CN109755524B - Modified LiNi0.6Co0.2Mn0.2O2Preparation method of ternary cathode material, product and battery - Google Patents
Modified LiNi0.6Co0.2Mn0.2O2Preparation method of ternary cathode material, product and battery Download PDFInfo
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Abstract
The invention discloses a modified LiNi0.6Co0.2Mn0.2O2A preparation method of a ternary cathode material, a product and a battery. The preparation method of the ternary cathode material comprises the following steps: the method comprises the steps of firstly introducing magnesium element when preparing a nickel-cobalt-manganese hydroxide precursor, then using an ammonium metatungstate aqueous solution as a complexing agent at the later stage of a coprecipitation reaction, hydrolyzing ammonium metatungstate in water, and then allowing ammonia ions and tungstate ions to appear, wherein the ammonia ions are used as the complexing agent for compensating the coprecipitation reaction, and the tungstate ions are partially deposited on the surface of the nickel-cobalt-manganese hydroxide precursor formed in a precipitation reaction stage, so that the in-situ introduction of tungsten element is realized, and then carrying out lithiation treatment to obtain ternary cathode powder with the surface containing tungsten element. According to the invention, by adding magnesium element and in-situ doping tungsten element on the surface, the charge and discharge performance, the cycle performance and the like of the modified ternary cathode powder are effectively improved.
Description
Technical Field
The invention relates to a nickel-cobalt-manganese ternary positive electrode material with high nickel content, in particular to modified LiNi0.6Co0.2Mn0.2O2A preparation method of a ternary cathode material, a product and a battery.
Background
The lithium ion battery adopts materials capable of reversibly inserting and extracting lithium ions as a positive electrode material and a negative electrode material of the battery, and is combined with a proper electrolyte or a solid electrolyte powder film to form a lithium ion secondary battery system. Since the energy of a battery depends on the product of its voltage and capacity, a means for increasing the energy density of the battery is to use positive and negative electrode materials of high voltage and high capacity. For the same negative electrode material, the higher the capacity and potential of the positive electrode material, the higher the energy density of the battery. The energy density of the lithium ion battery is improved, and the development of the ternary cathode powder with higher specific capacity and high nickel content is the main direction of battery research and development.
Compared with spinel-structured lithium manganate with low theoretical specific capacity and olivine-structured lithium iron phosphate (the theoretical specific capacity is 170mAh/g) with 280mAh/g, the layered-structured ternary composite positive electrode material (LiNi) has low theoretical specific capacityxCoyMnzO2) The ternary composite positive electrode material has obvious advantages, and the actual capacity of the ternary positive electrode with the layered structure in the lithium ion battery is increased along with the increase of the Ni content, so that the ternary composite positive electrode material with the nickel proportion of more than 60% in the three elements of the nickel, the cobalt and the manganese is the preferred positive electrode of the high-energy-density lithium ion battery at present.
The ternary positive electrode powder with high nickel content is generally synthesized by coprecipitation-high temperature solid phase reaction, namely, a nickel-cobalt-manganese hydroxide precursor is prepared by a coprecipitation method, and then a lithium source such as lithium hydroxide or lithium carbonate is added for mixed sintering to prepare the nickel-cobalt-manganese acid lithium positive electrode powder. As is well known, the morphology, the granularity and the like of precursor powder in the coprecipitation-high temperature solid phase reaction process influence various performances of the anode powder in the lithium ion battery, and the surface doping and coating of the nickel-cobalt-manganese ternary anode powder with high nickel content become an effective method for improving the performances of the anode powder. The existing research shows that the coating layer can relieve the corrosion of the electrolyte on the surface of the nickel-cobalt-manganese ternary positive electrode powder with high nickel content, the doping elements can also inhibit the crystal structure change of the surface part of the ternary positive electrode powder, and the cycle stability and the thermal stability of the ternary material are improved.
There are many researches on the improvement of the electrochemical stability of nickel cobalt lithium manganate ternary positive electrode powder coated by metal oxide, for example, patent of invention with publication number CN104393277A discloses a preparation method of lithium ion battery ternary positive electrode material with surface coated by metal oxide, which comprises: adding soluble metal salt into solution with macromolecular polyacrylamide as dispersant for uniform dispersion, adding ternary anode material powder into the solution, stirring and mixing; thirdly, adding an aqueous solution of alkali metal hydroxide into the mixed solution, adjusting the pH value of the solution to 9-12, precipitating, filtering and drying to obtain a positive electrode material with the surface coated with the hydroxide; fourthly, the anode material with the surface coated with the hydroxide is subjected to heat treatment at the temperature of 400-700 ℃ to obtain the ternary anode material with the surface coated with the metal oxide. Also, for example, patent publication No. CN108777296A discloses a method for forming a surface modified layer of a high-nickel ternary cathode material, in which two surface modified substances are coated on an inner core of the high-nickel ternary cathode material, one of the surface modified substances is yttria-stabilized zirconia, and the other surface modified substance is selected from metal oxides, metal fluorides, metal phosphates or C, and the surface modified substance is coated on the surface of the bulk material, so that side reactions between the high-nickel ternary cathode material and the electrolyte are reduced, and irreversible capacity loss of the ternary cathode material is suppressed. And then, as disclosed in the patent publication No. CN105576233A, a surface modification method of a nickel-based ternary cathode material is disclosed, in which one or more of a titanate coupling agent, an aluminate coupling agent and a silane coupling agent are reacted and compounded in an organic solvent on the surface of a nickel-based ternary cathode material obtained by mixing and calcining nickel-cobalt-manganese hydroxide precursor powder and a lithium salt, and the nickel-based ternary cathode material coated and modified by titanium, aluminum or silicon oxide is obtained by calcining and heat-treating. Although similar metal oxide coating modification treatments can improve the cycle performance and thermal stability of the positive electrode powder to some extent, they also have negative effects because the coated metal oxide is an inert material, inhibiting the transport of lithium ions and electrons.
