CN114744160A - Preparation method of lithium ion battery positive plate - Google Patents
Preparation method of lithium ion battery positive plate Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
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Abstract
The invention discloses a preparation method of a lithium ion battery positive plate, which comprises the following specific steps: the method comprises the steps of uniformly mixing a high-nickel anode material and a magnetic material through mechanical stirring to obtain high-nickel anode slurry, coating the high-nickel anode slurry on the surface of a current collector, enabling the magnetic material to be directionally arranged in the high-nickel anode slurry through alternate loading and magnetic field removal, preparing a thick polar plate with a graded multidimensional through channel by utilizing an ice crystal effect, and recovering the magnetic material in the thick polar plate by adopting a magnetic recovery device to prepare the lithium ion battery anode plate, wherein the Ni content in the high-nickel anode material is more than or equal to 80wt%, and the magnetic material is iron-doped gadolinium gallium garnet magnetic nanoparticles. The thick electrode of the hierarchical multidimensional through channel constructed by the invention is applied to the lithium ion battery, and the rapid charge and discharge capacity of the lithium ion battery is realized on the premise of not sacrificing the utilization rate and the capacity of an active material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a lithium ion battery positive plate.
Background
Lithium ion batteries are the most widely used secondary batteries due to their advantages of high voltage, high energy density and long cycle life. However, with the continuous development of miniaturization and long standby of portable electronic devices and the use of high-power and high-energy devices such as electric bicycles and electric automobiles, people have made higher and higher demands on the energy density of lithium ion batteries.
There are various ways to increase the energy density of lithium ion batteries: from the structural design angle, the volume of a cell structural design space is increased so as to increase the total amount of active substances; from the electrochemical design angle, the proportion of inactive material components is reduced (the usage of positive and negative current collectors and diaphragms is reduced, the material cost is saved), and the proportion of active materials in the electrode is improved; and thirdly, from the design angle of a material system, the thickness of the current collector is reduced or the proportion of the active substance to the current collector (copper and aluminum foil) is increased, namely the coating amount of the electrode is increased. In contrast, increasing the thickness of the electrode sheet is the most direct method for increasing the energy density of the lithium ion battery.
The thick electrode design can greatly increase the loading capacity of active materials on the current collector, greatly increase the capacity of a monomer cell and reduce the ratio of inactive components, thereby improving the energy density of the lithium ion battery and reducing the cost. However, thick electrode designs suffer from the following problems: 1. along with the increase of the thickness of the electrode, the coating process is not easy to dry, the bonding strength of the electrode coating and a current collector is reduced, active substances are easy to fall off, meanwhile, the baking temperature of the pole piece is high, the adhesive and the conductive agent float upwards along with a solvent, the stripping force of the pole piece is easy to be poor, and the conductive agent and pores are unevenly distributed; 2. along with the increase of the thickness of the electrode, the difficulty of the electrolyte penetrating into the boundary between the dressing layer and the current collector is increased, and the battery is easy to fully electrolyze and precipitate lithium at a high multiplying power because the electrode is not fully soaked by the electrolyte, so that potential safety hazards are generated; 3. the increase of the thickness of the electrode can prolong the transmission path of electrons and lithium ions, reduce the conductivity of the ions and the electrons, and cause the deterioration of multiplying power performance and cycle performance; 4. electrodes made by conventional particulate slurry coating methods exhibit randomly distributed porosity and high tortuosity (tortuous path for liquid electrolyte to penetrate within the electrode).
Therefore, how to construct a novel thick electrode of the lithium ion battery and improve the rate capability and the cycle performance of the lithium ion battery are very important.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of a lithium ion battery positive plate, the thick electrode of the grading multidimensional through channel constructed by the method is applied to the lithium ion battery, and on the premise of not sacrificing the utilization rate and the capacity of an active material, the problems existing in the design of the thick electrode are effectively solved, and the rapid charging and discharging capacity of the battery is realized.
The invention adopts the following technical scheme for solving the technical problems: a preparation method of a lithium ion battery positive plate is characterized by comprising the following specific steps: the method comprises the steps of uniformly mixing a high-nickel positive electrode material and a magnetic material through mechanical stirring to obtain high-nickel positive electrode slurry, coating the high-nickel positive electrode slurry on the surface of a current collector aluminum foil, enabling the magnetic material to be directionally arranged in the high-nickel positive electrode slurry through alternate loading and magnetic field removal, constructing an ice crystal effect to prepare a thick polar plate with a graded multidimensional through channel, and then recovering the magnetic material in the thick polar plate by adopting a magnetic recovery device to prepare a lithium ion battery positive plate, wherein the Ni content in the high-nickel positive electrode material is more than or equal to 80wt%, and the magnetic material is iron-doped gadolinium gallium garnet magnetic nanoparticles. The electrode plate with the structure can reduce the tortuosity of the electrode and generate gradient porosity, and a molecular channel which is beneficial to lithium ion transportation is formed, so that the high-speed conduction of lithium ions is promoted.
