CN108565452B - Method for treating lithium ion battery anode material by using acidic high polymer - Google Patents
Method for treating lithium ion battery anode material by using acidic high polymer Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a method for treating a lithium ion battery anode material by utilizing an acidic high polymer, which comprises the following steps: preparing an acidic high polymer with hydrophobicity; uniformly mixing an acidic high polymer with hydrophobicity and an organic solvent to obtain an organic solution; stirring and reacting the organic solution and the anode material at normal temperature to obtain a mixture; and further heating and evaporating the obtained mixture to form the cathode material with reduced alkalinity and hydrophobicity, so that the cycle performance of the material is further improved. The preparation method of the cathode material comprises the step of treating the cathode material by using a solvent with certain acidity and hydrophobicity, wherein the solvent can react with the cathode material mildly and keep the crystal structure of the cathode material complete, and the treated cathode material has a smooth surface, is low in alkalinity and has surface hydrophobicity.
Description
Technical Field
The invention relates to a method for treating a lithium ion battery anode material, in particular to a method for treating a lithium ion battery anode material by using an acidic high polymer.
Background
In the 80's of the 20 th century, lithium cobaltate (LiCoO) was first discovered by American scholars J.B2) Can be used as a positive electrode material for releasing and inserting lithium ionsSince then, lithium cobaltate was successfully applied to a positive electrode material of a lithium ion battery for commercialized small electronic products by the japan sony corporation in the early 90 s of the 20 th century by virtue of excellent electrochemical properties and good electrode processability. Nowadays, lithium ion batteries have been widely used in various small portable electronic products and electric tools, and are increasingly used in the new energy automobile market in large quantities. The positive electrode material in the lithium battery industry is the key for manufacturing the lithium ion battery, and the specific capacity of the positive electrode material is obviously lower than that of a common negative electrode material, so that the performance of the negative electrode material cannot be fully exerted, and the performance of the positive electrode material directly influences various indexes of the final battery.
At present, lithium cobaltate materials are not suitable for being used as anode materials of lithium ion batteries, particularly power lithium ion batteries due to the defects of high cost, poor thermal stability and the like. In addition, for the lithium ion battery material, because excessive lithium needs to be added in the preparation process to obtain the cathode material with good crystallinity, the Li/M ratio is slightly increased (namely, the lithium salt is properly excessive) in the compounding process to compensate the loss caused in the sintering process, so that a small amount of Li remains (Li remains at high temperature)2In the form of O), Li after the temperature has dropped to room temperature2O can adsorb CO in the air2And H2O to form LiOH and Li2CO3And the like, the positive electrode material has a problem of excessive lithium residues on the surface.
In addition, active oxygen anions on the surface of the cathode material can react with CO in the air if exposed to the air during storage2Reacts with moisture to generate carbonate radical, and lithium ions migrate from the bulk to the surface to form Li on the surface of the material2CO3. The pH value of the surface of the lithium ion battery is too high, so that the lithium ion battery is easy to absorb moisture in the preparation process of the positive electrode slurry, the slurry is in a jelly state, the slurry cannot be coated, the consistency of the battery is poor, the failure rate of the battery is increased, the subsequent pole piece absorbs moisture in the air, the lithium residues can deteriorate the electrochemical environment of the battery, the decomposition of electrolyte is promoted, the performance of the battery is reduced, and the problem of poor electrode processing performance is caused. The method greatly influences the industrialization process of the anode material, in particular to the ternary system anode material。
For the above problems, the existing solution is to use a water washing method and perform a secondary sintering process at a lower temperature to reduce the content of residual alkaline lithium on the surface of the lithium ion battery cathode material. The method can thoroughly clean the alkaline lithium residue on the surface, but the capacity performance of the treated positive electrode material is obviously reduced. And inorganic acid is used for treatment, so that the structure of the anode material is easily changed due to the acidity of the inorganic acid, and the integrity of the crystal structure of the anode material of the lithium ion battery is influenced.
Therefore, it is an urgent need of the art to provide a simple method for reducing the alkalinity of the lithium ion battery cathode material, making it hydrophobic, and not affecting the electrochemical performance of the cathode material.
