CN106410157B - High-magnification long-life cathode material and preparation method thereof - Google Patents
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Abstract
A high-multiplying-power long-life anode material and its preparing process are disclosed, which includes surface coatingA coating having the formula: lixNi1‑yMyO21.0 ≦ x ≦ 1.2, 0.1 ≦ Y ≦ 0.7, M ≦ one or more of Co, Mn, Al, Ca, Ti, Mg, B, Zr, Nb, Y, La, V, F; the surface coating layer is a metal oxide containing Al and Li. According to the invention, a porous hydroxide precursor is synthesized by a liquid-phase coprecipitation method, then the precursor, a lithium salt and an additive are uniformly mixed at the same time and then sintered at a high temperature, and the lithium metal oxide obtained by sintering is subjected to deposition coating and heat treatment in a liquid state to obtain the target cathode material. The primary crystal grains of the material are agglomerated and loose, the gap is large, the surface and the surface of the internal crystal grains are provided with the coating layers, the structure is favorable for the permeation of electrolyte, the diffusion speed of Li ions is improved, meanwhile, the large gap is favorable for relieving the shrinkage expansion stress of the crystal grains in the charging and discharging processes, the structural stability of the material is improved, and the cycle life of the battery is obviously prolonged.
Description
Technical Field
The invention relates to a porous cage type high-magnification long-life ternary cathode material and a preparation method thereof, in particular to a high-magnification long-life cathode material and a preparation method thereof.
Background
The lithium ion battery has the characteristics of high energy density, long service life, safety, environmental protection and the like, and is widely applied to the fields of intelligent communication equipment, tablet computers, electric tools, electric vehicles, energy storage systems and the like. The lithium ion battery anode material is the most critical part of the battery and directly determines the performance and cost of the battery. Currently, lithium cobaltate, lithium manganate, lithium iron phosphate and ternary materials are the mainstream positive electrode materials in the market. The cobalt in the lithium cobaltate is a scarce resource and is high in price, and the lithium cobaltate has potential safety hazards and cannot be used in a large battery; the gram capacity of lithium manganate is low, the structural stability at high temperature is poor, and the use requirements of high energy density and long cycle batteries cannot be met; lithium iron phosphate has low energy density, low conductivity, poor processability and poor low-temperature performance, and cannot be used in a high-energy-density battery. The nickel-based ternary material integrates the advantages of various metal elements, has obvious synergistic effect, and has the characteristics of high energy density, excellent cycle performance, stable safety performance, moderate price and the like. With the rise of new energy automobiles, the automobile battery simultaneously needs to consider energy density, power characteristics, cycle life and safety and stability, and ternary materials become the most promising positive materials.
The synthesis of ternary materials generally involves two stages: the synthesis of the ternary precursor and the synthesis of the lithium metal oxide both have decisive influence on the material performance. The ternary precursor is mainly synthesized by a liquid-phase coprecipitation method, multiple metal ions are uniformly mixed in a solution at a molecular level, and the multiple metal ions are simultaneously precipitated and the size and the morphology of particles are controlled by adding a precipitator and controlling kinetic parameters. The lithium metal oxide is synthesized by a high-temperature solid phase method, and the ternary precursor and the lithium salt are mixed and then sintered for a certain time at a high temperature to obtain the cathode material with a well-developed crystal structure. In general, the higher the nickel content in the ternary material, the greater the synthesis difficulty, and the poorer the structural stability and surface stability of the material.
The ternary material is mainly applied to 3C digital products at present, is not mature in application in the field of power batteries, and particularly cannot be applied in large batch due to poor interface stability of the ternary material with high nickel content. The invention aims to provide a ternary material synthesis method applicable to digital batteries and automobile power batteries, and overcomes the defects of the materials in the aspects of circulation stability, power performance, safety performance and the like.