Further limited, the preparation method of the lithium ion battery positive plate is characterized by comprising the following specific steps:
step S1: gd is added2O3And Ga2O3Uniformly mixing with a nitric acid solution, condensing and refluxing to obtain a gadolinium-gallium mixed nitrate solution, adding a ferric nitrate solution, regulating the pH of a mixed system to 2.5-3.0 by using concentrated ammonia water, then using an ammonium bicarbonate solution as a precipitator, controlling the pH of the mixed system to 7.5-8.0 after titration, standing and aging, drying and transferring a precipitate to a muffle furnace to calcine at 800-950 ℃ to obtain iron-doped gadolinium-gallium garnet magnetic nanoparticles, adding a surfactant, stirring by using an oil bath at 80 ℃, cooling to room temperature, separating a magnetic nanoparticle crude product from the solution by adopting magnetic field separation, washing with ethanol and deionized water alternately for several times, and drying to obtain superfine iron-doped gallium garnet magnetic nanoparticles;
step S2: according to the high nickel anode material: binder PVDF: respectively weighing raw materials according to the mass ratio of 90% to 5% of the conductive agent SP, dispersing a high-nickel anode material into an ethanol solution to obtain a suspension containing the high-nickel anode material, adding the ultrafine iron-doped gadolinium gallium garnet magnetic nanoparticles prepared in the step S1 into the suspension containing the high-nickel anode material, uniformly mixing, and uniformly mixing with the binder PVDF, the conductive agent SP, acetic acid and the solvent NMP to obtain high-nickel anode slurry;
step S3: adjusting the coating thickness to be 100-1000 mu m by a scraper, and coating the high-nickel anode slurry prepared in the step S2 in a mold with an aluminum foil placed at the bottom;
step S4: placing the die in the step S3 in a sealed drying chamber, alternately loading and removing the magnetic field, regulating and controlling the magnetic field intensity to be 6-8T, loading the magnetic field for 0.5-1.5 min, removing the magnetic field for 2-4 min, and circulating for 3-5 times, then transferring the electrode into a low-temperature low-pressure chamber to sublimate the ice crystals, wherein the original positions of the ice crystals form vertical channels, so that the thick electrode with the hierarchical multidimensional through channel, which is cooperatively constructed by the magnetic effect and the ice crystal effect, is generated;
step S5: and (4) adopting a magnetic recovery device, setting the magnetic field intensity to be 2-4T, and recovering and recycling the magnetic nanoparticles in the thick electrode prepared in the step S4 to finally prepare the lithium ion battery positive plate.
Further defined, the surfactant in step S1 is sodium stearate, potassium stearate, sodium oleate, potassium oleate, sodium laurate, or potassium laurate.
Further defined, the high-nickel cathode material in the step S2 is an NCM811 high-nickel ternary cathode material.
Further limiting, in the step S2, the mass ratio of the ultrafine iron-doped gadolinium gallium garnet magnetic nanoparticles to the high-nickel positive electrode material is 0.1-0.5%, the mass ratio of acetic acid to the high-nickel positive electrode material is 0.02-0.05%, and the viscosity of the high-nickel positive electrode slurry is 4000-9000 mPa · S.
Further, in the step S3, the coating thickness is adjusted to 250-350 μm by a doctor blade.
Further limiting, in the step S4, the low temperature and low pressure chamber has a low temperature of-5 to-10 ℃ and a low pressure of 1 to 2 Pa.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the prepared magnetic nano-particles are very small in size, a layer of stable surfactant is coated on the surfaces of the particles, the magnetic materials can be prevented from being oxidized, the agglomeration of the particles caused by van der waals force is overcome, the magnetostatic attraction is weakened, the surface properties of the magnetic nano-particles are changed, and the magnetic nano-particles can not agglomerate even under the action of a strong magnetic field. One end of the surfactant can be chemically adsorbed on the surface of the magnetic nano-particles to form a solvation film, the other end of the surfactant has higher affinity with NMP, so that the surfactant can freely extend and swing in the NMP, and meanwhile, the molecules of the surfactant have a certain chain length to overcome the van der Waals attraction among particles, so that the magnetic nano-particles have the magnetism of common magnetic materials and the liquidity of liquid.