Disclosure of Invention
In view of the above, the present invention provides a method for treating a lithium ion battery positive electrode material by using an acidic high polymer, in order to solve the problems of difficult electrode processing due to a large amount of lithium residues on the surface of the positive electrode material and excessive alkalinity, and reduced electrochemical performance due to contact between the positive electrode material and moisture in the air.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for treating a lithium ion battery cathode material by using an acidic high polymer comprises the following steps:
the method comprises the following steps: concentrated inorganic acid and water are mixed according to the volume ratio of 1: diluting at a ratio of 1.5-100 to obtain a base solution; mixing a low-surface-energy dopant and a polymer monomer according to a mass ratio of 1: adding the mixture into the base solution in a ratio of 20-1000; adding an oxidant every 1-3 minutes in the stirring process at the temperature of 5-8 ℃, and washing with distilled water to obtain a hydrophobic acidic high polymer;
step two: mixing an acidic high polymer and an organic solvent according to a mass ratio of 1: dissolving the materials in a proportion of 50-1000, and stirring to prepare an organic solution;
step three: and D, mixing the positive electrode material and the organic solution obtained in the step two according to the mass ratio of 1: mixing at a ratio of 0.1-50, and stirring to obtain a solid-liquid mixture;
step four: heating and evaporating the solid-liquid mixture at 100-200 ℃, and evaporating and drying the obtained solid powder at 50-200 ℃ in vacuum to obtain the lithium ion battery cathode material with reduced alkalinity and hydrophobicity;
the total dosage of the oxidant in the first step is 1.5-5 times of the mass of the polymer monomer, and the reaction time is 120-360 min;
the stirring treatment time in the second step is 30-60 min;
the stirring treatment time in the third step is 30-180 min;
the vacuum evaporation drying time in the fourth step is 0.5-12 hours, and the mass content of the high polymer in the lithium ion battery anode material is 0.1-6%.
By adopting the technical scheme, the invention has the following beneficial effects:
preferably, the inorganic acid in the first step is one or a mixture of two of hydrochloric acid and phosphoric acid.
Preferably, the low surface energy dopant in step one is one or more of acetic acid, dodecanoic acid, perfluorooctanoic acid (PFOA), perfluorosebacic acid (PFSEA), perfluorooctanesulfonic acid (PFOS), threonine, proline, arginine, valine, lithium trifluoromethanesulfonate, Sodium Dodecylbenzenesulfonate (SDBS), dinonylnaphthalenesulfonic acid, dioctyl sulfosuccinate.
By adopting the preferable scheme, the invention has the following beneficial effects:
the use of one or a mixture of both of an inorganic acid hydrochloric acid and phosphoric acid enables the polymer to be acidic and an acidic polymer to be produced.
The use of low surface energy dopant can improve the surface properties of the prepared high polymer to make it hydrophobic.
Preferably, the polymer monomer in the first step is one or more of aniline, lactic acid, glycolic acid and ethylene glycol.
Preferably, the oxidant in the first step is (NH)4)2S2O8、K2Cr2O7、KIO3、FeCl3、H2O2、MnO2One or more mixtures thereof.
Preferably, the acidic polymer with hydrophobicity prepared in the first step is Polyaniline (PANI), polylactic acid (PLA), polyglycolic acid (PGA), polylactic-co-glycolic acid (PLGA), polyaniline-co-polyethylene glycol (PANI-PEG) and one or more mixtures of the above polymer monomers and other monomer copolymers.
By adopting the preferable scheme, the invention has the following beneficial effects:
by using these oxidizing agents, the polymer monomer used can be efficiently oxidized into a polymer having excellent stability and performance. And the prepared high polymer has hydrophobicity and acidity simultaneously due to the use of inorganic acid and low surface energy dopant.
Preferably, the organic solvent in the second step is one or a mixture of several of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), dichloromethane, trichloromethane, benzene, toluene, diethyl ether, isopropanol, hexafluoroisopropanol, acetone and N-hexane.