On the other hand, carbon coating is also used for improving the conductivity of the ternary cathode material powderThe method disclosed in the patent publication No. CN103474628A discloses a method for improving ternary cathode material powder by carbon coating, which comprises the following steps: preparing a precursor of a ternary positive electrode material by taking nickel salt, cobalt salt and manganese salt as raw materials; dispersing conductive carbon in water containing organic carbon source to prepare conductive carbon dispersion liquid; thirdly, adding the precursor of the ternary positive electrode material and a lithium compound into the conductive carbon dispersion liquid to obtain a uniform mixture; fourthly, drying the mixture under the vacuum condition; fifthly, the dried mixture is processed at high temperature under the closed condition or the atmosphere protected by inert gas to obtain the carbon-coated ternary cathode material. The invention indicates that the multiplying power performance of the ternary cathode material can be improved by coating the conductive carbon powder and the ternary cathode material in the conductive medium amorphous carbon with a network shape. The invention patent with publication number CN104733721A discloses a method for preparing a nickel cobalt lithium manganate ternary positive electrode material by liquid-phase sugar coating spray drying, and specifically relates to a method for preparing a ternary composite precursor (Ni) by mixing sulfate solutions of Ni, Co and Mn and then carrying out coprecipitation under an alkaline conditionxCoyMnz)(OH)2Filtering, washing, drying, adding into solvent with sugar dissolved, mixing, spray drying to obtain sugar-coated and rare earth element-doped ternary precursor, and calcining at high temperature to obtain carbon-containing layer and rare earth element-doped ternary material LiNixCoyMnzRnO2And (3) powder.
In addition, the invention patent with publication number CN107895793A discloses a preparation method of a lithium battery anode material with a surface coated with tungsten-doped boride, which specifically comprises dissolving a tungsten source in water, spraying the tungsten source into a ternary precursor and lithium source mixed raw material in a spraying manner, stirring to obtain a dry material, and then roasting to obtain a tungsten-doped ternary anode material; and adding the metal boride into the tungsten-doped ternary cathode material, uniformly stirring, and sintering at a certain temperature to obtain the tungsten-doped boride-coated lithium battery cathode material.
Although the surface coating or doping treatment methods of the ternary cathode powder are described above, the methods are all the coatings superposed on the surface of the ternary cathode powderThe coating is not based on doping tungsten elements to replace nickel, cobalt and manganese atoms in a crystal structure of the surface part of the ternary cathode powder, namely, the valence change of the nickel, cobalt and manganese elements in a layered crystal structure in the charging and discharging process is not reduced by utilizing the high valence of the tungsten elements, and meanwhile, the vacancy concentration is not increased due to the fact that the high valence tungsten elements are doped in the layered crystal structure, so that the lithium ions are favorably diffused to achieve the purpose of improving the performance of the ternary cathode powder through doping. On the other hand, as is well known to those skilled in the art, the surface of the ternary cathode powder with high nickel content is alkaline, and if the ternary cathode powder is directly applied to the subsequent size mixing process, the problem that the size becomes gel (jelly colloid) when the size is prepared under the conventional conditions (dew point-30 ℃) is caused; if the alkalinity on the surface of the ternary cathode powder is removed, although a water washing operation can be adopted, lithium ions on the surface are lost, and the discharge capacity of the ternary cathode material is reduced. Therefore, there is a need for LiNi which has a high charge and discharge capacity and does not cause the problem of gelation of the slurry when it is subjected to pulping under conventional conditions (dew point-30 ℃ C.)0.6Co0.2Mn0.2O2A ternary cathode material and a preparation method thereof.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a modified LiNi0.6Co0.2Mn0.2O2Preparation method of ternary cathode material, product and battery, and LiNi prepared by method0.6Co0.2Mn0.2O2The ternary cathode material not only has higher charge-discharge capacity, but also has no problem that slurry becomes gel when the ternary cathode material is pulped under the conventional condition (dew point-30 ℃).
