CN109706320B - Method for recovering Co and Li in waste lithium battery by wet process by taking ethanol as reducing agent - Google Patents
Method for recovering Co and Li in waste lithium battery by wet process by taking ethanol as reducing agent Download PDFInfo
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- CN109706320B CN109706320B CN201910084974.5A CN201910084974A CN109706320B CN 109706320 B CN109706320 B CN 109706320B CN 201910084974 A CN201910084974 A CN 201910084974A CN 109706320 B CN109706320 B CN 109706320B
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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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W30/84—Recycling of batteries or fuel cells
Abstract
A method for recovering Co and Li in waste lithium batteries by a wet method by using ethanol as a reducing agent belongs to the metallurgical field of recovery of precious metals in positive electrode materials of waste lithium batteries. The method comprises the following steps: adding the pretreated solid powder of lithium cobaltate into an acid leaching mixed solution of dilute sulfuric acid and ethanol, continuously stirring at 80-90 ℃, filtering the acid leaching reaction solution, adding a NaOH solution into the leaching solution, and separating out Co to obtain Co (OH)2The precipitated mixture solution is to contain Co (OH)2Washing, drying and calcining the filter residue to obtain Co3O4(ii) a To contain Li+Adding NaOH dropwise into the filtrate, evaporating and concentrating, and adding saturated Na2CO3Stirring to react to obtain Li2CO3The precipitate is filtered and then dried to obtain Li2CO3. The method has the advantages of high leaching rate, environmental protection, generation of organic matters such as aldehyde, ether, ester and the like.
Description
Technical Field
The invention relates to the field of metallurgy for recovering precious metals from anode materials of waste lithium ion batteries, in particular to a method for recovering Co and Li in waste lithium batteries by a wet method by using ethanol as a reducing agent.
Background
The modernization of society requires more and more mobile electronic and electric vehicles, which rely mainly on Lithium Ion Batteries (LIBs). As the demand for LIBs increases, the supply of battery materials such as lithium salts and transition metals has also increased. Among the commonly used battery materials, lithium (Li) and cobalt (Co) play a crucial role. However, limited Co resources, uneven distribution of Li minerals and uneven concentration of Li reserves in salt and sea water lead to higher production costs. Therefore, Li and Co are considered as elements having influence. Compared with natural resources, the waste LIBs have much higher Li and Co concentrations and are rich in Li and Co. In view of the environmental issues posed by disposal of waste LIBs, recycling of LIBs may be a sustainable approach while meeting the growing demand of the battery industry for Li and Co.
At present, the pyrometallurgical and hydrometallurgical routes are used for recycling waste LIBsTwo exemplary methods. Generally, the waste batteries should be pretreated, such as discharged, dismantled, etc. The pre-treated electrode material is then further processed. Pyrometallurgy melts the waste electrode material by slag separation and carbothermic reduction using a high temperature furnace to obtain Li and Co oxides by a pyrometallurgical process, followed by separation. Pyrometallurgical processes are often associated with the emission of harmful gases and are complex in process. The hydrometallurgy is to LiCoO2Because they have benefits such as high efficiency and less toxic emissions to the atmosphere, and can be produced industrially. Among the hydrometallurgical techniques for recycling spent LIB, acid leaching is the most cost effective and simple and environmentally friendly.
Disclosure of Invention
The invention aims to provide a method for recovering Co and Li in a waste lithium battery by a wet process by taking ethanol as a reducing agent2The method is a hydrometallurgical process for recovering the precious metals in the waste lithium batteries, which is environment-friendly, energy-saving, low-consumption, green and safe. The method has the advantages of high leaching rate, environmental protection, generation of organic matters such as aldehyde, ether, ester and the like.