By adopting the preferable scheme, the invention has the following beneficial effects:
the prepared high polymer is diluted by using an organic solvent, so that the consumption of the high polymer can be reduced, and the cost is saved.
Preferably, the positive electrode material of the layered structure is LiNixCoyMnzM1-x-y-zO2Wherein x is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and M is one or more of Mg, Al, Fe, Zr, Sm, Pr, Nb, Ga, Zn, Y, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La and Bi.
Preferably, the stirring manner in the first step is one of mechanical stirring, magnetic stirring or ultrasonic stirring.
Preferably, the positive electrode material in step three includes, but is not limited to, one or a mixture of two or more of layered or spinel lithium cobaltate, lithium manganate, lithium nickel cobalt aluminate and layered lithium-rich manganese-based solid solution.
By adopting the preferable scheme, the invention has the following beneficial effects:
the acid high polymer with hydrophobicity prepared by doping modification has wide application range, can act on various anode materials, cleans residues on the surfaces of the anode materials, further obtains the anode materials with surface hydrophobicity, effectively avoids the contact with moisture in the air, and effectively improves the performance of the anode materials.
In summary, compared with the prior art, the invention discloses a method for treating a lithium ion battery anode material by using an acidic high polymer, which has the following main effects:
1. in the treatment process of the acid high polymer on the surface of the lithium ion battery cathode material, the acid high polymer firstly reacts with alkaline lithium residues on the surface, such as Li2O、Li2CO3Reacting with LiOH to dissolve the residual alkaline lithium on the surface, so that the surface of the lithium ion battery anode material is smoother and the alkalinity is reduced;
2. the anode material treated by the hydrophobic acidic high polymer has surface hydrophobicity, and can effectively avoid contact with moisture in the air;
3. the washing method disclosed by the invention is mild in reaction process, and compared with the traditional washing method with water and acid liquor, the crystal structure of the lithium ion battery anode material is not changed, the integrity of the crystal is kept, and no side effect is caused on the lithium ion battery;
4. the preparation process is simple, the material cost is low, and the method is suitable for industrial production.
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 description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows Li (Ni), a starting material used in example 1 of the present invention0.8Co0.1Mn0.1)O2Scanning electron microscope images of the lithium ion battery anode material;
FIG. 2 shows Li (Ni) as a starting material used in example 1 of the present invention0.8Co0.1Mn0.1)O2Scanning electron microscope images of the lithium ion battery anode material;
FIG. 3 is a hydrophobic polyaniline-washed Li (Ni) prepared in example 1 of the present invention0.8Co0.1Mn0.1)O2Scanning electron microscope images of the lithium ion battery anode material;
FIG. 4 is a hydrophobic polyaniline-washed Li (Ni) prepared in example 1 of the present invention0.8Co0.1Mn0.1)O2Scanning electron microscope images of the lithium ion battery anode material;
FIG. 5 is a hydrophobic polyaniline-washed Li (Ni) prepared in example 1 of the present invention0.8Co0.1Mn0.1)O2The X-ray diffraction fine correction map of the lithium ion battery anode material;
FIG. 6 is hydrophobic polyaniline-treated Li (Ni) prepared in example 10.8Co0.1Mn0.1)O2Comparing electrochemical cycle curves of the lithium ion battery anode material and the anode material subjected to common water washing with the original material;
FIG. 7 is a hydrophobic polyaniline-washed Li (Ni) prepared in example 10.8Co0.1Mn0.1)O2And the multiplying power curves of the lithium ion battery anode material and the further coated anode material and the original material are compared.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses a method for treating a lithium ion battery anode material by using an acidic high polymer, which mainly comprises the following steps:
step one, mixing concentrated inorganic acid according to the proportion of 1: diluting the mixture as a base solution at a volume ratio of 1.5-100, and mixing a low-surface-energy dopant and a polymer monomer in a ratio of 1: adding the mixture into a base solution according to a mass ratio of 20-1000, adding an oxidant at a temperature of 5-8 ℃ and stirring every 1-3 minutes, wherein the total amount of the oxidant is 1.5-5 times of the mass of a polymer monomer, reacting for 120-360 min, and washing for three times by using distilled water to obtain a hydrophobic acidic polymer;
step two, mixing the acidic high polymer and the organic solvent according to the ratio of 1: dissolving the materials in a mass ratio of 50-1000, and stirring for 30-60 min to prepare an organic solution;
step three, mixing the anode material and the organic solution in a ratio of 1: mixing the materials in a mass ratio of 0.1-50, and stirring for 30-180 min to obtain a solid-liquid mixture;
and step four, heating and evaporating the solid-liquid mixture at 100-200 ℃, and carrying out vacuum evaporation drying on the obtained solid powder at 50-200 ℃ for 0.5-12 h to obtain the lithium ion battery cathode material with reduced alkalinity and hydrophobicity, wherein the mass content of the high polymer in the obtained cathode material is 0.1-6%.