In order to solve the technical problems, the modified LiNi of the invention0.6Co0.2Mn0.2O2The preparation method of the ternary cathode material comprises the following steps:
1) preparing a nickel-cobalt-manganese hydroxide precursor:
1.1) dissolving nickel salt, cobalt salt and manganese salt in water to obtain a first mixed solution, controlling the concentration of total metal ions in the first mixed solution to be 2mol/L, and controlling the molar ratio of the nickel ions to the cobalt ions to the manganese ions to be 6: 2;
1.2) adding magnesium sulfate into the mixed solution, and dissolving to obtain a second mixed solution; wherein the addition amount of the magnesium sulfate is 0.05-0.25 percent of the total molar amount of the nickel ions, the cobalt ions and the manganese ions;
1.3) adding a precipitator and a complexing agent into the second mixed solution to carry out coprecipitation reaction, wherein:
the coprecipitation reaction process comprises two stages, namely a first reaction stage and a second reaction stage, wherein the reaction time of the second reaction stage accounts for 12-20% of the total reaction time of the coprecipitation reaction;
the complexing agent comprises a first complexing agent and a second complexing agent, wherein the first complexing agent is ammonia water, and the second complexing agent is an ammonium metatungstate aqueous solution;
adding a first complexing agent in a first reaction stage of the coprecipitation reaction, wherein the first complexing agent is uniformly added in the whole process of the first reaction stage; when the first complexing agent is 25% (NH)3The mass fraction of the first mixed solution is 25%, the same applies below), the adding amount is calculated by adding 10-50mL of first complexing agent into each liter of the first mixed solution;
a second complexing agent is added in the second reaction stage, and the second complexing agent is uniformly added in the whole process of the second reaction stage; when the concentration of the second complexing agent is 0.2-0.5mol/L, the adding amount is calculated by adding 40-60mL of the second complexing agent into each liter of the first mixed solution;
in the whole coprecipitation reaction process, the amount of a precipitator is 10-13 of the pH value of a control system, after the reaction is finished, the obtained reaction material is filtered, and precipitates are collected and dried to obtain a nickel-cobalt-manganese hydroxide precursor containing tungsten on the surface;
2) uniformly mixing the precursor of nickel-cobalt-manganese hydroxide with tungsten on the surface with a lithium source, and carrying out heat treatment in an oxidizing atmosphere to obtain LiNi with tungsten on the surface0.6Co0.2Mn0.2O2A powder;
3) obtaining a polyamic acid solution;
4) the surface of the LiNi containing tungsten0.6Co0.2Mn0.2O2Putting the powder into a polyamic acid solution, stirring and mixing for a certain time, taking out, and drying to obtain the polyamic acid coated LiNi0.6Co0.2Mn0.2O2Powder;
5) the resulting polyamic acid-coated LiNi0.6Co0.2Mn0.2O2The powder is put under vacuum condition for low-temperature heat treatment, and then is subjected to medium-temperature heat treatment in oxidizing atmosphere, thus obtaining the modified LiNi0.6Co0.2Mn0.2O2A ternary positive electrode material.
In step 1.1) of the above preparation method, the selection of the nickel salt, cobalt salt and manganese salt is the same as that in the prior art, specifically, the nickel salt may be one or a combination of two or more of nickel sulfate, nickel nitrate and nickel chloride, the cobalt salt may be one or a combination of two or more of cobalt sulfate, cobalt nitrate and cobalt chloride, and the manganese salt may be one or a combination of two or more of manganese sulfate, manganese nitrate and manganese chloride.
In step 1.2) of the above preparation method, the amount of magnesium sulfate added is preferably 0.1 to 0.2% of the total molar amount of nickel ions, cobalt ions and manganese ions.
In step 1.3) of the preparation method, the amount of the precipitant is controlled to control the pH of the system to be 10.5-11.5 during the whole coprecipitation reaction process; the selection of the precipitant is the same as that of the prior art, and specifically can be sodium hydroxide solution or potassium hydroxide solution with the concentration of 1-5mol/L, and the like. In this step, the total time of the coprecipitation reaction can be designed as required, and the applicant has found in experiments that it is suitable when the total time of the coprecipitation reaction is designed to be 6 hours, under which condition, it is further preferable that the reaction time of the second reaction stage is 15-18% of the total reaction time of the coprecipitation reaction (i.e. 0.9-1.08 hours, and the remaining 4.92-5.1 hours are the reaction time of the first reaction stage).
In step 2) of the above preparation method, the lithium source is conventionally selected in the prior art, and specifically may be lithium hydroxide and/or lithium carbonate, and the amount of the lithium source is LiNi to be prepared0.6Co0.2Mn0.2O2Required theoretical amount of ingredientIn the actual operation process, 1.01-1.1 times of theoretical amount is usually weighed. The nickel-cobalt-manganese hydroxide precursor containing tungsten on the surface and the lithium source are uniformly mixed by adopting the conventional mechanical mixing mode, such as a drum-type high-speed stirrer or a ball mill. The heat treatment after uniform mixing is to complete the lithiation reaction, the process is the same as the prior conventional technology, and the lithiation reaction is generally completed by keeping the temperature at 720-800 ℃ for 6-8 h.
In step 3) of the above preparation method, the polyamic acid solution can be obtained by a conventional method, for example, by placing a diamine (e.g., 4' -diaminodiphenyl ether (ODA), etc.) and a dianhydride (e.g., pyromellitic dianhydride (PMDA), etc.) in a polar aprotic solvent (e.g., N-methyl-2-pyrrolidone (NMP), etc.) to perform a polycondensation reaction. In the present application, it is preferable to use a polyamic acid solution having a solid content of 0.001 to 0.005% by mass (the same applies hereinafter). For polyamic acid solutions having solids contents outside this range, polar aprotic solvents may be used to dilute to the desired solids content.