2. The mass ratio of the magnetic nano particles in the high-nickel cathode material is lower than 0.5%, and the utilization rate of active substances is not influenced. In addition, the existence of simple substance iron in the high-nickel anode material can cause short circuit of the battery, the battery can be disabled under severe conditions, magnetic substances (such as iron) in the high-nickel anode material are mainly metal equipment abrasion impurities and metal impurities brought by raw materials, and the metal impurities which are not removed in the high-nickel anode material can be well adsorbed and removed through separation and recovery of magnetic nanoparticles. The particle size of the high-nickel anode material is micron-sized, the particle size of the prepared magnetic nanoparticles is nano-sized, and due to the large size difference, the magnetic nanoparticles can be conveniently removed in situ from a particle stacking system of the high-nickel anode material under the action of a magnetic field. Therefore, impurity metal and magnetic nanoparticles can be effectively removed through the magnetic recovery device, and potential safety hazards caused by the fact that magnetic impurities pierce the diaphragm in the charging and discharging process are effectively avoided.
3. When no magnetic field exists, the magnetic nanoparticles are stressed unevenly under various forces such as gravity, intermolecular force and the like, when the magnetic nanoparticles are stressed under the magnetic force, the magnetic liquid is subjected to orientation deflection to present anisotropy, a multidirectional distribution structure is changed very rapidly, a uniform multidirectional distribution branched channel is formed by regulating and controlling the magnetic field intensity in situ, and the transmission path of electrons and ions is shortened. When the magnetic field strength is too weak, the magnetic material cannot be effectively deflected and cannot form multiple channels. When the magnetic field intensity is too strong, the magnetic material is enriched at the magnetic pole to form a rich magnetic area and a poor magnetic area, and a three-dimensional through channel cannot be formed; the magnetic field intensity loaded by the invention is 6-8T, so that the magnetic nano material can be uniformly distributed in the slurry, and a hierarchical three-dimensional through channel is further formed.
4. As the content of nickel (Ni is more than or equal to 0.8) of the high-nickel cathode material is increased, the nickel-like oxides of the high-nickel cathode material are easy to react with water and carbon dioxide in the air to form residual alkali on the surface spontaneously. The residual alkali not only aggravates the failure problem caused by gas generation in the operation process of the battery, but also easily leads the slurry to be gelled in the coating process, which is the main challenge in the mass production of the high nickel layered oxide. The higher fatty acid alkali metal surfactant on the surface of the magnetic particles can be ionized in a solvent to generate trace fatty acid radicals and alkali metal Na+、K+. H with fatty acid radical ionized with trace acetic acid in slurry+The generated fatty acid can neutralize residual alkali in the slurry, avoid gelation of the slurry, and simultaneously etch the surface of the aluminum foil to form uniform and rich open pits to enhanceThe adhesive force of the dressing layer and the aluminum foil is improved; when a magnetic field is loaded, the magnetic particles are directionally arranged on the surface of the aluminum foil under the action of the magnetic field, so that the depth of directionally etching the aluminum foil is further increased, the roughness of the surface of the aluminum foil is improved, the adhesion force between the coating layer and the aluminum foil is further improved, and residual alkali in the slurry is further neutralized. In addition, Na+And K+Has an ionic radius greater than Li+Trace sodium and potassium will also take part in electrochemical reaction in charging and discharging process, Na+And K+Can broaden Li+Thereby realizing Li+The acceleration of the transmission.
5. The gadolinium gallium garnet magnetic nano material can generate a freezing effect below 20K, so that a solvent can be rapidly cooled to form a large amount of ice nuclei, and because the integral temperature in the slurry is extremely low instantaneously, a large amount of ice crystals at each position in the slurry are formed at the same time, so that the electrode material and the ice crystals are more uniformly distributed. The magnetic iron ions replace part of non-magnetic gallium ions, and due to the super-exchange effect between the iron ions and the gallium ions, the local magnetic moments are ordered, the Curie temperature can be effectively reduced, and the freezing effect is further improved. By using repeated loading magnetic field magnetism and removing magnetic field, the magnetic nano material can uniformly absorb and release heat from the interior of slurry, and can uniformly regulate and control the growth speed of ice crystal, so that the constructed electrode channel is more regular and uniform.
6. The constructed multi-stage multi-dimensional pore structure uniform from the current collector to the surface of the dressing layer provides a multi-dimensional open permeation channel, is beneficial to rapid infiltration of electrolyte from the surface of the dressing layer to the direction of the current collector, effectively improves the rate capability and the cycle performance of the thick electrode lithium ion battery, and reduces the risk of lithium precipitation under high-rate charge and discharge.
7. In the thick electrode prepared by the traditional method, the pole piece on the upper surface layer is stressed firstly in the rolling process, although the designed compaction density is achieved, the porosity of the pole piece is easily caused to be small on the upper layer and large in the bottom layer, the infiltration of electrolyte is not facilitated, and further the Li is not facilitated+The technical scheme of constructing the hierarchical multidimensional through channel can ensure that all particles of the thick pole piece are uniformly received in the rolling processThe force further increases the compaction density, which in turn increases the energy density of the battery.
