CN103526035B - The method of valuable metal is reclaimed from waste and old lithium ion battery and/or its material - Google Patents
The method of valuable metal is reclaimed from waste and old lithium ion battery and/or its material Download PDFInfo
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- CN103526035B CN103526035B CN201310531016.0A CN201310531016A CN103526035B CN 103526035 B CN103526035 B CN 103526035B CN 201310531016 A CN201310531016 A CN 201310531016A CN 103526035 B CN103526035 B CN 103526035B
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Abstract
The invention provides a kind of method reclaiming valuable metal from waste and old lithium ion battery and/or its material, comprise the following steps: waste and old lithium ion battery and/or its material, metallurgical coke are mixed with flux and/or containing the waste material of one or more in Cu, Co and Ni, obtains mixture; Described metallurgical coke accounts for 0 ~ 20wt% of mixture; In described mixture, CaO/SiO
2>=1 or (CaO+MgO)/SiO
2>=1; Described mixture is carried out retailoring at the temperature of 1400 DEG C ~ 1600 DEG C, obtains the alloy containing valuable metal and slag.The present invention adopts basic slag melting, can realize the high efficiente callback of valuable metal, reduces the content of valuable metal in slag.
Description
Technical field
The present invention relates to resource and environment technical field, particularly a kind of method reclaiming valuable metal from waste and old lithium ion battery and/or its material.
Background technology
Lithium ion battery is since nineteen ninety commercialization, because it has that energy density is large, operating voltage is high, has extended cycle life and the advantage such as memory-less effect, be widely used in the communication such as mobile phone and notebook computer electronic product and various electronic instrument and power tool.As the production and consumption big country of lithium ion battery in the world, China only lithium ion battery ultimate production of 2012 just reaches 4,000,000,000.And along with the universal fast of hyundai electronics communication equipment and the development of power truck industry etc., the consumption of secondary cell increases severely, a large amount of waste and old lithium ion batteries can be produced thereupon.Waste and old lithium ion battery is on the one hand containing valuable metals such as more cobalt, nickel and lithiums, and recovery value is high; On the other hand, its poisonous or hazardous compound contained is also more, as directly discarded or mishandling, not only waste resource, and can cause more serious problem of environmental pollution, therefore, must recycle waste and old lithium ion battery by sophistication.
In recent years, much research has been carried out to the recovery and reuse technology of waste and old lithium ion battery both at home and abroad.Press adopted smelting technology different, the recovery processing technique of waste and old lithium ion battery can be divided into wet method and pyrogenic process two class.At present, the recycling technology of the waste and old lithium ion battery of domestic-developed mainly concentrates on wet processing process, as the publication number Chinese patent literature that is CN102517448A discloses the reclaiming method of metal ion in a kind of waste and old lithium ion battery, waste and old lithium ion battery discharges, disassembles and obtain positive electrode material by the method, then positive electrode material described in N-Methyl pyrrolidone (NMP) supersound process is used, the more obtained LiCoO of calcining
2powder, after acid-soluble, adds manganese salt and nickel salt and LiOH, directly obtained tertiary cathode material.This wet processing process needs to carry out to waste and old lithium ion battery the pretreatment process that machinery disassembles; because this process exists the risk of environmental pollution of explosion safety risk or organism volatilization; generally adopt now and to disassemble in protective atmosphere or cryogenic freezing is disassembled; but; this just makes recycling ability be limited by very large, facility investment and running cost higher.
And in thermal process, as US716920B2 patent discloses the one developed by Umicore company containing cobalt, nickel-based battery list stove retailoring treatment process, old and useless battery and disintegrate material, the furnace refractory of iron content and flux are specifically put in a high temperature shaft furnace by it, by controlling the redox condition in shaft furnace, output is containing the alloy of Co, Ni and the slag containing Fe >=20wt%, Co≤20wt%, Ni≤20wt%, then this alloy is processed further, reclaim Co, Ni.The safe explosion that this technique has can process all kinds battery waste, avoid battery to disassemble exists in process and the advantage of risk of environmental pollution, but, it adopts acid slag melting, in slag, Co, Cu content is still respectively up to 1.5wt%, 0.9wt%, slag cannot directly be abandoned, need further dilution process, complex process.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of method reclaiming valuable metal from waste and old lithium ion battery and/or its material, method provided by the invention can realize the high efficiente callback of valuable metal, reduce the content of valuable metal in slag, avoid the requirement that slag needs further dilution process, technique is simple.
