet that gives up can directly enter step (2);
(2) the useless sheet 50g of clean positive pole is immersed in the remover of ethanolic solution of the sulfuric acid that 500ml is 50% containing mass concentration, the medicine face on anodal useless sheet is effectively contacted, lower maintenance 0.1h in 120 ℃ with remover;
(3) medicine face nature in remover that the anodal useless sheet of shake (ultrasonic, all can to stir) contains active material gently comes off from aluminium foil, removes aluminium foil;
(4) with 50ml absolute ethanol washing, cross filter solid 3 times; Absolute ethyl alcohol after washing can enter step (2) and use;
(5) by the 150 ℃ of dry 1h of solid active agents after step (4) washing, reclaiming solid gross mass is 35g;
(6) lithium ion content of analyzing in dry rear solid active agents is 5.9%, usings lithium acetate as lithium source, by lithium ion content, is that 8 % add the amount of lithium acetate to be about 6.176g;
(7) after adding solid active agents behind lithium source to mix, put into Muffle furnace, first temperature is raised to 500 ℃, insulation 0.5h, subsequently, is elevated to 600 ℃ by temperature, and insulation 10h is last, and temperature is elevated to 950 ℃, insulation 10h;
(8) with the naturally cooling rear collection solid matter of furnace temperature, be the positive active material of regeneration.
embodiment 7
(1) to the LiNiO collecting
2the useless sheet of anode of secondary battery sorts, the sordid positive pole of effects on surface useless sheet for ethanol, acetone or 1-METHYLPYRROLIDONE clean, make to enter step (2) after surperficial cleaning, the clean positive pole sheet that gives up can directly enter step (2);
(2) the useless sheet 50g of clean positive pole is immersed in the remover of sulfuric acid that 2000ml is 75% containing mass concentration and the mixed solution of ethanol and ethylene glycol, the medicine face on anodal useless sheet is effectively contacted with remover, in 40 ℃ under maintenance 0.5h;
(3) medicine face nature in remover that the anodal useless sheet of shake (ultrasonic, all can to stir) contains active material gently comes off from aluminium foil, removes aluminium foil;
(4) with 50ml absolute ethanol washing, cross filter solid 3 times, the absolute ethyl alcohol after washing can enter step (2) and use;
(5) by the 100 ℃ of dry 10h of solid active agents after step (4) washing, reclaiming solid gross mass is 32.3g;
(6) lithium ion content of analyzing in dry rear solid active agents is 6.1%, usings lithium carbonate as lithium source, by lithium ion content, is that 9 % add the amount of lithium carbonate to be about 4.93g;
(7) after adding solid active agents behind lithium source to mix, put into Muffle furnace, first temperature is raised to 300 ℃, insulation 5h, subsequently, is elevated to 450 ℃ by temperature, and insulation 10h is last, and temperature is elevated to 980 ℃, insulation 10h;
(8) with the naturally cooling rear collection solid matter of furnace temperature, be the positive active material of regeneration.
embodiment 8
(1) to the LiCoO collecting
2, ternary material, LiMn
2o
4the useless sheet of secondary cell blended anode sorts, the sordid positive pole of effects on surface useless sheet for ethanol, acetone or 1-METHYLPYRROLIDONE clean, make to enter step (2) after surperficial cleaning, the clean positive pole sheet that gives up can directly enter step (2);
(2) the useless sheet 50g of clean positive pole is immersed in the remover of ethanolic solution of the sulfuric acid that 1000ml is 50% containing mass concentration, the medicine face on anodal useless sheet is effectively contacted, lower maintenance 5h in 25 ℃ with remover;
(3) medicine face nature in remover that the anodal useless sheet of shake (ultrasonic, all can to stir) contains active material gently comes off from aluminium foil, removes aluminium foil;
(4) with 200ml absolute ethanol washing, cross filter solid 3 times, the absolute ethyl alcohol after washing can enter step (2) and use;
(5) by the 100 ℃ of dry 1h of solid active agents after step (4) washing, reclaiming solid gross mass is 31g;
(6) lithium ion content of analyzing in dry rear solid active agents is 5.7%, usings lithium carbonate as lithium source, by lithium ion content, is that 8.5 % add the amount of lithium carbonate to be about 4.57g;
(7) after adding solid active agents behind lithium source to mix, put into Muffle furnace, first temperature is raised to 400 ℃, insulation 4h, subsequently, is elevated to 540 ℃ by temperature, and insulation 10h is last, and temperature is elevated to 980 ℃, insulation 24h;
(8) with the naturally cooling rear collection solid matter of furnace temperature, be the positive active material of regeneration.
Above embodiment has described basic principle of the present invention, principal character and advantage.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification, describes just illustrates principle of the present invention; do not departing under the scope of the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.
Claims (6)
1. the regeneration technology of the useless sheet active material of a lithium ion cell positive, it is characterized in that mainly comprising the following steps: (1) mode with spray, drip washing, dipping or immersion contacts with anodal useless sheet by remover, and-10-120 ℃ maintenance 0.1-36h, wherein remover is that mass concentration is the ethylene glycol solution of the sulfuric acid solution of 30%-90% or the ethanolic solution of sulfuric acid or sulfuric acid or the mixed solution of sulfuric acid and ethanol and ethylene glycol; (2) sieve or sort out aluminium foil, by the remover mixture filtration that contains active material or centrifugal, washing, isolates solid active agents and liquid remover; (3) solid active agents step (2) being obtained in 40-250 ℃ dry, in dried solid active agents, add lithium source, three steps calcinings after mixing; (4) after calcining, make the naturally cooling collection solid matter of furnace temperature be the positive active material of regeneration.