The problems existing in the prior art are as follows: under the current technical conditions, the ternary material precursor is prepared by a coprecipitation process, and the precursor and the anode material are both prepared by tightly agglomerating primary particles into secondary particles. In the process of charging and discharging of the battery, lithium ions are repeatedly inserted and extracted in the body of the positive electrode material, along with the expansion and contraction of the particle volume, because the primary particles of the material are tightly agglomerated, the volume change generated by the expansion and contraction of the particles cannot be released in the secondary particles, and the secondary particles are cracked and pulverized, so that the deterioration of the cycle performance and the safety performance of the material is caused.
Disclosure of Invention
The invention aims to provide a high-rate long-life cathode material and a preparation method thereof, and solves the problems in the background art.
The invention is realized by adopting the following technical scheme:
the high-magnification long-life cathode material has a porous cage structure, obvious primary crystal grain gaps on the surface and inside of the material and a coating layer on the surface, and the structural formula of the material is as follows: lixNi1-yMyO21.0 ≦ x ≦ 1.2, 0.1 ≦ Y ≦ 0.7, M ≦ one or more of Co, Mn, Al, Ca, Ti, Mg, B, Zr, Nb, Y, La, F; the coating layer is a metal oxide containing Al and Li.
A high-magnification long-life cathode material and a preparation method thereof comprise the following steps:
s1: weighing soluble nickel, cobalt and manganese salts according to a molar ratio, preparing the soluble nickel, cobalt and manganese salts and deionized water into a solution, and adding a surfactant into the solution to form a solution A; preparing an alkali solution B, preparing a complexing agent solution C, pumping the three solutions into a reaction kettle under the protection of nitrogen or argon atmosphere through a metering pump, and aging, centrifuging, washing and drying the reacted precipitate to obtain a porous hydroxide precursor;
s2: uniformly mixing the prepared porous hydroxide precursor, lithium salt and an additive, and sintering at high temperature in the air or oxygen atmosphere to obtain a positive electrode material matrix;
s3: dissolving aluminum salt into deionized water or absolute ethyl alcohol, slowly dropwise adding a precipitator until the pH value reaches 5-10, stopping stirring for 10-60 min, adding an anode material substrate, stirring for 30-90 min, filtering and drying the precipitate, and sintering in the air or oxygen atmosphere to obtain the high-magnification long-life anode material.
In the invention, the soluble nickel, cobalt and manganese salt in S1 is at least one of sulfate, nitrate and acetate, the surfactant is one of polyethylene glycol 2000, polyethylene glycol 5000, polyethylene glycol 10000 and polyethylene glycol 20000, the addition amount of the surfactant is 1-6% of the mass sum of the soluble salts, and the concentration of the solution A is 1-5 mol/L; the alkali solution is a sodium hydroxide solution, and the concentration of the alkali solution is 3-10 mol/L; the complexing agent is at least one of ammonia water or ammonium sulfate, and the concentration of the complexing agent is 3-10 mol/L.
In the invention, the temperature in the reaction kettle in S1 is 45-65 ℃, the stirring speed is 500-1500 rpm, the pH value in the reaction kettle is controlled to be 10.5-14 by an online pH meter, and the molar ratio of the pumping quantity of the complexing agent solution C to the pumping quantity of the mixed solution A is controlled to be 0.05-0.2 by a metering pump: 1, the reaction time is 4-32 h.
In the invention, the lithium salt in S2 is one or more of lithium hydroxide, lithium carbonate, lithium nitrate and lithium acetate, and the molar ratio of lithium to metal is 1.0-1.2; the additive is one or more of Al, Ca, Ti, Mg, B, Zr, Nb, Y, La and F compounds, and the addition amount is 0.05-0.5 percent of the mass of the porous hydroxide precursor; the sintering temperature is 680-980 ℃, and the sintering time is 8-24 h; the atmosphere is air or oxygen atmosphere.
In the invention, the aluminum salt in S3 is at least one of aluminum nitrate, aluminum isopropoxide and aluminum phosphate, and the addition amount of Al accounts for 0.05-0.3% of the mass of the matrix of the cathode material; the precipitator is at least one of sodium hydroxide, ammonia water, ammonium hydrogen phosphate and ammonium dihydrogen phosphate; the sintering temperature is 400-700 ℃, and the sintering time is 6-15 h.