The invention provides a kind of method reclaiming valuable metal from waste and old lithium ion battery and/or its material, comprise the following steps:
Waste and old lithium ion battery and/or its material, metallurgical coke are mixed with flux and/or containing the waste material of one or more in Cu, Co and Ni, obtains mixture; Described metallurgical coke accounts for 0 ~ 20wt% of mixture; In described mixture, CaO/SiO2>=1 or (CaO+MgO)/SiO
2>=1;
Described mixture is carried out retailoring at the temperature of 1400 DEG C ~ 1600 DEG C, obtains the alloy containing valuable metal and slag.
Preferably, in described mixture, CaO/SiO
2=1.01 ~ 3 or (CaO+MgO)/SiO
2=1.01 ~ 3.
Preferably, described flux is one or more in Wingdale, rhombspar, silica and aluminum oxide.
Preferably, described is one or more in copper smelting slag, cobalt metallurgical slag and nickel fibers slag containing the waste material of one or more in Cu, Co and Ni.
Preferably, described waste and old lithium ion battery is one or more in waste and old lithium-ion battery with steel shell, waste aluminum case lithium ion battery and waste polymer lithium ion battery;
Described waste and old lithium ion battery material is containing one or more lithium ion battery processing waste in Cu, Co and Ni.
Compared with prior art, the present invention with waste and old lithium ion battery and/or its material for recycling object, with a certain amount of metallurgical coke, and flux and/or containing one or more waste material mixing in Cu, Co and Ni, form mixture, then at the temperature of 1400 DEG C ~ 1600 DEG C, carry out retailoring, obtain the alloy containing valuable metal and slag; In described mixture, CaO/SiO
2>=1 or (CaO+MgO)/SiO
2>=1.In the retailoring process of one or more battery wastes containing Co or Ni, temperature is 1400 DEG C ~ 1600 DEG C, in described battery waste, graphite carbon and aluminium etc. by Cu, Co and Ni reduction in mixture, can form the alloy containing valuable metal, as Cu-Co-Ni alloy; SiO
2, CaO, Al
2o
3can with impurity element effect, formed slag.The present invention controls the CaO/SiO of mixture
2>=1 or (CaO+MgO)/SiO
2>=1, namely adopt basic slag melting, while the high efficiente callback realizing valuable metal, reduce the content of valuable metal in slag.Experiment display, in the alloy of method institute provided by the invention output the rate of recovery of Cu, Co and Ni all >=95wt%, in slag the content of Cu, Co and Ni all≤0.5wt%, slag can directly be discarded without the need to further dilution, simplifies technique.
Accompanying drawing explanation
The process flow sheet reclaiming valuable metal from waste and old lithium ion battery and/or its material that Fig. 1 provides for the embodiment of the present invention.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The invention provides a kind of method reclaiming valuable metal from waste and old lithium ion battery and/or its material, comprising:
Steps A) by waste and old lithium ion battery and/or its material;
Metallurgical coke; With
Flux and/or containing one or more waste material mixing in Cu, Co and Ni, obtains mixture;
Described metallurgical coke accounts for 0 ~ 20wt% of mixture;
In described mixture, CaO/SiO
2>=1 or (CaO+MgO)/SiO
2>=1;
Step B) described mixture is carried out retailoring at the temperature of 1400 DEG C ~ 1600 DEG C, obtain the alloy containing valuable metal and slag.
For the deficiency existed in current waste and old lithium ion battery recovery and reuse technology, the present invention proposes a kind of novelty by waste and old lithium ion battery and/or its material Direct Reductive Melting, with the method for high efficiente callback copper, cobalt, nickel valuable metal, this technique has significant economy, environment and social benefit.
Fig. 1 is the process flow sheet reclaiming valuable metal from waste and old lithium ion battery and/or its material that the embodiment of the present invention provides.
See Fig. 1, first the embodiment of the present invention by waste and old lithium ion battery, metallurgical slag, Wingdale and silica and metallurgical coke mixing, obtains mixture.