In order to further describe the technical scheme of the invention, the invention will be further discussed by specific embodiments:
example 1
The embodiment discloses a method for treating a lithium ion battery anode material by using an acidic high polymer, which comprises the following steps:
(1) concentrated hydrochloric acid was diluted at a volume ratio of 1:3 to prepare a base solution, and perfluorooctanoic acid (PFOA) and aniline were mixed at a ratio of 1: adding the mixture into the base solution according to the mass ratio of 50, and adding (NH) into the base solution at the temperature of 5-8 ℃ every 2 minutes under the condition of stirring4)2S2O8，(NH4)2S2O8The total dosage is 2.5 times of the mass of the aniline, the reaction time is 240min, and the acidic polyaniline with hydrophobicity is obtained by washing the polyaniline with distilled water for three times;
(2) dissolving the polyaniline with hydrophobicity obtained in the step (1) into N-methylpyrrolidone according to the mass ratio of 1:200, and carrying out ultrasonic stirring treatment for 60min to prepare an organic solution containing polyaniline;
(3) mixing a nickel-cobalt-manganese-lithium positive electrode material and a polyaniline detergent in a ratio of 1:20, and performing ultrasonic stirring treatment for 60min to obtain a solid-liquid mixture;
(4) and (3) evaporating and drying the solid-liquid mixture at the temperature of 120 ℃ for 8 hours in vacuum to obtain the lithium ion battery cathode material with reduced alkalinity.
Example 2
The embodiment discloses a method for treating a lithium ion battery anode material by using an acidic high polymer, which comprises the following steps:
(1) adding concentrated hydrochloric acid according to the weight ratio of 1: 5 volume ratio dilution as a base solution, Sodium Dodecylbenzenesulfonate (SDBS) and lactic acid were diluted in a ratio of 1: adding the mixture into the base solution according to the mass ratio of 50, and adding K into the base solution at the temperature of 5-8 ℃ every 2 minutes under the stirring condition2Cr2O7，K2Cr2O7The total amount of the polylactic acid is 2 times of the mass of the used lactic acid, the reaction time is 300min, and the polylactic acid with hydrophobicity is obtained by washing the polylactic acid with distilled water for three times;
(2) dissolving the polylactic acid obtained in the step (1) into N, N-Dimethylformamide (DMF) according to the mass ratio of 1:150, and carrying out ultrasonic stirring treatment for 50min to prepare a polylactic acid-containing organic solution;
(3) mixing a nickel-cobalt-manganese-lithium positive electrode material and a polylactic acid detergent in a ratio of 1:15, and carrying out ultrasonic stirring treatment for 45min to obtain a solid-liquid mixture;
(4) and (3) evaporating and drying the solid-liquid mixture at the temperature of 100 ℃ for 12h in vacuum to obtain the lithium ion battery cathode material with reduced alkalinity.