In the present invention, the soluble manganese salt may be replaced with a soluble aluminum salt.
The technical principle is as follows: the invention utilizes PEG with large molecular weight as a surfactant, controls the nucleation and growth of crystals by controlling the pH value in a reaction kettle and the molar ratio of a complexing agent to transition metal ions, and finally obtains a ternary precursor with a porous structure, thereby providing a good basis for the subsequent preparation of the ternary cathode material with fast mass transfer of lithium ions, good rate capability, stable circulation and excellent performance. The Al and Li metal oxide coating avoids inhibiting the corrosion of the electrolyte to the material, and further improves the electrochemical new energy of the material. Porous cage structure multielement cathode material primary crystalline grain is gathered loose, and the clearance is great, and solution infiltration gets into inside the granule during the cladding for granule surface and inside crystalline grain all form the surface coating, have promoted the interface stability of material. The porous structure of the target material is beneficial to the permeation of electrolyte, the diffusion speed of Li ions is increased, and the multiplying power performance of the material is improved; on the other hand, the larger gap is beneficial to relieving the shrinkage and expansion stress of the crystal grains in the charging and discharging processes, and the structural stability of the material is improved; in addition, the coating layers on the surfaces and inside the particles can improve the interface stability of the material, inhibit the side reaction of the material and electrolyte, and remarkably prolong the cycle life and safety performance of the battery.
Has the advantages that: aiming at the problems of pulverization and fragmentation of the material in the circulating process, a precursor with a porous structure is obtained by controlling parameters of a coprecipitation synthesis process of the precursor; and then, by controlling parameters of the sintering process and increasing surface coating, the surface-coated porous cage-type anode material is obtained. Appropriate gaps are formed among primary particles of the positive electrode material, so that volume change caused by lithium ion embedding and releasing in a circulation process can be buffered, the wettability of electrolyte can be improved, a diffusion channel of lithium ions is increased, and the multiplying power performance of the material is improved. Meanwhile, through infiltration deposition coating, coating liquid permeates into the surfaces and gaps of the particles, and slowly deposits on the surfaces and the inner primary particle surfaces to form uniform inert coating films, so that the interface stability of the material is improved. The target material has the characteristics of stable circulation, excellent safety performance, outstanding rate performance and the like, the synthesis process is simple and controllable, and the large-scale industrial production can be realized.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product of example 1;
FIG. 2 is a first charge and discharge curve of the product of example 1;
FIG. 3 is a graph showing the rate comparison of the product of example 2 and a comparative sample;
FIG. 4 is a cyclic comparison of the product of example 3 to a control.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further explained below by combining the specific drawings.
Example 1
A, B, C three solutions were prepared: preparing a 1.5mol/L transition metal ion mixed solution according to a molar ratio of Ni to Co to Mn of 6 to 2, and adding polyethylene glycol 10000 accounting for 2% of the total mass to form a mixed solution A; preparing a sodium hydroxide solution B with the molar concentration of 4 mol/L; preparing complexing agent solution ammonia water C with the molar concentration of 4 mol/L. Pumping the three solutions into a reaction kettle under the protection of nitrogen atmosphere by a metering pump, controlling the temperature of the solution in the kettle to be 50 ℃, and controlling the stirring speed to be 700 r/min. Controlling the pH value in the reaction kettle to be about 11.3 +/-0.05 by a metering pump for controlling an alkaline solution through an online pH meter, and controlling and keeping the molar ratio of the pumping amount of the complexing agent solution C to the mixed solution A to be 0.1 by the metering pump; stopping the reaction after the reaction lasts for 12 hours, and aging, centrifuging, washing and drying the reaction materials to obtain a precursor Ni with a porous structure0.6Co0.2Mn0.2(OH)2。
Respectively weighing the prepared precursor and lithium carbonate according to the molar ratio of lithium metal of 1.05, and weighing an additive TiO according to the mass fraction of 0.1%2All the three components are combinedAfter uniform mixing, sintering for 15h at 875 ℃ in air atmosphere to obtain the Ti-doped porous cage type anode material matrix.