The present invention reclaims copper, cobalt, nickel valuable metal from waste and old lithium ion battery and/or its material, described waste and old lithium ion battery and material thereof comprise waste and old lithium ion battery and waste and old lithium ion battery material, wherein, described waste and old lithium ion battery material is preferably containing one or more lithium ion battery processing waste in Cu, Co and Ni, namely produces the cell exhaust material containing Cu, Co, Ni or the defective material of output in lithium ion battery process; Described waste and old lithium ion battery is preferably one or more in waste and old lithium-ion battery with steel shell, waste aluminum case lithium ion battery and waste polymer lithium ion battery, is more preferably at least one in waste and old lithium-ion battery with steel shell and waste aluminum case lithium ion battery.Alternatively, in the present invention, described waste and old lithium ion battery comprises box hat, aluminum hull and polymkeric substance three types.In the present invention, described waste and old lithium ion battery and material thereof can directly enter stove melting without the need to disassembling, and avoid the environmental pollution in the process of disassembling and risk of explosion.
In an embodiment of the present invention, the typical composition of described waste and old lithium ion battery and material thereof is: Fe1wt% ~ 40wt%; Cu5wt% ~ 10wt%; Co5wt% ~ 16wt%; Ni2wt% ~ 2.5wt%; Al1wt% ~ 35wt%; C5wt% ~ 15wt%.To those skilled in the art, described waste and old lithium ion battery and material thereof also comprise inevitable impurity element, and the present invention is not particularly limited this.
The present invention adopts metallurgical coke and flux and/or is raw material containing the waste material of one or more in Cu, Co and Ni, with described waste and old lithium ion battery and/or its material mixing, obtains mixture.
Wherein, the present invention can be raw material containing the waste material of one or more in Cu, Co and Ni, and it is preferably one or more in copper smelting slag (copper ashes), cobalt metallurgical slag (cobalt slag) and nickel fibers slag (nickel slag).Described metallurgical slag is the waste material containing Cu, Co or Ni etc. well known to those skilled in the art, preferably comprises: the SiO of 15wt% ~ 60wt%
2; The CaO of 1wt% ~ 15wt%; The MgO of 0 ~ 15wt%.The present invention makes full use of the SiO wherein contained
2with CaO etc., Some substitute or completely alternative flux, significantly can reduce the consumption of flux, contribute to reducing production cost.
In an embodiment of the present invention, the typical composition of copper ashes is: Cu0.5wt% ~ 9.6wt%; TFe22wt% ~ 55wt%; SiO
218wt% ~ 40wt%; CaO1wt% ~ 6wt%; Al
2o
30.9wt% ~ 5wt%; MgO0.9wt% ~ 5wt%.Wherein, Cu is preferably 1wt% ~ 5wt%; TFe is total iron well known to those skilled in the art or full iron, is preferably 30wt% ~ 45wt%.To those skilled in the art, described copper ashes also comprises inevitable impurity element, and the present invention is not particularly limited this.
In an embodiment of the present invention, the typical composition of cobalt slag is: Co3wt% ~ 3.5wt%; Cu3wt% ~ 4wt%; TFe22wt% ~ 55wt%; SiO
218wt% ~ 40wt%; CaO1wt% ~ 5wt%; Al
2o
32wt% ~ 5wt%; MgO3wt% ~ 5wt%.Wherein, TFe is total iron well known to those skilled in the art or full iron, is preferably 30wt% ~ 45wt%.To those skilled in the art, described cobalt slag also comprises inevitable impurity element, and the present invention is not particularly limited this.
In an embodiment of the present invention, the typical composition of nickel slag is: Ni0.2wt% ~ 0.5wt%; Co0.05wt% ~ 0.2wt%; Cu0.2wt% ~ 0.5wt%; TFe20wt% ~ 50wt%; SiO
222wt% ~ 60wt%; CaO1wt% ~ 5wt%; Al
2o
30 ~ 10wt%; MgO5wt% ~ 10wt%.Wherein, Ni is preferably 0.2wt% ~ 0.3wt%; Cu is preferably 0.2wt% ~ 0.3wt%; TFe is total iron well known to those skilled in the art or full iron, is preferably 30wt% ~ 45wt%.To those skilled in the art, described nickel slag also comprises inevitable impurity element, and the present invention is not particularly limited this.
The present invention can allocate flux into as required, and described flux is preferably one or more in Wingdale, rhombspar, silica and aluminum oxide, is more preferably at least one in Wingdale and silica.Described flux is well known to those skilled in the art, and the present invention preferably adopts the flux being crushed to 10mm ~ 50mm.
