CN114671424B - Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery - Google Patents
Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery Download PDFInfo
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- C01G45/12—Manganates manganites or permanganates
- C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
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- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention provides a method for regenerating a lithium ion battery anode material, the anode material and a lithium ion battery. The regeneration method comprises the steps of adding a positive electrode powder material into alkali liquor, heating, and converting lithium hexafluorophosphate and lithium fluoride in the positive electrode powder material into lithium carbonate under the action of the alkali liquor; then under the action of hydrogen iodide, lithium carbonate in the mixed powder is further converted into lithium iodide; and adding a precursor and a reducing agent corresponding to the anode material, converting lithium iodide in the composite slurry into an iodine simple substance under the action of the reducing agent and sublimating, reacting the added precursor corresponding to the anode material with lithium to generate a corresponding anode material, and finally obtaining the commercial lithium ion battery anode material lithium iron phosphate or nickel cobalt lithium manganate. The method greatly reduces the problem of lithium salt separation in the battery recovery process, fully utilizes lithium resources by integrally supplementing lithium, reduces battery recovery processes, reduces the battery material cost, improves the purity of recovered materials, and has greater innovation.
Description
Technical Field
The invention relates to the technical field of lithium ion battery material recycling, in particular to a method for recycling a lithium ion battery anode material, the lithium ion battery anode material and a lithium ion battery.
Background
With the application of lithium ion batteries in power batteries, the problem of treatment of waste lithium ion batteries is gradually highlighted. The waste lithium battery contains more important limited resources, including nickel, cobalt, manganese, lithium, graphite, electrolyte solvent, fluorine and other resources. The current lithium battery recovery process comprises a wet method and a pyrogenic method, and the resources are mainly converted into a solution and a compound through a thermal reaction or an acid-base reaction, and then are recycled through processes such as purification, extraction, filtration and the like. For example, the wet process mainly uses various acid-base solutions as transfer media to transfer metal ions from electrode materials into leachate, and utilizes various chemical reactions and physical-chemical separation means to extract metal elements from the solutions. In order to avoid the separation of metal and impurities, the pH value of the solution is also required to be controlled in the metal recovery process, and the control conditions in the recovery process are increased. The complex process flow and reaction requires the consumption of a large amount of reaction materials and reagents, and increases the recovery cost.
Particularly, electrolyte components added in the production process of the lithium ion battery are particularly difficult in the battery recovery process, and the current lithium ion battery electrolyte comprises a carbonate micromolecular solvent and more than 10% of lithium salt, mainly lithium hexafluorophosphate. In the process of battery recovery, the solvent can be vaporized and volatilized by vacuum heating after the battery is disassembled. But the lithium salt is extremely difficult to recover, and lithium hexafluorophosphate is partially deeply combined with battery powder in the using process of the battery and is difficult to separate by the traditional method. Moreover, the lithium salt generates hydrogen fluoride during powder recovery, and the hydrogen fluoride can cause serious harm to battery recovery equipment, environment and personnel. And lithium accounts for a relatively high proportion in lithium hexafluorophosphate, and if the lithium hexafluorophosphate is not well recovered, better economic benefit is difficult to realize, and huge waste is caused.
In a word, the recovery of lithium salt in the electrolyte in the battery recovery process is a key bottleneck problem in the current recovery system, and if the lithium salt is not properly treated, the problems of complex process, low yield, environmental pollution, production safety and the like can be caused, the resource waste can be caused, the battery recovery commercialization is seriously influenced, the battery recovery value is reduced, and the chain adverse effect is generated.
Disclosure of Invention
In view of the above, the present invention provides a method for regenerating a positive electrode material of a lithium ion battery and a systematic solution for integrated utilization of lithium salts, which are directed to the key problem of lithium salt recovery difficulty in battery recovery, so as to solve the above problems or at least partially solve the above problems.
In a first aspect, the present invention provides a method for regenerating a lithium ion battery cathode material, comprising the following steps:
disassembling the waste lithium ion battery, separating and crushing to obtain a positive electrode powder material;
adding the positive electrode powder material into alkali liquor, heating, and filtering to obtain mixed powder;
adding a hydrogen iodide solution into the mixed powder, and stirring for reaction to obtain a composite slurry;
adding a precursor corresponding to the anode material according to the molar ratio of elements in the composite slurry, simultaneously adding a reducing agent, heating at 300-500 ℃ for 2-12 h, and then heating at 700-800 ℃ for 6-24 h to obtain the anode material.