Weighing a certain amount of the matrix, weighing aluminum nitrate according to the mass fraction of 0.2 percent of Al, dissolving the aluminum nitrate in water, slowly dropwise adding ammonia water until the pH value is 7.5, stirring for 30min, adding the matrix, continuously stirring for 60min, filtering and drying the precipitate, and sintering the dried material in an air atmosphere furnace at 700 ℃ for 8h to obtain the target product.
The active material obtained in this example, PVDF, and acetylene black were mixed in a mass ratio of 92:4:4, and NMP was added thereto and stirred together to prepare a slurry. Coating the slurry on an aluminum foil, drying at 120 ℃ and preparing into a positive plate. Taking a metal lithium sheet as a negative plate; the diaphragm is an imported polypropylene microporous film; the electrolyte is 1mol/L LiPF 6/ethylene carbonate + dimethyl carbonate, and is assembled into a CR2032 button type experimental battery in an argon glove box. And (3) carrying out an electrical property test at 25 ℃, wherein the charging and discharging interval is 3.0-4.3V, the charging and discharging are carried out at the current density of 0.2C, and the first discharging specific capacity of the battery is 180.9 mAh/g. Referring to fig. 1 and 2, the X-ray diffraction pattern of the product of example 1 and the first charge-discharge curve of the product of example 1 are shown.
Example 2
A, B, C three solutions were prepared: preparing a 2.0mol/L transition metal ion mixed solution according to the molar ratio of Ni to Co to Mn being 8 to 1, and adding 2% of polyethylene glycol 20000 in the total mass to form a mixed solution A; preparing a sodium hydroxide solution B with the molar concentration of 5 mol/L; preparing complexing agent solution ammonia water C with the molar concentration of 5 mol/L. Pumping the three solutions into a reaction kettle under the protection of nitrogen atmosphere by a metering pump, controlling the temperature of the solution in the kettle to be 50 ℃, and controlling the stirring speed to be 1200 r/min. Controlling the pH value in the reaction kettle to be about 11.8 +/-0.05 by a metering pump for controlling an alkaline solution through an online pH meter, and controlling and keeping the molar ratio of the pumping amount of the complexing agent solution C to the mixed solution A to be 0.1 by the metering pump; stopping the reaction after the reaction lasts for 8 hours, and aging, centrifuging, washing and drying the reaction materials to obtain a precursor Ni with a porous structure0.8Co0.1Mn0.1(OH)2。
Respectively weighing the prepared precursor and lithium hydroxide according to the molar ratio of lithium metal of 1.06, weighing an additive LiF according to the mass fraction of 0.1%, uniformly mixing the three, and sintering at 780 ℃ for 18h in an oxygen atmosphere to obtain the porous cage type cathode material matrix.
Weighing a certain amount of the matrix, weighing aluminum isopropoxide according to the mass fraction of 0.15% of Al, dispersing the aluminum isopropoxide in absolute alcohol, slowly adding a sodium hydroxide solution until the pH value is 8.0, stirring for 45min, adding the matrix, continuously stirring for 40min, filtering and drying the precipitate, and sintering the dried material in an oxygen atmosphere furnace at 700 ℃ for 8h to obtain the target product.
The button cell is assembled by the material obtained in the embodiment, the cell process is the same as that of the embodiment 1, and the discharge capacity retention rate of the cell 5C is 84.3%. Referring specifically to fig. 3, the magnification comparison curve of the product of example 2 versus the control.