The invention discloses a method for recovering Co and Li in a waste lithium battery by a wet method by taking ethanol as a reducing agent, which comprises the following steps:
step 1: pretreatment of
Discharging and disassembling the waste lithium battery to obtain a positive plate;
putting the positive plate into a sodium hydroxide solution, dissolving to remove aluminum, and obtaining a lithium cobaltate black powder mixed solution;
filtering the lithium cobaltate black powder mixed solution, drying, calcining and grinding filter residues to obtain solid powder of lithium cobaltate;
step 2: acid leaching reaction
Mixing dilute sulfuric acid and ethanol to obtain acid leaching mixed liquor; wherein, in the acid leaching mixed solution, the volume fraction of ethanol is 5-20%, and the balance is dilute sulfuric acid; the molar concentration of the dilute sulfuric acid is 4-6 mol/L;
adding lithium cobaltate solid powder into the acid leaching mixed solution, continuously stirring at 80-90 ℃, monitoring the recovery rate of Co and Li in the reaction solution in real time, and obtaining the acid leaching reaction solution when the recovery rate of Co and Li is not changed any more; wherein, according to the solid-liquid ratio, the lithium cobaltate solid powder: acid leaching mixed liquor (20-40) g: 1L;
and step 3: precipitation of
Filtering the acid leaching reaction solution for the first time to obtain a leaching solution;
adding NaOH solution into the leaching solution to separate out Co to obtain Co (OH)2The precipitated mixture was filtered for the second time to obtain a mixture containing Co (OH)2Precipitated filter residue and Li-containing+The filtrate of (1);
will contain Co (OH)2Washing, drying and calcining the filter residue to obtain Co3O4；
To contain Li+Adding NaOH dropwise into the filtrate, adjusting the pH value to 9-10, and then evaporating and concentrating until Li is in the filtrate+Adding saturated Na at a concentration of above 10g/L2CO3Stirring to react to obtain Li2CO3The precipitate is filtered and then dried to obtain Li2CO3(ii) a Wherein, saturated Na2CO3The addition amount of (a) is 1-1.2 times of the theoretical amount of the reaction.
In the step 1, the waste lithium battery is discharged by soaking the waste lithium battery in a saturated sodium chloride solution for 10-12 hours.
In the step 1, lithium cobaltate on the positive electrode sheet is attached to the aluminum foil sheet, and the aluminum is dissolved and removed by NaOH with the molar concentration of 2-3 mol/L, wherein the amount of the NaOH is the amount capable of fully dissolving the aluminum foil.
In the step 1, the drying is carried out for 50-80 ℃, the drying time is 8-12 h, the calcining temperature is 500-600 ℃, and the calcining time is 6-8 h.
In the step 1, an agate mortar is adopted for grinding, the grinding time is 30-40 min, the grinding aims to uniformly disperse particles, and the particle size of the lithium cobaltate solid powder is 200-300 meshes.
In the step 2, stirring is carried out at a stirring speed of 200-400 r/min.
In the step 2, during the continuous stirring process, a condensing device is added to reflux the volatilized ethanol.
In the step 2, the method for monitoring the recovery rates of Co and Li in the reaction solution in real time comprises the following steps: elemental composition analysis was performed on the reaction solution, and the contents of Co and Li were calculated.
In the step 3, the molar concentration of the NaOH solution is 2-4 mol/L, the adding method is that the pH value of the leaching solution is firstly adjusted to 6.0-6.5, and when precipitation occurs, NaOH is dripped until the precipitation is not increased any more.
In the method for recovering Co and Li in the waste lithium battery by using ethanol as a reducing agent through a wet method, the water is deionized water.
In the method for recovering Co and Li in waste lithium batteries by using ethanol as reducing agent through wet method, the generated Co3O4Electrochemical separation into Co and oxygen occurs in the molten carbonate.
The method for recovering Co and Li from waste lithium batteries by a wet process by using ethanol as a reducing agent has the recovery rate of Co of 70.9-90.4% and the recovery rate of Li of 94.6-99.9%.
In the invention, the water is deionized water unless otherwise specified, and the purity of the raw materials is analytically pure or higher.
The method for recovering Co and Li in the waste lithium battery by using ethanol as a reducing agent through a wet method has the beneficial effects that:
1. the invention relates to a method for treating pretreated anode material powder of waste lithium batteries by an acid leaching process, aiming at reducing LiCoO by using a new reducing agent ethanol to replace hydrogen peroxide in the traditional process2Co salts and Li salts are obtained. Then Co2+By adding NaOH solution with Co (OH)2Collected in the form of (1) and then calcined in air to convert it to Co3O4. Can then obtainCo of (A)3O4Electrochemical separation into Co and oxygen occurs in the molten carbonate. Li of Li2CO3Is collected in the form of (1).
2. The principle of the method of the invention is as follows: co is used as the reducing agent for reducing the cobalt and lithium in the lithium cobaltate in the presence of sulfuric acid2+And Li+Is dissociated, and Co is dissociated based on the principle3+Reducing the cobalt into the solution to recover the cobalt and the lithium. Provides H required by the reaction in an acidic environment+And the solubility of cobalt and lithium is ensured.