Preferably, the method for regenerating the lithium ion battery anode material comprises the steps of adding the anode powder material into alkali liquor, heating for 2-12 hours at 30-95 ℃, and filtering to obtain mixed powder.
Preferably, in the method for regenerating a positive electrode material of a lithium ion battery, the alkali solution includes at least one of a lithium hydroxide alkali solution, a sodium hydroxide solution, a potassium hydroxide solution and ammonium hydroxide.
Preferably, the method for regenerating the lithium ion battery cathode material comprises the steps of adding a hydrogen iodide solution with the concentration of 0.01-5 mol/L into the mixed powder, and stirring and reacting for 4-12 h at the temperature of 70-90 ℃.
Preferably, in the method for regenerating the lithium ion battery cathode material, the reducing agent comprises one or more of ascorbic acid, sodium borohydride, sodium citrate, hydroxylamine hydrochloride, glucose, sucrose, hydrazine hydrate, formaldehyde, sodium citrate or tannic acid.
Preferably, in the method for regenerating a positive electrode material of a lithium ion battery, the positive electrode material of the lithium ion battery includes any one of lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt manganese oxide, lithium manganese oxide, and lithium cobalt oxide.
Preferably, in the method for regenerating the lithium ion battery anode material, if the lithium ion battery anode material is lithium iron phosphate, a precursor corresponding to the anode material is iron phosphate;
if the anode material of the lithium ion battery is lithium manganese iron phosphate, the precursor corresponding to the anode material is ferric manganese phosphate;
if the positive electrode material of the lithium ion battery is nickel cobalt lithium manganate, a precursor corresponding to the positive electrode material is nickel cobalt manganese hydroxide;
if the positive electrode material of the lithium ion battery is lithium manganate, the precursor corresponding to the positive electrode material is manganese hydroxide;
and if the anode material of the lithium ion battery is lithium cobaltate, the precursor corresponding to the anode material is cobalt hydroxide.
In a second aspect, the invention also provides a positive electrode material prepared by the regeneration method.
In a third aspect, the invention also provides a lithium ion battery, which comprises the cathode material.
Compared with the prior art, the method for regenerating the anode material of the waste lithium ion battery has the following beneficial effects:
the regeneration method of the anode material of the waste lithium ion battery fully combines the problem of pain points of difficult electrolyte lithium salt recovery in the waste lithium ion battery recovery process, and combines a series of chemical methods, and after the anode powder material is added into alkali liquor and heated, lithium hexafluorophosphate and lithium fluoride in the anode powder material are further converted into lithium carbonate under the action of the alkali liquor; then under the action of hydrogen iodide, lithium carbonate in the mixed powder is further converted into lithium iodide; and adding a precursor and a reducing agent corresponding to the anode material, converting lithium iodide in the composite slurry into an iodine simple substance under the action of the reducing agent and sublimating, reacting the added precursor corresponding to the anode material with lithium to generate a corresponding anode material, and finally obtaining the commercial lithium ion battery anode material lithium iron phosphate or nickel cobalt lithium manganate. The method greatly reduces the problem of lithium salt separation in the battery recovery process, fully utilizes lithium resources by integrally supplementing lithium, reduces battery recovery processes, reduces the battery material cost, improves the purity of recovered materials, and has greater innovation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic flow chart of a method for regenerating a lithium ion battery positive electrode material according to the present invention;
fig. 2 is an XRD spectrum of the lithium iron phosphate cathode material recovered in the preparation of example 1 of the present invention;
fig. 3 is an SEM image of lithium iron phosphate as a cathode material recovered in the preparation of example 1 of the present invention;
FIG. 4 is an XRD spectrum of a cathode material nickel cobalt lithium manganate recovered in the preparation of example 1 of the present invention;
FIG. 5 is an SEM spectrum of a cathode material nickel cobalt lithium manganate recovered in the preparation of example 4 of the invention;
fig. 6 is a charge-discharge curve diagram of a lithium ion battery assembled by using the lithium iron phosphate as the cathode material recovered in example 1;
FIG. 7 is a charge-discharge curve diagram of a lithium ion battery assembled by using a lithium iron phosphate cathode material recovered in a conventional method;
FIG. 8 is a charge-discharge curve diagram of a lithium ion battery assembled by the positive electrode material nickel cobalt lithium manganate recycled in example 2;
fig. 9 is a charge-discharge curve diagram of a lithium ion battery assembled by the nickel cobalt lithium manganate which is the cathode material recycled in the conventional method.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the application provides a method for regenerating a lithium ion battery cathode material, as shown in fig. 1, comprising the following steps:
s1, disassembling a waste lithium ion battery, and then separating and crushing to obtain a positive electrode powder material;
s2, adding the positive electrode powder material into carbonate-containing alkali liquor, heating, and filtering to obtain mixed powder;
s3, adding a hydrogen iodide solution into the mixed powder, and stirring for reaction to obtain a composite slurry;
and S4, adding a precursor corresponding to the anode material according to the molar ratio of the elements in the composite slurry, simultaneously adding a reducing agent, heating for 2-12 h at 300-500 ℃, and then heating for 6-24 h at 700-800 ℃ to obtain the anode material.