8. In the electrode prepared by the traditional knife coating method, the random stacking of the electrode components can form a porous structure with high bending degree. In this case, as the thickness of the electrode increases, the porous structure with high bending degree greatly increases the ion transmission path, increases the diffusion resistance of lithium ions in the electrode, so that the ion transmission becomes the rate-limiting step of the electrochemical reaction, and the specific power of the battery is low. The invention constructs the thick electrode of the grading multidimensional through channel by the cooperation of the magnetic effect and the ice crystal effect, reduces the curvature of the electrode, and reduces the curvature of the electrode in Li+In the insertion/extraction process, Li+The concentration gradient and the current density are uniformly distributed, so that the electrochemical reaction in the electrode is uniform. Meanwhile, the active material is regulated and controlled in the low-curvature electrode to form pore characteristics with high uniformity and strong regularity, so that the reaction kinetics in the high-load electrode are accelerated, and the Li is shortened+The overall diffusion path at the electrode significantly improves the capacity of the lithium ion battery at high rates.
Drawings
FIG. 1 is a schematic structural diagram of a positive plate of a lithium ion battery prepared by the invention;
FIG. 2 is a schematic view of a vertical channel constructed using the ice crystal effect;
fig. 3 is a graph showing rate charge and discharge performance of the positive electrode sheets of the lithium ion batteries prepared in examples and comparative examples.
Detailed Description
The invention uniformly mixes the magnetic nano particles with the high-nickel anode material, constructs a multidirectional branched channel through the magnetic effect, and further constructs a thick electrode with a graded multidimensional through channel through the ice crystal effect. Therefore, the invention forms an integrated realization technical scheme of microstructure property regulation and control of the thick electrode structure, construction and reinforcement of the dressing layer and the electrolyte as well as the current collector interface, and whole electron and ion conduction promotion, and finally realizes comprehensive promotion of the large-magnification charge-discharge performance and stability of the thick electrode.
In order to better explain the technical scheme, the technical scheme is described in detail with reference to specific embodiments. It should not be understood that the scope of the above-described subject matter is limited to the following examples, and any techniques implemented based on the above-described subject matter are within the scope of the present invention.
Electrochemical test is to assemble button cell, and charge and discharge test cabinet is adopted to test electrical property.
Examples
Step S1: 3mol of Gd2O3And 5mol of Ga2O3 And 300mL of 5 mol. L−1The mixed solution is condensed and refluxed for 6 hours at the constant temperature of 250 ℃ under the condition of strong stirring to obtain the gadolinium-gallium mixed nitrate solution. Then 100mL of a solution having a concentration of 4 mol. L was added−1The pH value of the mixed system is adjusted to 2.5-3.0 by using strong ammonia water. Ammonium bicarbonate solution is used as a precipitator, the titration speed is controlled at 2mL/min, and the pH of the mixed system is controlled at 7.5-8 in the process. After titration, stirring is continued for 1h, and then standing and aging are carried out for 12 h. And filtering, washing and alcohol washing the precipitate, and drying at 60 ℃ for 10 hours to obtain a loose precursor. And (3) porphyrizing and sieving the precursor in an agate mortar, and calcining the precursor in a muffle furnace at 900 ℃ for 4 hours to obtain the iron-doped gadolinium gallium garnet magnetic nanoparticle. Then 200mL of 1 mol. L was added-1Stirring the sodium oleate by an oil bath at the temperature of 80 ℃ for 1h, cooling to room temperature, separating a superfine magnetic nanoparticle crude product from the solution through magnetic field separation, alternately washing with ethanol and deionized water for several times, and drying in a vacuum drying oven at the temperature of 60 ℃ to obtain superfine iron-doped gadolinium gallium garnet magnetic nanoparticles for later use;
step S2: dispersing 50g of NCM811 high-nickel ternary cathode material in 1000mL of ethanol solution to obtain a suspension containing the high-nickel ternary cathode material, and adding 0.15g of the ultrafine iron-doped gadolinium gallium garnet magnetic nanoparticles prepared in the step S1 into the suspension containing the high-nickel ternary cathode material. The suspension was stirred for 2h, centrifuged and dried in a vacuum oven at 80 ℃ for 12 h. Uniformly mixing the obtained mixture with 2.7778g of binder PVDF, 2.7778g of conductive agent SP, 0.015g of acetic acid and solvent NMP to obtain high-nickel positive electrode slurry with the viscosity of 7000 mPas;
step S3: coating the high nickel anode slurry prepared in the step S2 in a mold with an aluminum foil placed at the bottom by adjusting the coating thickness to 300 μm through a scraper;
step S4: the mold in step S3 is placed in a drying chamber with good sealing properties. Loading a magnetic field in situ, wherein magnetic nanoparticles are directionally arranged under the action of the magnetic field by adjusting the intensity of the magnetic field to generate a multidirectional distribution branched channel; in addition, when a magnetic field acts on a magnetic substance, the magnetic moment arrangement in the magnetic nanoparticles is ordered, the entropy of the system is reduced, and heat is released to the high-nickel anode slurry; on the contrary, when the magnetic field is removed, the magnetic moment arrangement of the magnetic nano-particles tends to be disordered, the entropy increase of the system absorbs heat from the slurry, and the heat is repeatedly circulated, so that the ice crystal effect is generated. When the internal temperature of the high-nickel anode slurry is reduced to the freezing point of the solvent, the solvent crystals can be rapidly nucleated and grow on the surface of the aluminum foil, and the electrode material is extruded into the gaps of the ice crystals due to the low solubility of the electrode material in the ice crystals. Through regulating and controlling the magnetic field intensity field 7T, the time of loading the magnetic field is 1min, the time of removing the magnetic field is 3min, the cycle times are 4 times, and then the electrode is quickly transferred into a low-temperature low-pressure chamber with the low temperature of minus 10 ℃ and the low pressure of 2Pa, so that the ice crystals are sublimated, the original positions of the ice crystals can form vertical channels, and the thick electrode with the grading multidimensional through channel, which is cooperatively constructed by the magnetic effect and the ice crystal effect, is generated;
step S5: and (4) adopting a magnetic recovery device, setting the magnetic field intensity to be 3T, and recovering and recycling the magnetic nanoparticles in the thick electrode prepared in the step S4, wherein the recovery rate of the magnetic nanoparticles can reach 92%, and finally preparing the lithium ion battery positive plate.