In step 4) of the above preparation method, LiNi containing tungsten on the surface is subjected to low-moisture conditions (e.g., dew point-30 ℃ C.)0.6Co0.2Mn0.2O2The powder is placed in the polyamic acid solution and stirred and mixed for a certain time to ensure that the two are fully contacted, and the polyamic acid solution has a certain viscosity, so that the weakly acidic polyamic acid solution and the tungsten-containing LiNi with the alkaline surface are stirred and mixed on one hand0.6Co0.2Mn0.2O2The powders react with each other, and on the other hand, the tungsten-containing LiNi with alkaline surface of the polyamic acid solution is also realized0.6Co0.2Mn0.2O2And (4) coating the powder. The surface of the LiNi containing tungsten0.6Co0.2Mn0.2O2The material-liquid ratio of the powder and the polyamic acid solution can be designed according to requirements, and when the polyamic acid solution is a polyamic acid solution with the solid content of 0.001-0.005%, the LiNi with tungsten on the surface is adopted0.6Co0.2Mn0.2O2The feed-to-liquid ratio of the powder to the polyamic acid solution may be 1: 1 to 10, more preferably 1: 1 to 3. The mixing time is preferably 0.1h or more, usually 0.5 to 3 h. In the step of the method,the drying is typically carried out at 120-200 ℃.
In step 5) of the preparation method, the low-temperature heat treatment is to cure the polyamic acid, and the specific operation is to keep the temperature for 1-4h at the temperature of 300-400 ℃. The medium temperature heat treatment is heat preservation for 2-6h under the conditions of 600-680 ℃.
The invention also comprises the modified LiNi prepared by the method0.6Co0.2Mn0.2O2A ternary positive electrode material.
The invention also provides a lithium ion battery which comprises a positive plate, wherein the positive material used on the positive plate is the modified LiNi prepared by the method0.6Co0.2Mn0.2O2A ternary positive electrode material.
Compared with the prior art, the invention is characterized in that:
1. in the later stage of the coprecipitation reaction (i.e. the second reaction stage), ammonium metatungstate aqueous solution is used as a complexing agent, ammonium metatungstate is hydrolyzed in water and then appears as ammonia ions and tungstate ions, wherein the ammonia ions are used as the complexing agent for compensating the coprecipitation reaction, and the tungstate ions are partially deposited on the surface of the nickel-cobalt-manganese hydroxide precursor formed in the earlier stage to realize the in-situ introduction of tungsten element, and then the tungsten element is subjected to lithiation treatment to obtain LiNi containing the tungsten element on the surface0.6Co0.2Mn0.2O2Ternary positive electrode powder. According to the invention, by adding magnesium and in-situ doping tungsten on the surface, the vacancy beneficial to lithium ion diffusion can be increased while the nickel-cobalt-manganese layered crystal structure is stabilized, so that the obtained modified LiNi0.6Co0.2Mn0.2O2The charge and discharge performance, the cycle performance and the like of the ternary cathode powder are effectively improved.
2. Method for preparing LiNi containing tungsten on surface by adopting polyamic acid solution0.6Co0.2Mn0.2O2The ternary cathode powder is coated, and the alkaline compound on the surface of the ternary cathode material with high nickel content is removed through surface reaction, so that the problem that slurry becomes gel when the ternary cathode material with high nickel content is pulped under the conventional condition is solved.
3. IntoOne-step polyamic acid coated LiNi0.6Co0.2Mn0.2O2Curing the ternary positive electrode powder at low temperature, and then carbonizing at medium temperature to obtain the LiNi coated with a surface carbon (amorphous carbon) layer0.6Co0.2Mn0.2O2A ternary positive electrode material.
4. The surface-modified LiNi prepared by the method of the invention0.6Co0.2Mn0.2O2The ternary cathode material keeps the original layered crystal structure of the ternary cathode material and does not generate impurity phases. The electrochemical performance of the anode material is tested by using the button cell, the problem of anode capacity reduction caused by the increase of the diffusion resistance of lithium ions after the coating treatment similar to metal oxide does not occur, the charge and discharge capacity is high and stable, the first discharge specific capacity is more than 190mAh/g under the condition of 0.2C, and the cycle performance is good; the problem that the slurry becomes gel and loses efficacy does not occur in the subsequent size mixing process.