The present invention can adopt metallurgical coke as reductive agent, described metallurgical coke be for smelting iron, the general name of the coke of molten iron, ferroalloy smelting and non-ferrous metal.Described metallurgical coke adopts this area to commonly use, and the present invention is not particularly limited it.
In embodiments of the present invention, CaO and SiO is contained by this mixture be mixed to get containing the raw material such as waste material, Wingdale and silica of one or more in Cu, Co and Ni of described metallurgical slag
2deng, and, CaO/SiO
2>=1, be preferably 1.01 ~ 3, be more preferably 1.1 ~ 2; Or (CaO+MgO)/SiO
2>=1, be preferably 1.01 ~ 3, be more preferably 1.1 ~ 2.The present invention adopts basic slag melting, while the high efficiente callback realizing valuable metal, reduces the content of valuable metal in slag.
The present invention is got the raw materials ready in proportion by above-mentioned material, is obtained by mixing mixture, and concrete batching can be: describedly preferably account for 0 ~ 50wt% of mixture containing the waste material of one or more in Cu, Co and Ni, is more preferably 1wt% ~ 49.8wt%; Partially or completely can substitute flux due to described containing the waste material of one or more in Cu, Co and Ni, described flux preferably accounts for 0 ~ 50wt% of mixture, is more preferably 1wt% ~ 45wt%; Because the carbon in waste and old lithium ion battery and material thereof and metallic aluminium can make reductive agent, the present invention can not add melting under metallurgical coke, output Cu-Co-Ni alloy, and described metallurgical coke accounts for 0 ~ 20wt% of mixture, is preferably 1 ~ 15wt%; Surplus is waste and old lithium ion battery and/or its material.Wherein, described flux and containing in Cu, Co and Ni one or more waste material should different time be 0.
After obtaining mixture, the embodiment of the present invention is dropped in shaft furnace carries out retailoring, and temperature is 1400 DEG C ~ 1600 DEG C, obtains Cu-Co-Ni alloy as Cu-Co-Ni-Fe alloy, and slag and flue dust.
It is equipment well known to those skilled in the art that the present invention carries out retailoring shaft furnace used, and it can be divided into preheating zone, pyrolysis zone and three, retailoring district part from top to bottom.Described shaft furnace has alloy mouth and slag notch, is respectively used to release alloy and slag.
After dropping into mixture to described shaft furnace, in preheating zone, in-furnace temperature controls below 300 DEG C, and old and useless battery material slowly heats up, and avoids battery explosion; In pyrolysis zone, in-furnace temperature is elevated to about 700 DEG C, the organism generation pyrolysis such as the plastics in battery material, and the heat of generation can be preheating zone gas provides energy; In retailoring district, in-furnace temperature is 1400 DEG C ~ 1600 DEG C, be preferably 1450 DEG C ~ 1550 DEG C, more than 1300 DEG C, in battery material, graphite carbon and aluminium and metallurgical coke can by Cu, Co and Ni reduction in mixture, form Cu-Co-Ni alloy, described Cu-Co-Ni alloy is alloy well known to those skilled in the art; SiO
2, CaO, Al
2o
3can with impurity element effect, can be formed containing Cu, Co and Ni all≤slag of 0.5wt%, namely in described slag the grade of Cu, Co and Ni all≤0.5wt%.And rise to the temperature of the flue gas of furnace roof at 250 DEG C ~ 700 DEG C, due in flue gas containing the organism such as fluorine and chlorine, need by the process of high-temperature flue gas quench system, to avoid the generation of Dioxins.
The present invention is not particularly limited charging capacity, adopts this area conventional process, if rate of feeding is 300kg/h; Smelting time can be 30min ~ 90min.
After obtaining Cu-Co-Ni alloy and slag, the present invention carries out analysis of chemical elements to it.Experiment display, in the alloy of method output provided by the invention the rate of recovery of Cu, Co and Ni all >=95wt%, organic efficiency is higher; In slag the content of Cu, Co and Ni all≤0.5wt%, avoid the requirement that slag needs further dilution process, technique is simple.
Described Cu-Co-Ni alloy by powder by atomization and further powder leach, leach liquefaction and separating-purifying etc., obtaining can the metal of market sale or compound products; And described slag can be used as material of construction use.
In sum, the present invention adopts CaO/SiO
2>=1 or (CaO+MgO)/SiO
2the mixture of>=1 carries out melting, namely basic slag melting is adopted, realize cell exhaust material and containing one or more waste material in Cu, Co and Ni as discarded metallurgical slag in valuable metal high efficiente callback while, in effective reduction slag, the content of valuable metal, has significant economy, environmental and social benefits.