Comparative example 1 (non-magnetic nanoparticles, no graded three-dimensional through channel)
Step S1: adopting a universal wet mixing process, uniformly mixing 50g of NCM811 high-nickel ternary positive electrode material, 2.7778g of binder PVDF, 2.7778g of conductive agent SP, 0.015g of acetic acid and solvent NMP to prepare high-nickel positive electrode slurry with the viscosity of 7000mPa & s;
step S2: the high nickel positive electrode slurry prepared in step S1 was coated in a mold with an aluminum foil placed on the bottom by adjusting the coating thickness to 300 μm by a doctor blade.
Comparative example 2 (with magnetic nanoparticles, without ice crystal effect, construction of multiway-distributed branched channels by magnetic effect only)
Step S1: 3mol of Gd2O3And 5mol of Ga2O3 And 300mL of 5 mol. L−1The mixed solution is condensed and refluxed for 6 hours at the constant temperature of 250 ℃ under the condition of strong stirring to obtain the gadolinium-gallium mixed nitrate solution. Then 100mL of a solution having a concentration of 4 mol. L was added−1The pH value of the mixed system is adjusted to 2.5-3.0 by using strong ammonia water. Ammonium bicarbonate solution is used as a precipitator, the titration speed is controlled at 2mL/min, and the pH of the mixed system is controlled at 7.5-8 in the process. After the titration is finished, stirring is continued for 1h, and then standing and aging are carried out for 12 h. And filtering, washing and alcohol washing the precipitate, and drying at 60 ℃ for 10 hours to obtain a loose precursor. And (3) grinding and sieving the precursor in an agate mortar, and calcining for 4h at 900 ℃ in a muffle furnace to obtain the iron-doped gadolinium gallium garnet magnetic nanoparticles. Then 200mL of 1 mol. L was added-1Stirring the sodium oleate by an oil bath at the temperature of 80 ℃ for 1h, cooling to room temperature, separating a superfine magnetic nanoparticle crude product from the solution through magnetic field separation, alternately washing with ethanol and deionized water for several times, and drying in a vacuum drying oven at the temperature of 60 ℃ to obtain superfine iron-doped gadolinium gallium garnet magnetic nanoparticles for later use;
step S2: 50g of NCM811 high-nickel ternary cathode material is dispersed in 1000mL of ethanol solution, and then 0.15g of the ultrafine iron-doped gadolinium gallium garnet magnetic nanoparticles prepared in step S1 is added into the suspension containing the high-nickel ternary cathode material. The suspension was stirred for 2h, centrifuged and dried in a vacuum oven at 80 ℃ for 12 h. Uniformly mixing the obtained product with 2.7778g of binder PVDF, 2.7778g of conductive agent SP, 0.015g of acetic acid and solvent NMP to obtain high-nickel positive electrode slurry with the viscosity of 7000 mPas;
step S3: coating the high nickel anode slurry prepared in the step S2 in a mold with an aluminum foil placed at the bottom by adjusting the coating thickness to 300 μm through a scraper;
step S4: the mold in step S3 is placed in a drying chamber with good sealing properties. Loading a magnetic field in situ, and adjusting the magnetic field intensity to 7T to ensure that the magnetic nanoparticles are directionally arranged under the action of the magnetic field to generate a multidirectional distribution branched channel;
step S5: and (4) adopting a magnetic recovery device, setting the magnetic field intensity to be 3T, and recycling the magnetic nanoparticles in the thick electrode prepared in the step S4 to finally prepare the lithium ion battery positive plate.