3. The method can recycle and resynthesize the cobalt and lithium in the waste lithium battery into the battery anode material with observable performance in a low-cost, environment-friendly and recycling manner, has simple and convenient operation and high leaching rate, and can be used for large-scale production.
Drawings
Fig. 1 is an XRD analysis chart of the calcined product of the positive electrode sheet of the battery in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
In the embodiment of the invention, the adopted waste mobile phone batteries are commercial products.
In the embodiment of the invention, the purity of the adopted ethanol is analytically pure.
In the embodiment of the invention, the purity of the adopted sodium hydroxide is analytically pure.
In the embodiment of the invention, the adopted sulfuric acid and sodium chloride have analytical purity.
In the embodiment of the invention, the adopted water bath kettle is a heat collection type constant temperature heating kettle, and the stirring speed is as follows: 300 r/min.
In the embodiment of the invention, the temperature of the water bath is 80 ℃.
In the embodiment of the invention, the drying box adopted for drying is a new seedling DZF-6020 type vacuum drying box.
In the embodiment of the invention, a muffle furnace is adopted for calcination.
In the embodiment of the invention, the adopted element analyzer is an atomic absorption spectrophotometer, and the model is as follows: BTS 4000.
In the embodiment of the invention, the heating of the reaction device is realized by placing the reactor in a water bath for heating.
Example 1
A method for recovering Co and Li in waste lithium batteries by a wet method by taking ethanol as a reducing agent comprises the following steps:
step 1: pretreatment of
Soaking the electrode end of the waste mobile phone battery in a saturated sodium chloride solution for 12 hours for full discharge, then manually disassembling, fully dissolving the disassembled positive plate by using a 2.5mol/L NaOH solution, and separating aluminum to obtain a lithium cobaltate black powder mixed solution;
and filtering the lithium cobaltate black powder mixed solution to obtain the filter residue of the positive electrode material. And then, drying the filter residue of the positive electrode material in a drying box at 60 ℃ for 8h, calcining the filter residue in a muffle furnace at 500 ℃ for 8h to obtain a calcined product, and grinding the calcined product for 30min to obtain lithium cobaltate solid powder with the particle size of 200-300 meshes. XRD analysis was performed on the obtained calcined product, and the XRD pattern obtained is shown in FIG. 1, from which it can be judged that the calcined product obtained by treatment and separation was lithium cobaltate.
Step 2: acid leaching
The acid leaching solution consists of ethanol and dilute sulfuric acid, wherein the concentration of the dilute sulfuric acid in the acid leaching solution is 5mol/L, the volume fraction of the ethanol is 20%, and the balance is the dilute sulfuric acid.
Adding 1g of lithium cobaltate solid powder into 50mL of acid leaching solution for reaction, arranging a condensing device in a reaction device, stirring at the rotating speed of 300r/min and the water bath temperature of 80 ℃ for 60min in the reaction process, carrying out element analysis on the obtained acid leaching reaction solution, and calculating the recovery rate of Co and Li.
And step 3: separation of
(1) Precipitated Co
Taking the acid leaching reaction solution after the reaction for the first filtration, reserving filtrate, adding 2mol/L NaOH solution into the filtrate, adjusting the pH value to be 6, then slowly dropwise adding the NaOH solution from the beginning of precipitation until the precipitation amount is not increased any more, and then carrying out the second filtration to obtain the productTo Co (OH)2Precipitated filter residue and Li-containing+The filtrate of (2), mixing Co (OH)2Calcining the precipitated filter residue to obtain Co3O4；
(2) And (3) precipitating Li: to contain Li+Adding 2mol/L NaOH solution to pH 9-10, heating in water bath, evaporating and concentrating to obtain Li+The concentration was adjusted to 10g/L and then saturated Na was added2CO3The addition amount is CO3 2-With Li+Reaction to give Li2CO31.2 times of the theoretical amount of (A), stirring to obtain precipitated Li2CO3Filtering and drying to obtain Li2CO3。
In this example, the recovery rate of Li was 99.3% and the recovery rate of Co was 77.1%.