Further, the present invention is in recovery battery while valuables material, solve the recycling problem containing valuable metal Cu, Co, Ni in one or more waste material in Cu, Co and Ni, develop a kind of novel process of the comprehensively recovering valuable metal that " gives up " with " giving up " smelting.
In addition, the present invention preferably adopts aluminum hull waste and old lithium ion battery and/or its material, and it contains a large amount of metal A l, and in the metallurgical material supplementary furnace that can add metal oxide or containing metal oxide, the oxygen of reaction zone, is converted into Al by the Al in battery material
2o
3, and discharge a large amount of heat energy, thus can pyritic smelting be realized.That is, the present invention utilizes plastics organic compound combustion and burning exothermic heat of reaction in battery material, can realize pyritic smelting; Utilize metal aluminum foil in battery material, graphite carbon makes reductive agent, cobalt, nickel metal oxide back can be become metal, take full advantage of the various compositions in battery material.
In order to understand the present invention further, below in conjunction with embodiment, the method reclaiming valuable metal from waste and old lithium ion battery and/or its material provided by the invention is specifically described.
The main moiety of the waste and old lithium ion battery used in following examples is see table 1, and table 1 is the main moiety of embodiment of the present invention waste and old lithium ion battery used.
The main moiety of table 1 embodiment of the present invention waste and old lithium ion battery used
Embodiment 1
Waste and old lithium-ion battery with steel shell, Wingdale, silica and metallurgical coke are mixed, obtains mixture, wherein, to get the raw materials ready mixing by the Wingdale of 23.7wt%, the silica of 17.3wt%, the metallurgical coke of 12wt%; In described mixture, CaO/SiO
2=1.3.
Put in shaft furnace by the speed of 300kg/h by described mixture and carry out retailoring, smelting temperature is 1450 DEG C, and smelting time is 60min, and furnace roof flue-gas temperature is 450 DEG C.Treat that slag is separated completely with alloy melt, superalloy and slag are released from alloy mouth and slag notch respectively, obtain Cu-Co-Ni alloy and slag.
In the alloy of output, the rate of recovery of Cu, Co and Ni is respectively 96.9%, 98.1% and 96.8%; 0.35wt%, 0.31wt% and 0.05wt% is respectively containing Cu, Co and Ni in slag.Result shows, the present invention, while the high efficiente callback realizing valuable metal, reduces the content of valuable metal in slag.
Embodiment 2
Waste and old lithium-ion battery with steel shell, copper ashes (Cu1wt%, TFe42wt%), nickel slag (Cu0.2wt%, Ni0.35wt%, TFe44wt%), cobalt slag (Cu3wt%, Co3.5wt%, TFe42wt%), Wingdale and metallurgical coke are mixed, obtain mixture, wherein, to get the raw materials ready mixing by the copper ashes of 10.4wt%, the cobalt slag of 6.9wt%, the nickel slag of 17.3wt%, the Wingdale of 21.7wt%, the metallurgical coke of 9wt%; In described mixture, CaO/SiO
2=1.3.
Put in shaft furnace by the speed of 300kg/h by described mixture and carry out retailoring, smelting temperature is 1450 DEG C, and smelting time is 60min, and furnace roof flue-gas temperature is 450 DEG C.Treat that slag is separated completely with alloy melt, superalloy and slag are released from alloy mouth and slag notch respectively, obtain Cu-Co-Ni alloy and slag.
In the alloy of output, the rate of recovery of Cu, Co and Ni is respectively 97.1%, 96.9% and 96.0%; 0.29wt%, 0.40wt% and 0.08wt% is respectively containing Cu, Co and Ni in slag.Result shows, the present invention, while the high efficiente callback realizing valuable metal, reduces the content of valuable metal in slag.
Embodiment 3
Waste aluminum case lithium ion battery, copper ashes (Cu1wt%, TFe42wt%) and Wingdale are mixed, obtains mixture, wherein, to get the raw materials ready mixing by the copper ashes of 49.8wt%, the Wingdale of 25.4wt%; In described mixture, CaO/SiO
2=1.3.