Example 3
A, B, C three solutions were prepared: preparing a metal ion mixed solution with the molar ratio of Ni to Co to Al of 88 to 10 to 2 of 2.0mol/L, and adding polyethylene glycol 20000 accounting for 2.5 percent of the total mass to form a mixed solution A; preparing a sodium hydroxide solution B with the molar concentration of 5 mol/L; preparing complexing agent solution ammonia water C with the molar concentration of 5 mol/L. Pumping the three solutions into a reaction kettle under the protection of nitrogen atmosphere by a metering pump, controlling the temperature of the solution in the kettle to be 50 ℃, and controlling the stirring speed to be 1300 r/min. Controlling the pH value in the reaction kettle to be about 12.0 +/-0.05 by a metering pump for controlling an alkaline solution through an online pH meter, and controlling and keeping the molar ratio of the pumping amount of the complexing agent solution C to the mixed solution A to be 0.1 by the metering pump; stopping the reaction after the reaction lasts for 7 hours, and aging, centrifuging, washing and drying the reaction materials to obtain a precursor Ni with a porous structure0.88Co0.1Al0.02(OH)2。
Respectively weighing the prepared precursor and lithium hydroxide according to the molar ratio of lithium metal of 1.03, uniformly mixing, and sintering at 720 ℃ for 20 hours in an oxygen atmosphere to obtain the porous cage type cathode material matrix.
Weighing a certain amount of the matrix, weighing aluminum nitrate according to the mass fraction of 0.15 percent of Al, dispersing the aluminum nitrate in deionized water, slowly dropwise adding ammonia water until the pH value is 8.0, stirring for 60min, adding the matrix, continuously stirring for 30min, filtering and drying the precipitate, and sintering the dried material in an oxygen atmosphere furnace at 650 ℃ for 8h to obtain the target product.
The button cell is assembled by the material obtained in the embodiment, the cell process is the same as that of the embodiment 1, and the capacity retention rate of the cell 1C after 100 weeks of circulation is 99.7%. Referring specifically to fig. 4, the cycle contrast curves for the product of example 3 versus the control.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be understood by those skilled in the art that the invention is not limited by the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (6)
1. The high-magnification long-life cathode material is characterized by having a porous cage structure, wherein the surface and the internal primary crystal grain gaps of the material are obvious, and the surface is provided with a coating layer, and the structural formula of the material is as follows: lixNi1-yMyO21.0 ≦ x ≦ 1.2, 0.1 ≦ Y ≦ 0.7, M = one or more of Co, Mn, Al, Ca, Ti, Mg, B, Zr, Nb, Y, La, F; the coating layer is a metal oxide containing Al and Li;
the high-magnification long-life cathode material is prepared by the following method, and the method comprises the following steps:
s1: weighing soluble nickel, cobalt and manganese salts according to a molar ratio, preparing the soluble nickel, cobalt and manganese salts and deionized water into a solution, and adding a surfactant into the solution to form a solution A; preparing an alkali solution B, preparing a complexing agent solution C, pumping the three solutions into a reaction kettle under the protection of nitrogen or argon atmosphere through a metering pump for coprecipitation, and aging, centrifuging, washing and drying the precipitate after reaction to obtain a porous hydroxide precursor; the temperature in the reaction kettle is 45-65 ℃, the stirring speed is 500-1500 rpm, the pH value in the reaction kettle is controlled to be 10.5-14 through an online pH meter, the molar ratio of the pumping quantity of the complexing agent solution C to the pumping quantity of the mixed solution A is controlled to be 0.05-0.2 through a metering pump: 1, the reaction time is 4-32 h;
s2: uniformly mixing the prepared porous hydroxide precursor, lithium salt and an additive, and sintering at high temperature in the air or oxygen atmosphere to obtain a positive electrode material matrix;
s3: dissolving aluminum salt into deionized water or absolute ethyl alcohol, slowly dropwise adding a precipitator until the pH value reaches 5-10, stopping stirring for 10-60 min, adding a positive electrode material substrate, stirring for 30-90 min, filtering and drying the precipitate, and sintering in the air or oxygen atmosphere to obtain the lithium ion battery positive electrode material.