Drawings
FIG. 1 is a view showing a modified LiNi obtained in example 1 of the present invention0.6Co0.2Mn0.2O2XRD pattern of ternary anode material;
FIG. 2 is a view showing a modified LiNi obtained in example 1 of the present invention0.6Co0.2Mn0.2O2SEM image of ternary positive electrode material;
FIG. 3 is a view showing a modified LiNi obtained in example 1 of the present invention0.6Co0.2Mn0.2O2A charge-discharge curve diagram of the ternary cathode material under the condition of 0.2C;
FIG. 4 is a view showing a modified LiNi obtained in example 1 of the present invention0.6Co0.2Mn0.2O2A charge-discharge curve diagram of the ternary cathode material under the condition of 1C;
FIG. 5 is a view showing LiNi obtained in comparative example 1 of the present invention0.6Co0.2Mn0.2O2XRD spectrum of ternary anode material;
FIG. 6 is a LiNi obtained in comparative example 1 of the present invention0.6Co0.2Mn0.2O2SEM image of ternary positive electrode material;
FIG. 7 is a LiNi film obtained by using comparative example 10.6Co0.2Mn0.2O2Picture of gel formed by ternary cathode material during the size mixing process.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
Example 1
1) Preparing a nickel-cobalt-manganese hydroxide precursor:
1.1) dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to obtain a first mixed solution, controlling the concentration of total metal ions in the first mixed solution to be 2mol/L, and controlling the molar ratio of nickel ions to cobalt ions to manganese ions to be 6: 2;
1.2) adding magnesium sulfate into the mixed solution, and dissolving to obtain a second mixed solution; wherein the addition amount of the magnesium sulfate is 0.1 percent of the total molar amount of the nickel ions, the cobalt ions and the manganese ions;
1.3) adding a precipitator and a complexing agent into the second mixed solution for coprecipitation reaction, wherein:
designing the total reaction time of the coprecipitation to be 6h, wherein the coprecipitation reaction process comprises two stages, namely a first reaction stage and a second reaction stage, wherein the reaction time of the first reaction stage is 5h, and the reaction time of the second reaction stage is 1h (accounting for 16.7 percent of the total reaction time of the coprecipitation reaction);
the precipitant is a sodium hydroxide solution with the concentration of 2mol/L, the dosage of the precipitant is to control the pH value of the system to be 11.0-11.5 in the whole coprecipitation reaction process, and the precipitant is dripped to penetrate through the whole coprecipitation reaction process; the complexing agent comprises a first complexing agent and a second complexing agent, wherein the first complexing agent is ammonia water with the concentration of 25%, and the second complexing agent is ammonium metatungstate water solution with the concentration of 0.3 mol/L;
adding a first complexing agent in a first reaction stage of the coprecipitation reaction, wherein the adding amount of the first complexing agent is calculated by adding 20mL of the first complexing agent into each liter of first mixed solution; the first complexing agent is uniformly dropwise added within 5 hours;
adding a second complexing agent in a second reaction stage of the coprecipitation reaction, wherein the adding amount of the second complexing agent is calculated by adding 50mL of the second complexing agent into each liter of the first mixed solution, and the second complexing agent is uniformly dropwise added within 1 h;
after the coprecipitation reaction is finished, filtering the obtained reaction material, collecting the precipitate, washing with water, and drying at the temperature of 80 ℃ to obtain a nickel-cobalt-manganese hydroxide precursor with tungsten on the surface;
2) putting a nickel-cobalt-manganese hydroxide precursor containing tungsten on the surface and lithium hydroxide into a drum-type high-speed stirrer to be uniformly mixed, wherein the dosage of the lithium hydroxide is in accordance with LiNi0.6Co0.2Mn0.2O2Is 1.03 times of the theoretical lithium content, and the obtained mixture is placed in an oxidizing atmosphere and is kept at 760 ℃ for 6 hours to obtain LiNi with tungsten on the surface0.6Co0.2Mn0.2O2Powder;
3) obtaining a polyamic acid solution with solid content of 0.002%;
4) weighing LiNi containing tungsten on the surface according to the mass ratio of 1: 10.6Co0.2Mn0.2O2Powder and a polyamic acid solution having a solid content of 0.002%, followed by subjecting the surface of tungsten-containing LiNi0.6Co0.2Mn0.2O2Putting the powder into a polyamic acid solution with the solid content of 0.002%, stirring and mixing for 3 hours, taking out, and drying at 150 ℃ to obtain the polyamic acid coated LiNi0.6Co0.2Mn0.2O2Powder;
5) the resulting polyamic acid-coated LiNi0.6Co0.2Mn0.2O2Placing the powder under vacuum condition, heating to 350 deg.C (heating rate of 5 deg.C/min), keeping for 1h, introducing into oxidizing atmosphere, heating to 650 deg.C (heating rate of 5 deg.C/min), and keeping for 5h to obtain modified LiNi0.6Co0.2Mn0.2O2Ternary positive electrode material (LiNi subjected to surface doping, cladding and carbonization treatment)0.6Co0.2Mn0.2O2Ternary positive electrode material).
The modified LiNi obtained in this example was subjected to0.6Co0.2Mn0.2O2Ternary positive electrode materialX-ray diffraction analysis and electron microscope scanning, and the obtained XRD spectrum and SEM image are shown in figure 1 and figure 2 respectively.
The modified LiNi prepared in this example was subjected to conventional lithium ion battery slurry preparation (dew point-30 ℃ C.), and then subjected to0.6Co0.2Mn0.2O2The ternary cathode material, the superconducting carbon black (SP) and the PVDF binder are mixed according to the weight ratio of 94: 3, NMP is used as a solvent to be beaten into slurry according to the conventional process, and the condition that the slurry is changed into gel (jelly colloid) does not occur.