Put in shaft furnace by the speed of 300kg/h by described mixture and carry out retailoring, smelting temperature is 1450 DEG C, and smelting time is 60min, and furnace roof flue-gas temperature is 450 DEG C.Treat that slag is separated completely with alloy melt, superalloy and slag are released from alloy mouth and slag notch respectively, obtain Cu-Co-Ni alloy and slag.
In the alloy of output, the rate of recovery of Cu, Co and Ni is respectively 95.8%, 97.0% and 95.2%; 0.45wt%, 0.41wt% and 0.10wt% is respectively containing Cu, Co and Ni in slag.Result shows, the present invention, while the high efficiente callback realizing valuable metal, reduces the content of valuable metal in slag.
Embodiment 4
Waste and old lithium-ion battery with steel shell, waste aluminum case lithium ion battery, copper ashes (Cu1wt%, TFe42wt%), Wingdale, silica and metallurgical coke are mixed, obtain mixture, wherein, the quality of waste and old lithium-ion battery with steel shell is 1.3 times of the quality of waste aluminum case lithium ion battery, to get the raw materials ready mixing by the copper ashes of 28.8wt%, the Wingdale of 28.3wt%, the metallurgical coke of 11.5wt%; In described mixture, CaO/SiO
2=1.5.
Put in shaft furnace by the speed of 300kg/h by described mixture and carry out retailoring, smelting temperature is 1450 DEG C, and smelting time is 60min, and furnace roof flue-gas temperature is 450 DEG C.Treat that slag is separated completely with alloy melt, superalloy and slag are released from alloy mouth and slag notch respectively, obtain Cu-Co-Ni alloy and slag.
In the alloy of output, the rate of recovery of Cu, Co and Ni is respectively 96.5%, 97.7% and 96.3%; 0.33wt%, 0.30wt% and 0.08wt% is respectively containing Cu, Co and Ni in slag.Result shows, the present invention, while the high efficiente callback realizing valuable metal, reduces the content of valuable metal in slag.
As seen from the above embodiment, in the alloy of method output provided by the invention the rate of recovery of Cu, Co and Ni all >=95wt%, organic efficiency is higher; In slag the content of Cu, Co and Ni all≤0.5wt%, slag is without the need to further dilution process, and can directly discard, technique is simple.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (2)
1. from waste and old lithium ion battery and/or its material, reclaim a method for valuable metal, comprise the following steps:
Waste and old lithium ion battery without the need to disassembling and/or its material, metallurgical coke being mixed with flux and/or containing the waste material of one or more in Cu, Co and Ni, obtaining mixture; Described metallurgical coke accounts for 0 ~ 20wt% of mixture; In described mixture, CaO/SiO
2=1.1 ~ 2 or (CaO+MgO)/SiO
2=1.1 ~ 2; Described waste and old lithium ion battery is one or more in waste and old lithium-ion battery with steel shell, waste aluminum case lithium ion battery and waste polymer lithium ion battery; Described waste and old lithium ion battery material is containing one or more lithium ion battery processing waste in Cu, Co and Ni; Described is one or more in copper smelting slag, cobalt metallurgical slag and nickel fibers slag containing the waste material of one or more in Cu, Co and Ni;
Described mixture is carried out retailoring at the temperature of 1400 DEG C ~ 1600 DEG C, obtains the alloy containing valuable metal and slag.
2. method according to claim 1, is characterized in that, described flux is one or more in Wingdale, rhombspar, silica and aluminum oxide.
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| CN104611566B (en) * | 2014-12-29 | 2017-02-22 | 长沙矿冶研究院有限责任公司 | Method for recycling valuable metals in waste lithium ion batteries |
| CN107012332A (en) * | 2017-04-18 | 2017-08-04 | 中科过程（北京）科技有限公司 | A kind of method that metal is reclaimed in nickeliferous, cobalt refuse battery and cupric electron wastes collaboration |
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| CN112176190A (en) * | 2020-09-17 | 2021-01-05 | 昆明理工大学 | Method for recovering cobalt, copper and iron from waste cobalt-containing lithium ion battery |
| CN112661201B (en) * | 2020-12-23 | 2022-11-15 | 广东邦普循环科技有限公司 | Method for preparing nickel cobalt lithium manganate through reverse positioning of power battery and application |
| CN113562990B (en) * | 2021-07-26 | 2022-04-29 | 广东飞南资源利用股份有限公司 | Slag regulation and control method for metallurgical slag resource utilization, slag shape regulation and control method, smelting method and building material |
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