Example 3
The embodiment discloses a method for treating a lithium ion battery anode material by using an acidic high polymer, which comprises the following steps:
(1) adding concentrated phosphoric acid according to the proportion of 1: 8 as a base solution, valine, aniline and lactic acid were diluted in a volume ratio of 1: 25: adding 25 mass percent of the mixture into the base solution, and stirring at the temperature of 5-8 DEG CFeCl was added every 2.5 minutes3，FeCl3The total dosage is 2.5 times of the mass of the aniline and the lactic acid, the reaction time is 360min, and the mixture of the polyaniline and the polylactic acid with hydrophobicity is obtained by washing the mixture for three times with distilled water;
(2) dissolving the mixture of polyaniline and polylactic acid obtained in the step (1) into acetone according to the mass ratio of 1:1, and carrying out ultrasonic stirring treatment for 45min to prepare a mixture organic solution containing polyaniline and polylactic acid;
(3) mixing a nickel-cobalt-manganese-lithium positive electrode material and a mixture detergent solution of polyaniline and polylactic acid in a ratio of 1:15, and carrying out ultrasonic stirring treatment for 45min to obtain a solid-liquid mixture;
(4) and (3) evaporating and drying the solid-liquid mixture for 10 hours in vacuum at the temperature of 120 ℃ to obtain the lithium ion battery cathode material with reduced alkalinity.
Example 4
The embodiment discloses a method for treating a lithium ion battery anode material by using an acidic high polymer, which comprises the following steps:
(1) concentrated hydrochloric acid was diluted at a volume ratio of 1:20 to prepare a base solution, and perfluorooctanesulfonic acid (PFOS) and glycolic acid were mixed at a ratio of 1: adding 100 mass percent of the KIO into the base solution, and adding the KIO into the base solution every 1 minute under the condition of stirring at the temperature of 5-8 DEG C3，KIO3The total dosage is 2 times of the mass of the aniline, the reaction time is 300min, and the acid polyglycolic acid with hydrophobicity is obtained by washing the mixture for three times with distilled water;
(2) dissolving the hydrophobic polyglycolic acid obtained in the step (1) into N-methyl pyrrolidone according to the mass ratio of 1:100, and carrying out ultrasonic stirring treatment for 60min to prepare an organic solution containing polyglycolic acid;
(3) mixing a nickel-cobalt-manganese-lithium positive electrode material and a polyvinyl alcohol acid washing agent in a proportion of 1:15, and carrying out ultrasonic stirring treatment for 60min to obtain a solid-liquid mixture;
(4) and (3) evaporating and drying the solid-liquid mixture at the temperature of 100 ℃ for 10 hours in vacuum to obtain the lithium ion battery cathode material with reduced alkalinity.
Example 5
The embodiment discloses a method for treating a lithium ion battery anode material by using an acidic high polymer, which comprises the following steps:
(1) adding concentrated phosphoric acid according to the proportion of 1:10 volume ratio dilution as a base solution, dinonylnaphthalenesulfonic acid and ethylene glycol in a ratio of 1: adding the MnO into the base solution according to the mass ratio of 100, and adding MnO every 2 minutes at the temperature of 5-8 ℃ under the condition of stirring2，MnO2The total dosage is 2.5 times of the mass of the used lactic acid, the reaction time is 270min, and the polyethylene glycol with hydrophobicity is obtained by washing the mixture for three times with distilled water;
(2) dissolving the polyethylene glycol obtained in the step (1) into isopropanol according to the mass ratio of 1:150, and carrying out ultrasonic stirring treatment for 60min to prepare an organic solution containing polyethylene glycol;
(3) mixing a nickel-cobalt-manganese-lithium positive electrode material and a polyethylene glycol detergent in a ratio of 1:10, and performing ultrasonic stirring treatment for 45min to obtain a solid-liquid mixture;
(4) and (3) evaporating and drying the solid-liquid mixture at the temperature of 120 ℃ for 12h in vacuum to obtain the lithium ion battery cathode material with reduced alkalinity.
In order to determine the electrochemical performance of the nickel cobalt lithium manganate positive electrode material prepared by adopting the surface modification technology, the inventor carries out further test experiments:
mixing the synthesized surface-modified nickel cobalt lithium manganate positive electrode material, acetylene black and PVDF (polyvinylidene fluoride) according to the ratio of 8:1:1 at normal temperature and normal pressure to form slurry, and uniformly coating the slurry on an aluminum foil substrate.