2. the regeneration technology of the useless sheet active material of lithium ion cell positive according to claim 1, is characterized in that: the ethanolic solution of sulfuric acid in described step (1), in the mixed solution of the ethylene glycol solution of sulfuric acid and sulfuric acid and ethanol and ethylene glycol the mass concentration of sulfuric acid be 10%-90%.
3. the regeneration technology of the useless sheet active material of lithium ion cell positive according to claim 1, is characterized in that: in described step (2) washing agent of washing be water, absolute ethyl alcohol, acetone or N-first class pyrrolidones one or more.
4. the regeneration technology of the useless sheet active material of lithium ion cell positive according to claim 1, is characterized in that: the liquid remover of described step (2) can recycle.
5. the regeneration technology of the useless sheet active material of lithium ion cell positive according to claim 1, is characterized in that: the lithium source in described step (3) is one or more in lithium carbonate, lithium hydroxide or lithium acetate.
6. the regeneration technology of the useless sheet active material of lithium ion cell positive according to claim 1, it is characterized in that: in described step (3), actual temp and the time of three step calcinings are respectively: first step 250-500 ℃, 0.5-5h, second step 400-750 ℃, 1-10h, the 3rd step 600-1200 ℃, 3-24h.
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CN106964534A (en) * | 2017-04-13 | 2017-07-21 | 池州西恩新材料科技有限公司 | A kind of cylinder screening machine, from tertiary cathode waste material separation of tertiary positive powder system and method |
CN109616713A (en) * | 2018-11-06 | 2019-04-12 | 广西师范大学 | The method that aluminium foil is separated with positive active material in waste and old lithium ion battery |
CN109837392A (en) * | 2019-01-25 | 2019-06-04 | 宁波行殊新能源科技有限公司 | The recycling and regeneration method of lithium ion battery anode material waste material |
CN114068909A (en) * | 2021-11-10 | 2022-02-18 | 中南大学 | Method for regenerating NCMA (non-volatile memory MA) cathode material from retired NCM cathode material |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1453897A (en) * | 2003-05-29 | 2003-11-05 | 南开大学 | Recovery method for leftover and residue of positive electrode of lithium ion battery |
CN1953269A (en) * | 2006-11-01 | 2007-04-25 | 浙江工业大学 | A recovery method for waste lithium ion cell |
CN100486889C (en) * | 2005-12-16 | 2009-05-13 | 比亚迪股份有限公司 | Method for producing active substance ferrous lithium phosphate as lithium-ion battery anode |
CN102017276A (en) * | 2009-12-28 | 2011-04-13 | 深圳市雄韬电源科技股份有限公司 | Reutilization method of a waste LiFeP04 power battery |
CN102868006A (en) * | 2012-09-21 | 2013-01-09 | 华东理工大学 | Method for preparing graphene through waste lithium batteries |
CN103199319A (en) * | 2013-03-22 | 2013-07-10 | 河南省冶金研究所有限责任公司 | Method for recycling lithium cobalt oxide from waste positive electrode of lithium cobalt oxide battery |
-
2013
- 2013-12-06 CN CN201310647489.7A patent/CN103633393A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1453897A (en) * | 2003-05-29 | 2003-11-05 | 南开大学 | Recovery method for leftover and residue of positive electrode of lithium ion battery |
CN100486889C (en) * | 2005-12-16 | 2009-05-13 | 比亚迪股份有限公司 | Method for producing active substance ferrous lithium phosphate as lithium-ion battery anode |
CN1953269A (en) * | 2006-11-01 | 2007-04-25 | 浙江工业大学 | A recovery method for waste lithium ion cell |
CN102017276A (en) * | 2009-12-28 | 2011-04-13 | 深圳市雄韬电源科技股份有限公司 | Reutilization method of a waste LiFeP04 power battery |
CN102868006A (en) * | 2012-09-21 | 2013-01-09 | 华东理工大学 | Method for preparing graphene through waste lithium batteries |
CN103199319A (en) * | 2013-03-22 | 2013-07-10 | 河南省冶金研究所有限责任公司 | Method for recycling lithium cobalt oxide from waste positive electrode of lithium cobalt oxide battery |
Non-Patent Citations (1)
Title |
---|
卢毅屏等: "废锂离子电池中集流体与活性物质的分离", 《中国有色金属学报》 * |
Cited By (6)
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CN106964534B (en) * | 2017-04-13 | 2024-02-20 | 池州西恩新材料科技有限公司 | System and method for separating ternary positive electrode powder from ternary positive electrode waste |
CN109616713A (en) * | 2018-11-06 | 2019-04-12 | 广西师范大学 | The method that aluminium foil is separated with positive active material in waste and old lithium ion battery |
CN109616713B (en) * | 2018-11-06 | 2022-01-07 | 广西师范大学 | Method for separating aluminum foil from positive active material in waste lithium ion battery |
CN109837392A (en) * | 2019-01-25 | 2019-06-04 | 宁波行殊新能源科技有限公司 | The recycling and regeneration method of lithium ion battery anode material waste material |
CN114068909A (en) * | 2021-11-10 | 2022-02-18 | 中南大学 | Method for regenerating NCMA (non-volatile memory MA) cathode material from retired NCM cathode material |
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