And coating the prepared slurry on an aluminum foil, and drying to obtain the positive plate. The electrochemical performance of the positive plate is tested by adopting a 2032 type button half cell, the negative electrode of the 2032 type button half cell is a metal lithium plate, and the electrolyte adopts LiPF6EC/DMC (1: 1 by volume) solution at a concentration of 1.0M, and commercial polyolefin was used for the separator. The first discharge capacity of the positive electrode under the condition of 0.2C is 193.7mAh/g, the capacity after 50 cycles is 184.6mAh/g, the capacity retention rate is 95.3%, and the charge-discharge curve is shown in figure 3; the capacity after 50 cycles under the condition of 1C is 176.8mAh/g, the capacity retention rate is 98.2 percent, and the charge-discharge curve is shown in figure 4. Thus, the LiNi prepared by the invention0.6Co0.2Mn0.2O2The ternary anode material has the characteristics of high discharge capacity and high electrochemical stability.
Comparative example 1
1) Preparing a nickel-cobalt-manganese hydroxide precursor:
1.1) dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to obtain a mixed solution, wherein the concentration of total metal ions in the mixed solution is controlled to be 2mol/L, and the molar ratio of nickel ions to cobalt ions to manganese ions is 6: 2;
1.2) adding a precipitator and a complexing agent into the mixed solution for coprecipitation reaction, wherein:
designing the total time of coprecipitation reaction to be 6 h;
the precipitant is a sodium hydroxide solution with the concentration of 2mol/L, the dosage of the precipitant is to control the pH value of the system to be 11.0-11.5 in the whole coprecipitation reaction process, and the precipitant is dripped to penetrate through the whole coprecipitation reaction process; the complexing agent is ammonia water with the concentration of 25%;
the complexing agent is uniformly added in a dropwise manner within 6 hours;
after the coprecipitation reaction is finished, filtering the obtained reaction material, collecting the precipitate, washing with water, and drying at the temperature of 80 ℃ to obtain a nickel-cobalt-manganese hydroxide precursor;
2) putting the precursor of nickel-cobalt-manganese hydroxide and lithium hydroxide into a drum-type high-speed stirrer to be uniformly mixed, wherein the dosage of the lithium hydroxide is in accordance with LiNi0.6Co0.2Mn0.2O21.03 times of the theoretical lithium content, placing the obtained mixture in an oxidizing atmosphere, and keeping the temperature for 6 hours at the temperature of 760 ℃ to obtain LiNi0.6Co0.2Mn0.2O2A ternary positive electrode material.
LiNi prepared for this comparative example0.6Co0.2Mn0.2O2The ternary cathode material is subjected to X-ray diffraction analysis and electron microscope scanning, and the obtained XRD spectrum and SEM image are respectively shown in FIG. 5 and FIG. 6.
LiNi prepared by the comparative example was subjected to the same lithium ion battery paste preparation environment as in example 10.6Co0.2Mn0.2O2The ternary positive electrode material, SP and PVDF binder were mixed at a weight ratio of 94: 3, and slurry was prepared by the same process as in example 1 using NMP as a solvent, and the slurry failed due to gel (jelly-like colloid) formation during the slurry mixing process, as shown in fig. 7.
LiNi prepared by the comparative example0.6Co0.2Mn0.2O2The ternary cathode material is washed and dried, and then is pulped according to the same pulping conditions in the embodiment 1, so that cathode slurry can be prepared. And then testing according to the same pole piece preparation conditions and battery assembly conditions of the example 1, wherein the first discharge capacity of the positive pole under the condition of 0.2C is only 142.8 mAh/g.
Comparative example 1 and comparative example 1, modified LiNi prepared by the method of the present invention0.6Co0.2Mn0.2O2The crystal structure of the ternary cathode material is not changed, and no impurity phase is generated; the discharge specific capacity is high, and the high nickel content ternary anode powder is eliminated while the stable electrochemical performance is maintainedThe problem that the battery slurry is easy to generate jelly colloid and lose efficacy in the conventional battery slurry preparation process.
Example 2
1) Preparing a nickel-cobalt-manganese hydroxide precursor:
1.1) dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to obtain a first mixed solution, controlling the concentration of total metal ions in the first mixed solution to be 2mol/L, and controlling the molar ratio of nickel ions to cobalt ions to manganese ions to be 6: 2;
1.2) adding magnesium sulfate into the mixed solution, and dissolving to obtain a second mixed solution; wherein the addition amount of the magnesium sulfate is 0.2 percent of the total molar amount of the nickel ions, the cobalt ions and the manganese ions;
1.3) adding a precipitator and a complexing agent into the second mixed solution to carry out coprecipitation reaction, wherein:
designing the total reaction time of coprecipitation to be 6h, wherein the coprecipitation reaction process comprises two stages, namely a first reaction stage and a second reaction stage, wherein the reaction time of the first reaction stage is 4.8h, and the reaction time of the second reaction stage is 1.2h (accounting for 20 percent of the total reaction time of the coprecipitation reaction);
the precipitant is sodium hydroxide solution with the concentration of 1mol/L, the dosage of the precipitant is to control the pH value of the system to be 10-11 in the whole coprecipitation reaction process, and the precipitant is dripped to penetrate through the whole coprecipitation reaction process; the complexing agent comprises a first complexing agent and a second complexing agent, wherein the first complexing agent is ammonia water with the concentration of 25%, and the second complexing agent is ammonium metatungstate water solution with the concentration of 0.2 mol/L;
adding a first complexing agent in a first reaction stage of the coprecipitation reaction, wherein the adding amount of the first complexing agent is calculated by adding 10mL of the first complexing agent into each liter of first mixed solution; the first complexing agent is uniformly added in a dropwise manner within 4.8 h;