It should be noted that, the method for regenerating the waste lithium ion battery positive electrode material provided in the embodiment of the present application specifically includes: firstly, disassembling a waste lithium ion battery, separating out solvent components of an electrolyte, further separating a battery diaphragm from a negative electrode to obtain a positive plate (comprising a positive active substance, a binder, a conductive agent, an aluminum foil current collector and the like), separating and crushing the aluminum foil current collector, and crushing again to obtain a positive powder material; specifically, the above-mentioned solvent refers to a solvent (for example, ethylene Carbonate (EC), diethyl carbonate (DEC), etc.) used in the electrolyte of the waste lithium ion battery, and these solvents can be removed by vacuum extraction process to volatilize the solvent in a gaseous state; the electrolyte in the waste lithium ion battery is completely absorbed by the positive and negative pole pieces, so that the positive powder material comprises a positive active substance, a binder, a conductive agent and lithium salts in the electrolyte (the lithium salts in the electrolyte cannot be volatilized in a gaseous state); the lithium salt is mainly lithium hexafluorophosphate, and during the use process of the battery, part of the lithium salt is converted into lithium fluoride and lithium carbonate, so that the lithium salt in the positive electrode powder material is mainly lithium hexafluorophosphate and part of lithium fluoride and lithium carbonate material; the positive active material mainly comprises lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium cobalt oxide and the like; step S2, adding the positive electrode powder material into an alkali liquor, and heating, wherein lithium hexafluorophosphate and lithium fluoride in the positive electrode powder material are further converted into lithium carbonate under the action of the alkali liquor; in the step S3, adding a hydrogen iodide solution into the mixed powder, stirring and reacting to obtain a composite slurry, and further converting lithium carbonate in the mixed powder into lithium iodide under the action of hydrogen iodide; in the step S4, the proportion of elements in the recovery is judged according to an ICP analysis method, a precursor corresponding to the corresponding anode material is added, lithium iodide and a certain proportion of reducing agent are simultaneously added according to the material molar ratio of the original slurry, the mixture is heated for 2 to 12 hours at the temperature of 300 to 500 ℃, and then the mixture is heated for 6 to 24 hours at the temperature of 700 to 800 ℃, so that the anode material is obtained. Specifically, lithium iodide in the composite slurry is converted into an iodine simple substance and sublimated under the action of a reducing agent, the simple substance iodine is obtained through condensation and recovery, a precursor corresponding to the added anode material reacts with lithium to generate a corresponding anode material, and a small amount of binder, conductive agent and the like which are originally present are calcined and volatilized after the anode material is heated at 700-800 ℃ for 6-24 h, so that the finally recovered anode material is only an anode active material and does not contain the binder, the conductive agent and the like.
According to the regeneration method of the lithium ion battery positive electrode material, the problem of pain points of difficult electrolyte lithium salt recovery in the waste lithium ion battery recovery process is fully combined, and a series of chemical methods are combined, so that after the positive electrode powder material is added into alkali liquor and heated, lithium hexafluorophosphate and lithium fluoride in the positive electrode powder material are further converted into lithium carbonate under the action of the alkali liquor; then under the action of hydrogen iodide, lithium carbonate in the mixed powder is further converted into lithium iodide; and adding a precursor and a reducing agent corresponding to the anode material, converting lithium iodide in the composite slurry into an iodine simple substance under the action of the reducing agent and sublimating, reacting the added precursor corresponding to the anode material with lithium to generate a corresponding anode material, and finally obtaining the commercial lithium ion battery anode material lithium iron phosphate or nickel cobalt lithium manganate. The method greatly reduces the problem of lithium salt separation in the battery recovery process, fully utilizes lithium resources by integrally supplementing lithium, reduces battery recovery processes, reduces the battery material cost, improves the purity of recovered materials, and has greater innovation.