Drying the obtained positive pole piece at 120 ℃, compacting under certain pressure, continuously drying at 120 ℃ for 10 hours, and then cutting the positive pole piece into pieces with the area of 1cm2The round sheet of (2) was used as a positive electrode, a lithium plate was used as a negative electrode, and LiPF was used at a concentration of 1mol/L6The EC + DMC (volume ratio 1: 1) solution of (A) was used as an electrolyte and assembled into an experimental cell in a glove box filled with argon.
The experimental cell was subjected to charge-discharge cycling tests using the novyi electrochemical test channel. The charge and discharge current was 200mA/g, the charge cut-off voltage was 4.30V, and the discharge cut-off voltage was 3.0V.
As can be seen from the charging and discharging curves shown in FIG. 6, the capacity of the nickel cobalt lithium manganate positive electrode material after washing is higher than that of the original material; and under the high-temperature condition, the cycle performance of the washed lithium ion battery anode material is obviously improved compared with that of an unmodified anode material.
As can be seen from the rate performance curve of fig. 7, the performance of the treated positive electrode material of the lithium ion battery is basically consistent with that of the unmodified material under low rate; however, under the condition of high multiplying power, the capacity is obviously improved.
The lithium ion battery anode material with surface hydrophobicity prepared by the surface modification technology is observed for the particle size and the shape on a Hitachi S-4000 electron scanning microscope.
As can be seen from the attached drawings 1-4, the nickel cobalt lithium manganate material prepared by the surface modification technology of the invention is not obviously different from the original material as a whole, and has complete spherical particles, the particle size is about 5-15 microns, the particle size is uniform, and the surface is smooth, which indicates that the surface modification technology of the invention can well maintain the original shape and structure of the anode material, and the washed material has cleaner surface under the condition of high resolution.
The crystal structure of the nickel cobalt lithium manganate positive electrode material prepared by the acid high polymer treatment of the invention is analyzed by a RigakuB/Max-2400X-ray diffractometer. From fig. 5, it can be seen that the surface modification material has a standard layered structure and no impurity phase exists, indicating that the surface modification technology of the present invention is a very mild technology and has no influence on the bulk structure of the material.
In order to further realize the technical scheme of the invention, the inorganic acid in the first step of the invention is one or a mixture of two of hydrochloric acid and phosphoric acid.
In order to further realize the technical scheme of the invention, the low surface energy dopant in the first step is one or a mixture of acetic acid, dodecanoic acid, perfluorooctanoic acid (PFOA), perfluorosebacic acid (PFSEA), perfluorooctanesulfonic acid (PFOS), threonine, proline, arginine, valine, lithium trifluoromethanesulfonate, Sodium Dodecylbenzenesulfonate (SDBS), dinonylnaphthalenesulfonic acid and dioctyl sulfosuccinate.
In order to further realize the technical scheme of the invention, the polymer monomer in the first step is one or a mixture of more of aniline, lactic acid, glycolic acid and ethylene glycol.
In order to further realize the technical scheme of the invention, the oxidant in the step one is (NH)4)2S2O8、K2Cr2O7、KIO3、FeCl3、H2O2、MnO2One or more mixtures thereof.
In order to further realize the technical scheme of the invention, the acidic polymer with hydrophobicity prepared in the first step is Polyaniline (PANI), polylactic acid (PLA), polyglycolic acid (PGA), polylactic-polyglycolic acid copolymer (PLGA), polyaniline-polyethylene glycol copolymer (PANI-PEG) and one or more mixtures of the above polymer monomers and other monomer copolymers.
In order to further realize the technical scheme of the invention, the positive electrode material of the layered structure is LiNixCoyMnzM1-x-y-zO2Wherein x is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and M is one or more of Mg, Al, Fe, Zr, Sm, Pr, Nb, Ga, Zn, Y, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La and Bi.
In order to further realize the technical scheme of the invention, the organic solvent in the second step is one or a mixture of several of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), dichloromethane, trichloromethane, benzene, toluene, diethyl ether, isopropanol, hexafluoroisopropanol, acetone and N-hexane.