Comparative example 3 (surfactant in magnetic nanoparticles, but acetic acid not in slurry)
Step S1: 3mol of Gd2O3And 5mol of Ga2O3 And 300mL of 5 mol. L−1The mixed nitrate solution is mixed and condensed and refluxed for 6 hours under the conditions of constant temperature of 250 ℃ and strong stirring to obtain the gadolinium-gallium mixed nitrate solution. Then 100mL of a solution having a concentration of 4 mol. L was added−1The pH value of the mixed system is adjusted to 2.5-3.0 by using strong ammonia water. Ammonium bicarbonate solution is used as a precipitator, the titration speed is controlled at 2mL/min, and the pH of the mixed system is controlled at 7.5-8 in the process. After the titration is finished, stirring is continued for 1h, and then standing and aging are carried out for 12 h. And filtering, washing with water and alcohol, and drying at 60 ℃ for 10 hours to obtain a loose precursor. And (3) grinding and sieving the precursor in an agate mortar, and calcining for 4h at 900 ℃ in a muffle furnace to obtain the iron-doped gadolinium gallium garnet magnetic nanoparticles. Then 200mL of 1 mol. L was added-1Stirring the sodium oleate by an oil bath at the temperature of 80 ℃ for 1h, cooling to room temperature, separating a superfine magnetic nanoparticle crude product from the solution through magnetic field separation, alternately washing with ethanol and deionized water for several times, and drying in a vacuum drying oven at the temperature of 60 ℃ to obtain superfine iron-doped gadolinium gallium garnet magnetic nanoparticles for later use;
step S2: 50g of NCM811 high-nickel ternary cathode material was dispersed in 1000mL of ethanol solution, and 0.15g of the ultrafine iron-doped gadolinium gallium garnet magnetic nanoparticles prepared in step S1 was added to the suspension containing the high-nickel ternary cathode material. The suspension was stirred for 2h, centrifuged and dried in a vacuum oven at 80 ℃ for 12 h. Uniformly mixing the nickel-base positive electrode slurry with 2.7778g of binder PVDF, 2.7778g of conductive agent SP and solvent NMP to prepare high-nickel positive electrode slurry with the viscosity of 7000 mPas;
step S3: coating the high nickel anode slurry prepared in the step S2 in a mold with an aluminum foil placed at the bottom by adjusting the coating thickness to 300 μm through a scraper;
step S4: the mold in step S3 is placed in a drying chamber with good sealing properties. Loading a magnetic field in situ, wherein magnetic nanoparticles are directionally arranged under the action of the magnetic field by adjusting the intensity of the magnetic field to generate a multidirectional distribution branched channel; in addition, when a magnetic field acts on a magnetic substance, the magnetic moment arrangement in the magnetic nanoparticles is ordered, the entropy of the system is reduced, and heat is released to the high-nickel anode slurry; on the contrary, when the magnetic field is removed, the magnetic moment arrangement of the magnetic nano-particles tends to be disordered, the entropy increase of the system absorbs heat from the slurry, and the heat is repeatedly circulated, so that the ice crystal effect is generated. When the internal temperature of the high-nickel anode slurry is reduced to the freezing point of the solvent, the solvent crystals can be rapidly nucleated and grow on the surface of the aluminum foil, and the electrode material is extruded into the gaps of the ice crystals due to the low solubility of the electrode material in the ice crystals. Through regulating and controlling the magnetic field intensity field 7T, the time of loading the magnetic field is 1min, the time of removing the magnetic field is 3min, the cycle times are 4 times, and then the electrode is quickly transferred into a low-temperature low-pressure chamber with the low temperature of minus 10 ℃ and the low pressure of 2Pa, so that the ice crystals are sublimated, the original positions of the ice crystals can form vertical channels, and the thick electrode with the grading multidimensional through channel, which is cooperatively constructed by the magnetic effect and the ice crystal effect, is generated;
step S5: and (4) adopting a magnetic recovery device, setting the magnetic field intensity to be 3T, and recycling the magnetic nanoparticles in the thick electrode prepared in the step S4 to finally prepare the lithium ion battery positive plate.