In some embodiments, the positive electrode powder material is added into an alkali liquor and heated for 2-12 h at 30-95 ℃, and then filtered to obtain mixed powder.
In some embodiments, the alkali fluid comprises at least one of a lithium hydroxide alkali fluid, a sodium hydroxide solution, a potassium hydroxide solution, and ammonium hydroxide.
Specifically, carbonate may be added to the lye to form carbonate, sodium carbonate, ammonium carbonate, and the like.
Specifically, the concentration of the alkali liquor is 0.5-5mol L -1 . The alkali liquor is a mixed alkali solution containing 1mol/L sodium carbonate and 1mol/L sodium hydroxide.
In some embodiments, hydrogen iodide solution with the concentration of 0.01mol/L to 5mol/L is added into the mixed powder, and the mixture is stirred and reacted for 4 to 12 hours at the temperature of 70 to 90 ℃.
In some embodiments, the reducing agent comprises one or more of ascorbic acid, sodium borohydride, sodium citrate, hydroxylamine hydrochloride, glucose, sucrose, hydrazine hydrate, formaldehyde, sodium citrate, or tannic acid.
In some embodiments, the positive electrode material of the lithium ion battery includes any one of lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt manganese oxide, lithium manganese oxide, and lithium cobalt oxide.
In some embodiments, if the positive electrode material of the lithium ion battery is lithium iron phosphate, the precursor corresponding to the positive electrode material is iron phosphate;
if the anode material of the lithium ion battery is lithium manganese iron phosphate, the precursor corresponding to the anode material is ferric manganese phosphate;
if the positive electrode material of the lithium ion battery is nickel cobalt lithium manganate, the precursor corresponding to the positive electrode material is nickel cobalt manganese hydroxide;
if the positive electrode material of the lithium ion battery is lithium manganate, the precursor corresponding to the positive electrode material is manganese hydroxide;
and if the anode material of the lithium ion battery is lithium cobaltate, the precursor corresponding to the anode material is cobalt hydroxide.
Specifically, if the waste lithium ion positive electrode material is lithium iron phosphate, the precursor is ferric phosphate; specifically, the iron phosphate precursor can be prepared by the existing process, and the iron phosphate precursor is mainly classified by the following synthesis modes: precipitation, hydrothermal, sol-gel, air oxidation, controlled crystallization, and the like. For example, (1) iron phosphate can be produced by reacting purified phosphoric acid (either thermally or wet) with ferrous sulfate; (2) Iron phosphate may also be prepared by reacting iron sulfate with phosphates, mainly monoammonium phosphate (monoammonium phosphate) and diammonium phosphate (diammonium phosphate) being common phosphates, monoammonium phosphate being the predominant phosphate.
Based on the same inventive concept, the embodiment of the application also provides a lithium ion battery, which comprises the positive electrode material.
Obviously, the lithium ion battery comprises a negative electrode, an electrolyte, a separator and the like besides the positive electrode material; the cathode, the electrolyte, the diaphragm and the like are made of materials which are conventional in the industry. Since the positive electrode material does not contain a binder, a conductive agent, or the like, the binder or the conductive agent may be added to the positive electrode material in actual use.
The method for regenerating a positive electrode material for a lithium ion battery according to the present invention will be described below with reference to specific examples.
Example 1
The invention provides a method for regenerating a waste lithium ion battery anode material, which comprises the following steps:
s1, discharging a waste lithium iron phosphate battery, disassembling the battery, separating a positive plate, crushing and crushing the positive plate, sequentially grading and separating, and screening through ultrasonic vibration to obtain a positive powder material, wherein the positive material contains a lithium salt component in an electrolyte;
s2, adding the positive electrode powder material obtained in the step S1 into a mixed alkali solution of 1mol/L sodium carbonate and 1mol/L sodium hydroxide for soaking, heating at 50 ℃ for 7 hours, and filtering to obtain mixed powder; in the action of the alkali solution, lithium carbonate is formed by the lithium salt and forms a mixture with the positive electrode substance;
s3, adding the mixed powder in the step S2 into a hydrogen iodide solution with the concentration of 1mol/L, stirring and reacting for 12 hours at 80 ℃, and gradually converting lithium carbonate into lithium iodide to obtain mixed slurry;
and S4, detecting the contents of lithium, iron and phosphorus in the substances by ICP (inductively coupled plasma) aiming at the slurry in the step S3, adding an iron phosphate precursor according to the metering ratio of the lithium iron phosphate, simultaneously adding a reducing agent ascorbic acid, heating for 6 hours at 400 ℃ in a vacuum atmosphere, and then heating for 12 hours at 750 ℃ to obtain the lithium iron phosphate serving as the cathode material.