In order to further realize the technical scheme of the invention, the stirring mode in the first step is one of mechanical stirring, magnetic stirring or ultrasonic stirring.
In order to further realize the technical scheme of the invention, the positive electrode material in the third step includes but is not limited to one or a mixture of two or more of layered or spinel type lithium cobaltate, lithium manganate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and layered lithium-rich manganese-based solid solution.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for processing a lithium ion battery anode material by using an acidic high polymer is characterized by comprising the following steps:
the method comprises the following steps: concentrated inorganic acid and water are mixed according to the volume ratio of 1: diluting at a ratio of 1.5-100 to obtain a base solution; mixing a low-surface-energy dopant and a polymer monomer according to a mass ratio of 1: adding the mixture into the base solution in a ratio of 20-1000; adding an oxidant every 1-3 minutes in the stirring process at the temperature of 5-8 ℃, and washing with distilled water to obtain a hydrophobic acidic high polymer;
step two: mixing an acidic high polymer and an organic solvent according to a mass ratio of 1: dissolving the materials in a proportion of 50-1000, and stirring to prepare an organic solution;
step three: and D, mixing the positive electrode material and the organic solution obtained in the step two according to the mass ratio of 1: mixing at a ratio of 0.1-50, and stirring to obtain a solid-liquid mixture;
step four: heating and evaporating the solid-liquid mixture at 100-200 ℃, and evaporating and drying the obtained solid powder at 50-200 ℃ in vacuum to obtain the lithium ion battery cathode material with reduced alkalinity and hydrophobicity;
the total dosage of the oxidant in the first step is 1.5-5 times of the mass of the polymer monomer, and the reaction time is 120-360 min;
the stirring treatment time in the second step is 30-60 min;
the stirring treatment time in the third step is 30-180 min;
the vacuum evaporation drying time in the fourth step is 0.5-12 hours, and the mass content of the high polymer in the lithium ion battery anode material is 0.1-6%;
the low surface energy dopant in the first step is one or a mixture of acetic acid, dodecanoic acid, perfluorooctanoic acid, perfluorosebacic acid, perfluorooctanesulfonic acid, threonine, proline, arginine, valine, lithium trifluoromethanesulfonate, sodium dodecylbenzenesulfonate, dinonylnaphthalenesulfonic acid and dioctyl sulfosuccinate;
the acidic polymer with hydrophobicity prepared in the first step is one or a mixture of polyaniline, polylactic acid, polyglycolic acid, polylactic-co-glycolic acid and polyaniline-co-polyethylene glycol.
2. The method of claim 1, wherein the inorganic acid in the first step is one or a mixture of hydrochloric acid and phosphoric acid.
3. The method of claim 1, wherein the polymer monomer in the first step is one or more of aniline, lactic acid, glycolic acid, and ethylene glycol.
4. The method of claim 1, wherein the oxidant in the first step is (NH)4)2S2O8、K2Cr2O7、KIO3、FeCl3、H2O2、MnO2One or more mixtures thereof.
5. The method for treating the lithium ion battery positive electrode material by using the acidic high polymer as claimed in claim 1, wherein the positive electrode material is LiNixCoyMnzM1-x-y-zO2Wherein x is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and M is one or more of Mg, Al, Fe, Zr, Sm, Pr, Nb, Ga, Zn, Y, Cr, Ca, Na, Ti, Cu, K, Sr, Mo, Ba, Ce, Sn, Sb, La and Bi.
6. The method of claim 1, wherein the organic solvent in the second step is one or a mixture of N-methylpyrrolidone, N-dimethylformamide, dichloromethane, chloroform, benzene, toluene, diethyl ether, isopropanol, hexafluoroisopropanol, acetone, and N-hexane.
7. The method of claim 1, wherein the stirring in the first step is one of mechanical stirring, magnetic stirring or ultrasonic stirring.
8. The method of claim 1, wherein the positive electrode material in step three comprises one or a mixture of two or more of layered lithium cobaltate, lithium manganate, lithium nickel cobalt aluminate, and layered lithium-rich manganese-based solid solution.
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