Example 2
The method for recovering Co and Li from waste lithium batteries by a wet method by using ethanol as a reducing agent is different from the method in example 1 in that:
in the step 2, the reaction temperature is 90 ℃ in acid leaching solution;
the other ways are the same.
In this example, the recovery rate of Li was 99.4% and the recovery rate of Co was 90.4%.
Example 3
The method for recovering Co and Li from waste lithium batteries by a wet method by using ethanol as a reducing agent is different from the method in example 1 in that:
in the step 2, during the acid leaching reaction, the molar concentration of dilute sulfuric acid is 4 mol/L;
the other ways are the same.
In this example, the recovery rate of Li was 99.9% and the recovery rate of Co was 73.6%.
Example 4
The method for recovering Co and Li from waste lithium batteries by a wet method by using ethanol as a reducing agent is different from the method in example 1 in that:
in the step 2, the molar concentration of the dilute sulfuric acid is 6 mol/L;
the other ways are the same.
In this example, the recovery rate of Li was 99.9%, and the recovery rate of Co was 70.9%.
Example 5
The method for recovering Co and Li from waste lithium batteries by a wet method by using ethanol as a reducing agent is different from the method in example 1 in that:
in the step 2, according to the solid-liquid ratio, lithium cobaltate solid powder: the acid leaching mixed solution is 30g/L,
the other ways are the same.
In this example, the recovery rate of Li was 94.6% and the recovery rate of Co was 72.2%.
Example 6
A method for recovering Co and Li in waste lithium batteries by a wet method by taking ethanol as a reducing agent comprises the following steps:
step 1: pretreatment of
Soaking the electrode end of the waste mobile phone battery in a saturated sodium chloride solution for 12 hours for full discharge, then manually disassembling, fully dissolving the disassembled positive plate by using a 2mol/L NaOH solution, and separating aluminum to obtain a lithium cobaltate black powder mixed solution;
and filtering the lithium cobaltate black powder mixed solution to obtain the filter residue of the positive electrode material. And then, drying the filter residue of the positive electrode material in a drying box at the temperature of 80 ℃ for 8h, calcining the filter residue in a muffle furnace at the temperature of 550 ℃ for 10h, and then grinding the filter residue for 40min to obtain lithium cobaltate solid powder with the particle size of 200-300 meshes.
Step 2: acid leaching
The acid leaching solution consists of ethanol and dilute sulfuric acid, wherein the concentration of the dilute sulfuric acid in the acid leaching solution is 5mol/L, the volume fraction of the ethanol is 20%, and the balance is the dilute sulfuric acid.
Adding 2g of lithium cobaltate solid powder into 50mL of acid leaching solution for reaction, wherein a condensation device is arranged in a reaction device, and in the reaction process, the stirring rotation speed is 200r/min, the water bath temperature is 90 ℃, and the reaction time is 90min, so as to obtain an acid leaching reaction solution; sampling every 10min, analyzing the content of Co and Li in the acid leaching reaction solution through an element component analyzer, and stopping the reaction when the content of Co and Li is not increased any more or the increase variable is less than 1%;
wherein, the condensing unit who sets up flows back the ethanol that evaporates to the reaction unit in, guarantees that the volume of ethanol in the device is stable.
And step 3: separation of
(1) Precipitated Co
Taking the acid leaching reaction solution after the reaction for the first filtration, reserving filtrate, adding 2mol/L NaOH solution into the filtrate, adjusting the pH value to be 6.5, then slowly dropwise adding the solution from the beginning of precipitation until the precipitation amount is not increased any more, and carrying out the second filtration to obtain Co (OH)2Precipitated filter residue and Li-containing+The filtrate of (2), mixing Co (OH)2Calcining the precipitated filter residue to obtain Co3O4；
(2) And (3) precipitating Li: to contain Li+Adding 2mol/L NaOH solution to pH 9-10, heating in water bath, evaporating and concentrating to obtain Li+The concentration was adjusted to 10g/L and then saturated Na was added2CO3The addition amount is CO3 2-With Li+Reaction to give Li2CO31.1 times of the theoretical amount of (A), stirring to obtain precipitated Li2CO3Filtering and drying to obtain Li2CO3。
In this example, the recovery rate of Li was 99.4% and the recovery rate of Co was 90.4%.
Comparative example 1
A method for recycling Co and Li in waste lithium batteries by a wet method, which is different from the method in the embodiment 1 in that:
in step 2, no ethanol is added to the acid leaching solution.