Example 2
The invention provides a method for regenerating a waste lithium ion battery anode material, which comprises the following steps:
s1, discharging a waste nickel cobalt lithium manganate ion battery, disassembling the battery, separating out a positive plate, crushing and crushing the positive plate, sequentially grading and separating, and screening by ultrasonic vibration to obtain a positive powder material, wherein the positive material contains a lithium salt component in an electrolyte;
s2, adding the positive electrode powder material obtained in the step S1 into a mixed alkali solution of 1mol/L sodium carbonate and 1mol/L sodium hydroxide for soaking, heating at 50 ℃ for 7 hours, and filtering to obtain mixed powder;
s3, adding the mixed powder obtained in the step S2 into a hydrogen iodide solution with the concentration of 1mol/L, and stirring and reacting at 80 ℃ for 12 hours to obtain mixed slurry;
and S4, detecting the contents of lithium, nickel, cobalt and manganese in the substances by ICP (inductively coupled plasma) according to the slurry in the step S3, adding a nickel-cobalt-manganese hydroxide precursor according to the metering ratio of the nickel-cobalt-manganese acid, simultaneously adding a reducing agent ascorbic acid, heating for 6 hours at 400 ℃ in a vacuum atmosphere, and then heating for 12 hours at 70 ℃ to obtain the nickel-cobalt-manganese acid cathode material of the cathode material.
Performance testing
The XRD spectrum of the lithium iron phosphate cathode material prepared in example 1 of the present application is shown in fig. 2, and the SEM spectrum is shown in fig. 3.
As can be seen from fig. 2, the positive electrode material prepared in example 1 corresponds to a standard spectrogram of lithium iron phosphate, and thus it can be determined that the positive electrode material prepared in example 1 is lithium iron phosphate.
The XRD spectrum of the lithium nickel cobalt manganese oxide as the cathode material prepared in the embodiment 2 is shown in figure 4, and the SEM spectrum is shown in figure 5.
As can be seen from fig. 4, the positive electrode material prepared in example 2 corresponds to a standard spectrogram of lithium nickel cobalt manganese oxide, so that it can be determined that the positive electrode material prepared in example 2 is lithium nickel cobalt manganese oxide.
The positive electrode material prepared in the embodiment 1 is adopted to assemble a lithium ion battery, wherein the proportion of the positive electrode plate is as follows according to a conventional scheme, and the active material: adhesive: the conductive agent 9 is 0.5, the diaphragm is made of conventional 12um PE, the electrolyte is made of EC, EMC, DEC =3, and contains 1mol of L-1 lithium hexafluorophosphate, and the negative electrode is a lithium sheet; the results of testing the charge and discharge curves of the lithium ion battery are shown in fig. 6.
The method comprises the following steps of (1) recovering a positive electrode material in a waste lithium iron phosphate battery by adopting a traditional regeneration process, namely directly recovering the prepared lithium iron phosphate material without adding hydrogen iodide in the recovery and regeneration process; specifically, the conventional regeneration process for recycling the anode material in the waste lithium iron phosphate battery comprises the following steps:
s1, discharging a waste lithium iron phosphate battery, disassembling the battery, and separating and crushing to obtain a positive electrode material;
s2, removing lithium salt from the positive electrode material, screening and sorting to obtain a positive electrode powder material;
and S3, adding a corresponding iron phosphate precursor according to the element molar ratio in the positive electrode powder material, simultaneously adding a reducing agent ascorbic acid, heating for 6 hours at 400 ℃ in a vacuum atmosphere, and then heating for 12 hours at 750 ℃ to obtain the recovered positive electrode material lithium iron phosphate.
And the cathode material recovered by the conventional method was assembled into a lithium ion battery in the same manner as in example 1 above, and the charge and discharge curve of the lithium ion battery was measured, with the result shown in fig. 7.
In fig. 6 to 7, a is a charge curve and b is a discharge curve.
As can be seen from comparison of fig. 6 to 7, the battery assembled by the lithium iron phosphate positive electrode material recovered by the method has higher charge and discharge capacity.
Using the cathode material prepared in example 2, the recovered cathode material was assembled into a lithium ion battery in the same manner as in example 1 above, and the charge and discharge curve of the lithium ion battery was tested, with the result shown in fig. 8.