Comparative example 4 (No iron ion added to magnetic nanoparticles)
Step S1: 3mol of Gd2O3And 5mol of Ga2O3 And 300mL of 5 mol. L−1The mixed solution is condensed and refluxed for 6 hours at the constant temperature of 250 ℃ under the condition of strong stirring to obtain the gadolinium-gallium mixed nitrate solution. Adjusting the pH value of the mixed system to 2.5-3.0 by using concentrated ammonia water. Ammonium bicarbonate solution is used as a precipitator, the titration speed is controlled at 2mL/min, and the pH of the mixed system is controlled at 7.5-8 in the process. After titration, stirring is continued for 1h, and then standing and aging are carried out for 12 h. And filtering, washing and alcohol washing the precipitate, and drying at 60 ℃ for 10 hours to obtain a loose precursor. The precursor is porphyrized and sieved in an agate mortar, and then calcined in a muffle furnace at 900 DEG C4h, obtaining the iron-doped gadolinium gallium garnet magnetic nanoparticles. Then 200mL of 1 mol. L was added-1Stirring the sodium oleate by an oil bath at the temperature of 80 ℃ for 1h, cooling to room temperature, separating a superfine magnetic nanoparticle crude product from the solution through magnetic field separation, alternately washing the crude product with ethanol and deionized water for several times, and drying the crude product in a vacuum drying oven at the temperature of 60 ℃ to obtain superfine iron-doped gadolinium gallium garnet magnetic nanoparticles for later use;
step S2: 50g of NCM811 high-nickel ternary cathode material was dispersed in 1000mL of ethanol solution, and 0.15g of the ultrafine iron-doped gadolinium gallium garnet magnetic nanoparticles prepared in step S1 was added to the suspension containing the high-nickel ternary cathode material. The suspension was stirred for 2h, centrifuged and dried in a vacuum oven at 80 ℃ for 12 h. Uniformly mixing the nickel-base positive electrode slurry with 2.7778g of binder PVDF, 2.7778g of conductive agent SP, 0.015g of acetic acid and solvent NMP to prepare high-nickel positive electrode slurry with the viscosity of 7000 mPas;
step S3: coating the high nickel anode slurry in the step S2 in a mold with an aluminum foil placed at the bottom by adjusting the coating thickness to 300 μm with a doctor blade;
step S4: the mold in step S3 is placed in a drying chamber with good sealing properties. Loading a magnetic field in situ, wherein magnetic nanoparticles are directionally arranged under the action of the magnetic field by adjusting the intensity of the magnetic field to generate a multidirectional distribution branched channel; in addition, when a magnetic field acts on a magnetic substance, the magnetic moment arrangement in the magnetic nanoparticles is ordered, the entropy of the system is reduced, and heat is released to the high-nickel anode slurry; on the contrary, when the magnetic field is removed, the magnetic moment arrangement of the magnetic nano-particles tends to be disordered, the entropy increase of the system absorbs heat from the slurry, and the heat is repeatedly circulated, so that the ice crystal effect is generated. When the internal temperature of the high-nickel anode slurry is reduced to the freezing point of the solvent, the solvent crystals can be rapidly nucleated and grow on the surface of the aluminum foil, and the electrode material is extruded into the gaps of the ice crystals due to the low solubility of the electrode material in the ice crystals. By regulating the magnetic field intensity field 7T, loading the magnetic field for 1min and removing the magnetic field for 3min, and circulating for 4 times, and then rapidly transferring the electrode into a low-temperature low-pressure chamber with the low temperature of minus 10 ℃ and the low pressure of 2Pa, so that the ice crystals are sublimated, the original positions of the ice crystals can form vertical channels, and the thick electrode with the graded multidimensional through channel, which is cooperatively constructed by the magnetic effect and the ice crystal effect, is generated;
step S5: and (4) adopting a magnetic recovery device, setting the magnetic field intensity to be 3T, and recovering the magnetic nanoparticles in the thick electrode prepared in the step S4 for later use to finally prepare the lithium ion battery positive plate.