2. The preparation method of the high-magnification long-life cathode material is characterized by comprising the following steps of:
s1: weighing soluble nickel, cobalt and manganese salts according to a molar ratio, preparing the soluble nickel, cobalt and manganese salts and deionized water into a solution, and adding a surfactant into the solution to form a solution A; preparing an alkali solution B, preparing a complexing agent solution C, pumping the three solutions into a reaction kettle under the protection of nitrogen or argon atmosphere through a metering pump for coprecipitation, and aging, centrifuging, washing and drying the precipitate after reaction to obtain a porous hydroxide precursor; the temperature in the reaction kettle is 45-65 ℃, the stirring speed is 500-1500 rpm, the pH value in the reaction kettle is controlled to be 10.5-14 through an online pH meter, the molar ratio of the pumping quantity of the complexing agent solution C to the pumping quantity of the mixed solution A is controlled to be 0.05-0.2 through a metering pump: 1, the reaction time is 4-32 h;
s2: uniformly mixing the prepared porous hydroxide precursor, lithium salt and an additive, and sintering at high temperature in the air or oxygen atmosphere to obtain a positive electrode material matrix;
s3: dissolving aluminum salt into deionized water or absolute ethyl alcohol, slowly dropwise adding a precipitator until the pH value reaches 5-10, stopping stirring for 10-60 min, adding an anode material substrate, stirring for 30-90 min, filtering and drying the precipitate, and sintering in the air or oxygen atmosphere to obtain the high-magnification long-life anode material.
3. The method for preparing the cathode material with high magnification and long service life according to claim 2, wherein the soluble nickel, cobalt and manganese salt in S1 is at least one of sulfate, nitrate and acetate, the surfactant is one of polyethylene glycol 2000, polyethylene glycol 5000, polyethylene glycol 10000 and polyethylene glycol 20000, the addition amount of the surfactant is 1-6% of the mass sum of the soluble salts, and the concentration of the solution A is 1-5 mol/L; the alkali solution is a sodium hydroxide solution, and the concentration of the alkali solution is 3-10 mol/L; the complexing agent is at least one of ammonia water or ammonium sulfate, and the concentration of the complexing agent is 3-10 mol/L.
4. The method for preparing the high-rate long-life cathode material as claimed in claim 2, wherein the lithium salt in S2 is one or more of lithium hydroxide, lithium carbonate, lithium nitrate and lithium acetate, and the molar ratio of lithium to metal is = 1.0-1.2; the additive is one or more of Al, Ca, Ti, Mg, B, Zr, Nb, Y, La and F compounds, and the addition amount is 0.05-0.5 percent of the mass of the porous hydroxide precursor; the sintering temperature is 680-980 ℃, and the sintering time is 8-24 h; the atmosphere is air or oxygen atmosphere.
5. The method for preparing the cathode material with high multiplying power and long service life as claimed in claim 2, wherein the aluminum salt in S3 is at least one of aluminum nitrate, aluminum isopropoxide and aluminum phosphate, and the addition amount of Al is 0.05-0.3% of the mass of the cathode material matrix; the precipitator is at least one of sodium hydroxide, ammonia water, ammonium hydrogen phosphate and ammonium dihydrogen phosphate; the sintering temperature is 400-700 ℃, and the sintering time is 6-15 h.
6. The method for preparing a high-rate long-life cathode material as claimed in claim 2, wherein the soluble manganese salt in S1 can be replaced by a soluble aluminum salt.
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| CN108807926B (en) * | 2018-06-22 | 2021-04-06 | 格林美（无锡）能源材料有限公司 | Co/B Co-coated nickel-cobalt-manganese-lithium ion positive electrode material and preparation method thereof |
| CN109244365B (en) * | 2018-11-09 | 2021-12-07 | 万华化学集团股份有限公司 | Lithium ion battery positive electrode material, preparation method thereof, positive electrode and lithium ion battery |
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| CN113735191A (en) * | 2021-08-24 | 2021-12-03 | 南通金通储能动力新材料有限公司 | Porous structure ternary precursor and preparation method thereof |
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