The method comprises the following steps of (1) recycling a positive electrode material in a waste nickel cobalt lithium manganate ion battery by adopting a traditional process, namely directly recycling the prepared nickel cobalt lithium manganate material without adding hydrogen iodide in a recycling process; specifically, the traditional regeneration process for recycling the positive electrode material in the waste nickel cobalt lithium manganate ion battery comprises the following steps:
s1, discharging a waste nickel cobalt lithium manganate ion battery, disassembling the battery, and separating and crushing to obtain a positive electrode material;
s2, removing lithium salt from the positive electrode material, screening and sorting to obtain a positive electrode powder material;
and S3, adding a corresponding nickel-cobalt-manganese hydroxide precursor and a reducing agent ascorbic acid according to the element molar ratio in the anode powder material, heating for 6 hours at 400 ℃ in a vacuum atmosphere, and then heating for 12 hours at 750 ℃ to obtain the recovered anode material lithium iron phosphate.
Assembling the recovered positive electrode material into a lithium ion battery according to the same method as in the above example 1; the results of testing the charge and discharge curves of the lithium ion battery are shown in fig. 9.
In fig. 8 to 9, a is a charge curve and b is a discharge curve.
As can be seen from comparison of FIGS. 8 to 9, the nickel cobalt lithium manganate positive electrode material obtained by recycling according to the method has higher charge and discharge capacity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (9)
1. A method for regenerating a lithium ion battery positive electrode material is characterized by comprising the following steps:
disassembling the waste lithium ion battery, separating and crushing to obtain a positive electrode powder material;
adding the positive electrode powder material into carbonate-containing alkali liquor, heating, and filtering to obtain mixed powder;
adding a hydrogen iodide solution into the mixed powder, and stirring for reaction to obtain a composite slurry;
adding a precursor corresponding to the anode material according to the molar ratio of the elements in the composite slurry, and simultaneously adding
Heating the raw material at 300 to 500 ℃ for 2 to 12h, and then heating at 700 to 800 ℃ for 6 to 24h to obtain a positive electrode material;
the positive electrode powder material comprises a positive electrode active substance, a binder, a conductive agent and lithium salt in electrolyte.
2. The method for regenerating the positive electrode material of the lithium ion battery as claimed in claim 1, wherein the positive electrode powder material is added into an alkali solution, heated for 2 to 12h at 30 to 95 ℃, and filtered to obtain a mixed powder.
3. The method for regenerating a positive electrode material for a lithium ion battery according to claim 1, wherein the alkali solution comprises at least one of a lithium hydroxide alkali solution, a sodium hydroxide solution, a potassium hydroxide solution, and ammonium hydroxide.
4. The method for regenerating the positive electrode material of a lithium ion battery according to claim 1, wherein a hydrogen iodide solution having a concentration of 0.01 to 5mol/L is added to the mixed powder, and the mixture is stirred and reacted at 70 to 90 ℃ for 4 to 12h.
5. The method for regenerating the positive electrode material of the lithium ion battery as claimed in claim 1, wherein the reducing agent comprises one or more of ascorbic acid, sodium borohydride, sodium citrate, hydroxylamine hydrochloride, glucose, sucrose, hydrazine hydrate, formaldehyde or tannic acid.
6. The method for regenerating a positive electrode material for a lithium ion battery according to claim 1, wherein the positive electrode material for a lithium ion battery includes any one of lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt manganese oxide, lithium manganese oxide, and lithium cobalt oxide.
7. The method for regenerating a positive electrode material of a lithium ion battery according to claim 6, wherein if the positive electrode material of the lithium ion battery is lithium iron phosphate, the precursor corresponding to the positive electrode material is iron phosphate;
if the anode material of the lithium ion battery is lithium manganese iron phosphate, the precursor corresponding to the anode material is ferric manganese phosphate;
if the positive electrode material of the lithium ion battery is nickel cobalt lithium manganate, a precursor corresponding to the positive electrode material is nickel cobalt manganese hydroxide;
if the positive electrode material of the lithium ion battery is lithium manganate, the precursor corresponding to the positive electrode material is manganese hydroxide;
and if the anode material of the lithium ion battery is lithium cobaltate, the precursor corresponding to the anode material is cobalt hydroxide.
8. A positive electrode material prepared by the method of any one of claims 1~7.
9. A lithium ion battery comprising the positive electrode material according to claim 8.
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