adding a second complexing agent in a second reaction stage of the coprecipitation reaction, wherein the adding amount of the second complexing agent is calculated by adding 60mL of the second complexing agent into each liter of the first mixed solution, and the second complexing agent is uniformly dropwise added within 1.2 h;
after the coprecipitation reaction is finished, filtering the obtained reaction material, collecting the precipitate, washing with water, and drying at 60 ℃ to obtain a nickel-cobalt-manganese hydroxide precursor with tungsten on the surface;
2) putting a nickel-cobalt-manganese hydroxide precursor containing tungsten on the surface and lithium hydroxide into a drum-type high-speed stirrer to be uniformly mixed, wherein the dosage of the lithium hydroxide is in accordance with LiNi0.6Co0.2Mn0.2O2Is 1.01 times of the theoretical lithium content, and the obtained mixture is put in an oxidizing atmosphere and is kept at 720 ℃ for 7 hours to obtain the LiNi containing tungsten on the surface0.6Co0.2Mn0.2O2Powder;
3) obtaining a polyamic acid solution with solid content of 0.005%;
4) weighing LiNi containing tungsten on the surface according to the mass ratio of 1: 10.6Co0.2Mn0.2O2Powder and a polyamic acid solution having a solid content of 0.005%, followed by converting the surface of the tungsten-containing LiNi0.6Co0.2Mn0.2O2Putting the powder into a polyamic acid solution with the solid content of 0.005%, stirring and mixing for 2h, taking out, and drying at 120 ℃ to obtain the polyamic acid coated LiNi0.6Co0.2Mn0.2O2Powder;
5) the resulting polyamic acid-coated LiNi0.6Co0.2Mn0.2O2Placing the powder under vacuum condition, heating to 400 deg.C (heating rate of 5 deg.C/min), keeping for 3h, introducing into oxidizing atmosphere, heating to 680 deg.C (heating rate of 5 deg.C/min), and keeping for 1h to obtain modified LiNi0.6Co0.2Mn0.2O2A ternary positive electrode material.
The modified LiNi prepared in this example was subjected to conventional lithium ion battery slurry preparation (dew point-30 ℃ C.), and then subjected to0.6Co0.2Mn0.2O2The ternary cathode material, the superconducting carbon black (SP) and the PVDF binder are mixed according to the weight ratio of 94: 3, NMP is used as a solvent to be beaten into slurry according to the conventional process, and the condition that the slurry is changed into gel (jelly colloid) does not occur.
Example 3
1) Preparing a nickel-cobalt-manganese hydroxide precursor:
1.1) dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to obtain a first mixed solution, controlling the concentration of total metal ions in the first mixed solution to be 2mol/L, and controlling the molar ratio of nickel ions to cobalt ions to manganese ions to be 6: 2;
1.2) adding magnesium sulfate into the mixed solution, and dissolving to obtain a second mixed solution; wherein the addition amount of the magnesium sulfate is 0.08 percent of the total molar amount of the nickel ions, the cobalt ions and the manganese ions;
1.3) adding a precipitator and a complexing agent into the second mixed solution to carry out coprecipitation reaction, wherein:
designing the total reaction time of coprecipitation to be 6h, wherein the coprecipitation reaction process comprises two stages, namely a first reaction stage and a second reaction stage, wherein the reaction time of the first reaction stage is 5.28h, and the reaction time of the second reaction stage is 0.72h (accounting for 12 percent of the total reaction time of the coprecipitation reaction);
the precipitant is a sodium hydroxide solution with the concentration of 5mol/L, the dosage of the precipitant is to control the pH value of the system to be 12-13 in the whole coprecipitation reaction process, and the precipitant is dripped to penetrate through the whole coprecipitation reaction process; the complexing agent comprises a first complexing agent and a second complexing agent, wherein the first complexing agent is ammonia water with the concentration of 25%, and the second complexing agent is ammonium metatungstate water solution with the concentration of 0.5 mol/L;
adding a first complexing agent in a first reaction stage of the coprecipitation reaction, wherein the adding amount of the first complexing agent is calculated by adding 25mL of the first complexing agent into each liter of first mixed solution; the first complexing agent is uniformly added in a dropwise manner within 5.28 h;
adding a second complexing agent in a second reaction stage of the coprecipitation reaction, wherein the adding amount of the second complexing agent is calculated by adding 40mL of the second complexing agent into each liter of the first mixed solution, and the second complexing agent is uniformly dropwise added within 0.72 h;
after the coprecipitation reaction is finished, filtering the obtained reaction material, collecting the precipitate, washing with water, and drying at the temperature of 80 ℃ to obtain a nickel-cobalt-manganese hydroxide precursor with tungsten on the surface;
2) putting a nickel-cobalt-manganese hydroxide precursor containing tungsten on the surface and lithium hydroxide into a drum-type high-speed stirrer to be uniformly mixed, wherein the dosage of the lithium hydroxide is in accordance with LiNi0.6Co0.2Mn0.2O2Is 1.05 times of the theoretical lithium content, and the obtained mixture is put in an oxidizing atmosphere and is kept at 780 ℃ for 6 hours to obtain the LiNi containing tungsten on the surface0.6Co0.2Mn0.2O2Powder;
3) obtaining a polyamic acid solution with solid content of 0.001%;
4) weighing LiNi containing tungsten on the surface according to the mass ratio of 1: 10.6Co0.2Mn0.2O2Powder and a polyamic acid solution having a solid content of 0.001%, followed by subjecting the surface of the tungsten-containing LiNi0.6Co0.2Mn0.2O2Putting the powder into a polyamic acid solution with the solid content of 0.001%, stirring and mixing for 1h, taking out, and drying at the temperature of 200 ℃ to obtain the polyamic acid coated LiNi0.6Co0.2Mn0.2O2Powder;
5) the resulting polyamic acid-coated LiNi0.6Co0.2Mn0.2O2Placing the powder under vacuum condition, heating to 300 deg.C (heating rate of 5 deg.C/min), keeping for 2h, introducing into oxidizing atmosphere, heating to 600 deg.C (heating rate of 5 deg.C/min), and keeping for 3h to obtain modified LiNi0.6Co0.2Mn0.2O2A ternary positive electrode material.