The other ways are the same.
In this comparative example, the recovery rate of Li was 93.4% and the recovery rate of Co was 55.5%. The comparison of the recovery rate of ethanol added in example 1 shows that the leaching rates of cobalt and lithium are obviously improved by adding ethanol. The addition of ethanol was shown to act to promote cobalt and lithium leaching.
Comparative example 2
The method for recovering Co and Li from waste lithium batteries by a wet method by using ethanol as a reducing agent is different from the method in example 1 in that:
in the step 2, the reaction temperature is 70 ℃ in acid leaching solution;
the other ways are the same.
In this comparative example, the recovery rate of Li was 83.1% and the recovery rate of Co was 50.1%. A comparison between this comparative example and example 1 shows that the acid leaching reaction temperature has a great influence on the recovery rate.
Comparative example 3
The method for recovering Co and Li from waste lithium batteries by a wet method by using ethanol as a reducing agent is different from the method in example 1 in that:
in the step 2, the reaction temperature is 60 ℃ in acid leaching solution;
the other ways are the same.
In this comparative example, the recovery rate of Li was 80.1% and the recovery rate of Co was 42.3%. By comparing this comparative example with example 1, it is demonstrated that the reduction in the acid leaching reaction temperature leads to a reduction in the recovery rate.
Comparative example 4
The method for recovering Co and Li from waste lithium batteries by a wet method by using ethanol as a reducing agent is different from the method in example 1 in that:
(1) in the step 2, during the acid leaching reaction, the molar concentration of dilute sulfuric acid is 2 mol/L;
the other ways are the same.
In this comparative example, the recovery rate of Li was 91.4% and the recovery rate of Co was 51.3%. By comparing this comparative example with example 1, it is shown that the addition of dilute sulfuric acid during acid leaching has a great influence on the acid leaching effect, thereby affecting the recovery rates of Li and Co, especially the recovery rate of Co.
Comparative example 5
The method for recovering Co and Li from waste lithium batteries by a wet method by using ethanol as a reducing agent is different from the method in example 1 in that:
in the step 2, during the acid leaching reaction, the molar concentration of dilute sulfuric acid is 3 mol/L;
the other ways are the same.
In this comparative example, the recovery rate of Li was 99.1%, and the recovery rate of Co was 67.1%. By comparing the comparative example with example 1, it is shown that the addition of dilute sulfuric acid during acid leaching has a great influence on the acid leaching effect, thereby affecting the recovery rate of Co.
Comparative example 6
The method for recovering Co and Li from waste lithium batteries by a wet method by using ethanol as a reducing agent is different from the method in example 1 in that:
in the step 2, according to the solid-liquid ratio, lithium cobaltate solid powder: the acid leaching mixed solution is 10g/L,
the other ways are the same.
In this comparative example, the recovery rate of Li was 95.8% and the recovery rate of Co was 66%, and a comparison between this comparative example and example 1 shows that the addition amount of the lithium cobaltate solid powder during the acid leaching process affects the recovery rate of Co.
Claims (10)
1. A method for recovering Co and Li in waste lithium batteries by a wet method by taking ethanol as a reducing agent is characterized by comprising the following steps:
step 1: pretreatment of
Discharging and disassembling the waste lithium battery to obtain a positive plate;
putting the positive plate into a sodium hydroxide solution, dissolving to remove aluminum, and obtaining a lithium cobaltate black powder mixed solution;
filtering the lithium cobaltate black powder mixed solution, drying, calcining and grinding filter residues to obtain solid powder of lithium cobaltate;
step 2: acid leaching reaction
Mixing dilute sulfuric acid and ethanol to obtain acid leaching mixed liquor; wherein, in the acid leaching mixed solution, the volume fraction of ethanol is 5-20%, and the balance is dilute sulfuric acid; the molar concentration of the dilute sulfuric acid is 4-6 mol/L;
adding lithium cobaltate solid powder into the acid leaching mixed solution, continuously stirring at 80-90 ℃, monitoring the recovery rate of Co and Li in the reaction solution in real time, and obtaining the acid leaching reaction solution when the recovery rate of Co and Li is not changed any more; wherein, according to the solid-liquid ratio, the lithium cobaltate solid powder: acid leaching mixed liquor (20-40) g: 1L;
and step 3: precipitation of
Filtering the acid leaching reaction solution for the first time to obtain a leaching solution;
adding NaOH solution into the leaching solution to separate out Co to obtain Co (OH)2A mixture of the precipitates is carried outSecond filtering to obtain a filtrate containing Co (OH)2Precipitated filter residue and Li-containing+The filtrate of (1);
will contain Co (OH)2Washing, drying and calcining the filter residue to obtain Co3O4；
To contain Li+Adding NaOH dropwise into the filtrate, adjusting the pH value to 9-10, and then evaporating and concentrating until Li is in the filtrate+Adding saturated Na at a concentration of above 10g/L2CO3Stirring to react to obtain Li2CO3The precipitate is filtered and then dried to obtain Li2CO3(ii) a Wherein, saturated Na2CO3The addition amount of (a) is 1-1.2 times of the theoretical amount of the reaction.