The modified LiNi prepared in this example was subjected to conventional lithium ion battery slurry preparation (dew point-30 ℃ C.), and then subjected to0.6Co0.2Mn0.2O2The ternary cathode material, the superconducting carbon black (SP) and the PVDF binder are mixed according to the weight ratio of 94: 3, NMP is used as a solvent to be beaten into slurry according to the conventional process, and the condition that the slurry is changed into gel (jelly colloid) does not occur.
Claims (4)
1. Modified LiNi0.6Co0.2Mn0.2O2The preparation method of the ternary cathode material comprises the following steps:
1) preparing a nickel-cobalt-manganese hydroxide precursor:
1.1) dissolving nickel salt, cobalt salt and manganese salt in water to obtain a first mixed solution, controlling the concentration of total metal ions in the first mixed solution to be 2mol/L, and controlling the molar ratio of the nickel ions to the cobalt ions to the manganese ions to be 6: 2;
1.2) adding magnesium sulfate into the mixed solution, and dissolving to obtain a second mixed solution; wherein the addition amount of the magnesium sulfate is 0.05-0.25 percent of the total molar amount of the nickel ions, the cobalt ions and the manganese ions;
1.3) adding a precipitator and a complexing agent into the second mixed solution for coprecipitation reaction, wherein the precipitator is a sodium hydroxide solution or a potassium hydroxide solution with the concentration of 1-5mol/L, and the method comprises the following steps: the coprecipitation reaction process comprises two stages, namely a first reaction stage and a second reaction stage, wherein the reaction time of the second reaction stage accounts for 12-20% of the total reaction time of the coprecipitation reaction; the complexing agent comprises a first complexing agent and a second complexing agent, wherein the first complexing agent is ammonia water, and the second complexing agent is an ammonium metatungstate aqueous solution; adding a first complexing agent in a first reaction stage of the coprecipitation reaction, wherein the first complexing agent is uniformly added in the whole process of the first reaction stage; when the first complexing agent is ammonia water with the concentration of 25%, the adding amount of the first complexing agent is calculated by adding 10-50mL of the first complexing agent into each liter of the first mixed solution; a second complexing agent is added in the second reaction stage, and the second complexing agent is uniformly added in the whole process of the second reaction stage; when the concentration of the second complexing agent is 0.2-0.5mol/L, the adding amount is calculated by adding 40-60mL of the second complexing agent into each liter of the first mixed solution; in the whole coprecipitation reaction process, the amount of a precipitator is 10-13 of the pH value of a control system, after the reaction is finished, the obtained reaction material is filtered, and precipitates are collected and dried to obtain a nickel-cobalt-manganese hydroxide precursor containing tungsten on the surface;
2) uniformly mixing the precursor of nickel-cobalt-manganese hydroxide with tungsten on the surface with a lithium source, and carrying out heat treatment in an oxidizing atmosphere to obtain LiNi with tungsten on the surface0.6Co0.2Mn0.2O2Powder;
3) obtaining a polyamic acid solution, wherein the polyamic acid solution has a solid content of 0.001-0.005%;
4) the surface of the LiNi containing tungsten0.6Co0.2Mn0.2O2Putting the powder into a polyamic acid solution, stirring and mixing for a certain time, taking out, and drying to obtain the polyamic acid coated LiNi0.6Co0.2Mn0.2O2Powder;
5) the resulting polyamic acid-coated LiNi0.6Co0.2Mn0.2O2The powder is put under vacuum condition for low temperature heat treatment, the low temperature heat treatment is heat preservation for 1-4h under the conditions of 300-0.6Co0.2Mn0.2O2A ternary positive electrode material.
2. The method of claim 1, wherein: in the step 1.3), the precipitant is used in the whole coprecipitation reaction process, and the pH of the system is controlled to be 10.5-11.5.
3. Modified LiNi prepared by the method of claim 1 or 20.6Co0.2Mn0.2O2A ternary positive electrode material.
4. A lithium ion battery comprises a positive plate and is characterized in that: the positive electrode material used for the positive electrode sheet is the modified LiNi according to claim 30.6Co0.2Mn0.2O2A ternary positive electrode material.
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