2. The method for wet recovery of Co and Li in waste lithium batteries by using ethanol as a reducing agent according to claim 1, wherein in the step 1, the waste lithium batteries are discharged by soaking the waste lithium batteries in a saturated sodium chloride solution for 10-12 h.
3. The method for wet recovery of Co and Li in waste lithium batteries by using ethanol as a reducing agent according to claim 1, wherein lithium cobaltate is attached to the aluminum foil in the step 1, and NaOH with a molar concentration of 2-3 mol/L is used to dissolve and remove aluminum, and the amount of NaOH is an amount capable of sufficiently dissolving the aluminum foil.
4. The method for recovering Co and Li from waste lithium batteries by a wet process by using ethanol as a reducing agent according to claim 1, wherein in the step 1, drying is performed for 50-80 ℃ for 8-12 h, calcining temperature is 500-600 ℃ and calcining time is 6-8 h.
5. The method as claimed in claim 1, wherein in the step 1, the grinding time is 30-40 min, and the particle size of the lithium cobaltate solid powder is 200-300 meshes.
6. The method for wet recovery of Co and Li in waste lithium batteries by using ethanol as a reducing agent according to claim 1, wherein in the step 2, the stirring is performed at a stirring speed of 200 to 400 r/min.
7. The method for wet recovery of Co and Li from waste lithium batteries using ethanol as a reducing agent according to claim 1, wherein the method for monitoring the recovery rate of Co and Li in the reaction solution in real time in step 2 comprises: elemental composition analysis was performed on the reaction solution, and the contents of Co and Li were calculated.
8. The method for recovering Co and Li from waste lithium batteries by a wet process by using ethanol as a reducing agent according to claim 1, wherein in the step 3, the molar concentration of the NaOH solution is 2-4 mol/L, the NaOH solution is added by firstly adjusting the pH value of the leaching solution to 6.0-6.5, and when precipitation occurs, NaOH is added dropwise until the precipitation does not increase any more.
9. The method for wet recycling of Co and Li from waste lithium batteries by using ethanol as a reducing agent according to any one of claims 1 to 8, wherein the Co and Li generated in the method for wet recycling of Co and Li from waste lithium batteries by using ethanol as a reducing agent3O4Electrochemical separation into Co and oxygen occurs in the molten carbonate.
10. The method for wet recycling Co and Li from waste lithium batteries by using ethanol as a reducing agent according to any one of claims 1 to 8, wherein the method for wet recycling Co and Li from waste lithium batteries by using ethanol as a reducing agent is adopted, wherein the recovery rate of Co is 70.9-90.4%, and the recovery rate of Li is 94.6-99.9%.
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| CN108396156A (en) * | 2015-11-27 | 2018-08-14 | 江苏理工学院 | A method of cobalt product is prepared by cobalt ammonia complex |
| CN107196007A (en) * | 2017-05-27 | 2017-09-22 | 南京博驰新能源股份有限公司 | A kind of lithium battery recycling method |
| CN107732352A (en) * | 2017-10-12 | 2018-02-23 | 南通新玮镍钴科技发展有限公司 | A kind of method that used Li ion cell positive electrode recycles |
| CN108172925A (en) * | 2017-12-27 | 2018-06-15 | 浙江中金格派锂电产业股份有限公司 | A kind of nickle cobalt lithium manganate ter-polymers cell anode waste recovery method |
| CN108360022A (en) * | 2018-05-02 | 2018-08-03 | 东北大学 | A kind of method that melten salt electriochemistry method recycles cobalt element in anode material of lithium battery |
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