COMPARATIVE EXAMPLE 5 (without recovery of magnetic form)
Step S1: 3mol of Gd2O3And 5mol of Ga2O3 And 300mL of 5 mol. L−1The mixed solution is condensed and refluxed for 6 hours at the constant temperature of 250 ℃ under the condition of strong stirring to obtain the gadolinium-gallium mixed nitrate solution. Then 100mL of a solution having a concentration of 4 mol. L was added−1The pH value of the mixed system is adjusted to 2.5-3.0 by using strong ammonia water. Ammonium bicarbonate solution is used as a precipitator, the titration speed is controlled at 2mL/min, and the pH of the mixed system is controlled at 7.5-8 in the process. After the titration is finished, stirring is continued for 1h, and then standing and aging are carried out for 12 h. And filtering, washing and alcohol washing the precipitate, and drying at 60 ℃ for 10 hours to obtain a loose precursor. And (3) grinding and sieving the precursor in an agate mortar, and calcining for 4h at 900 ℃ in a muffle furnace to obtain the iron-doped gadolinium gallium garnet magnetic nanoparticles. Then 200mL of 1 mol. L was added-1Stirring the sodium oleate by an oil bath at the temperature of 80 ℃ for 1h, cooling to room temperature, separating a superfine magnetic nanoparticle crude product from the solution through magnetic field separation, alternately washing with ethanol and deionized water for several times, and drying in a vacuum drying oven at the temperature of 60 ℃ to obtain superfine iron-doped gadolinium gallium garnet magnetic nanoparticles for later use;
step S2: 50g of NCM811 high-nickel ternary cathode material is dispersed in 1000mL of ethanol solution, and then 0.15g of the ultrafine iron-doped gadolinium gallium garnet magnetic nanoparticles prepared in step S1 is added into the suspension containing the high-nickel ternary cathode material. The suspension was stirred for 2h, centrifuged and dried in a vacuum oven at 80 ℃ for 12 h. Uniformly mixing the obtained mixture with 2.7778g of binder PVDF, 2.7778g of conductive agent SP, 0.015g of acetic acid and solvent NMP to obtain high-nickel positive electrode slurry with the viscosity of 7000 mPas;
step S3: coating the high nickel anode slurry prepared in the step S2 in a mold with an aluminum foil placed at the bottom by adjusting the coating thickness to 300 μm through a scraper;
step S4: the mold in step S3 is placed in a drying chamber with good sealing properties. Loading a magnetic field in situ, wherein magnetic nanoparticles are directionally arranged under the action of the magnetic field by adjusting the intensity of the magnetic field to generate a multidirectional distribution branched channel; in addition, when a magnetic field acts on a magnetic substance, the magnetic moment arrangement in the magnetic nanoparticles is ordered, the entropy of the system is reduced, and heat is released to the high-nickel anode slurry; on the contrary, when the magnetic field is removed, the magnetic moment arrangement of the magnetic nano-particles tends to be disordered, the entropy increase of the system absorbs heat from the slurry, and the heat is repeatedly circulated, so that the ice crystal effect is generated. When the internal temperature of the high-nickel anode slurry is reduced to the freezing point of the solvent, the solvent crystals can be rapidly nucleated and grow on the surface of the aluminum foil, and the electrode material is extruded into the gaps of the ice crystals due to the low solubility of the electrode material in the ice crystals. Through regulating and controlling the magnetic field intensity field 7T, the magnetic field loading time is 1min, the magnetic field removing time is 3min, the cycle times are 4 times, and then the electrode is quickly transferred into a low-temperature low-pressure chamber with the low temperature of minus 10 ℃ and the low pressure of 2Pa, so that the ice crystals are sublimated, the original positions of the ice crystals can form vertical channels, thereby generating the thick electrode which is constructed by the synergy of the magnetic effect and the ice crystal effect and has a graded multidimensional through channel, and finally preparing the lithium ion battery positive plate.
Comparative example 6 (construction of irregular, uniform vertical channel with pore passage by freeze-drying only without magnetic nanoparticles)
Step S1: uniformly mixing 50g of NCM811 high-nickel ternary positive electrode material, 2.7778g of binder PVDF, 2.7778g of conductive agent SP, 0.015g of acetic acid and solvent NMP to prepare high-nickel positive electrode slurry with the viscosity of 7000mPa & s;
step S2: coating the high nickel anode slurry in the step S1 in a mold with an aluminum foil placed at the bottom by adjusting the coating thickness to 300 μm with a doctor blade;
step S3: the mold in step S2 was freeze-dried at low temperature-80 deg.C for 6 h. When the temperature inside the slurry drops to the freezing point of the solvent, the solvent crystals will rapidly nucleate and grow at the surface of the aluminum foil and be expelled into the spaces between the ice crystals due to the lower solubility of the electrode material in the ice crystals. And then, rapidly transferring the electrode to a low-temperature low-pressure chamber with the low temperature of-10 ℃ and the low pressure of 2Pa, sublimating the ice crystals, forming vertical through holes at the original positions of the ice crystals, and finally preparing the lithium ion battery positive plate.
The lithium ion battery positive plate prepared by the embodiment of the invention has better rate capability and cycle stability. As can be seen from the electrical property test result in fig. 3, the lithium ion battery positive plate prepared in the example has better rate capability and capacity recovery capability.
Through analysis of the examples and comparative examples 1 to 6, the transmission capability of ions and electrons can be influenced to different degrees by controlling key factors such as the addition ratio of the magnetic nanoparticles, the magnetic coupling and anchoring of the positive electrode material and the current collector, the surface roughness treatment of the current collector, the low-temperature freezing effect, the recovery of the magnetic nanoparticles and the like. The invention further shows that the invention can realize the comprehensive improvement of the high-rate charge-discharge performance and stability of the thick electrode by the integrated realization technical scheme of the regulation and control of the microstructure property of the thick electrode, the construction reinforcement of the dressing layer, the electrolyte and the current collector interface, and the improvement of the integral electron and ion conduction.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (7)
1. A preparation method of a lithium ion battery positive plate is characterized by comprising the following specific steps: the method comprises the steps of uniformly mixing a high-nickel anode material and a magnetic material through mechanical stirring to obtain high-nickel anode slurry, coating the high-nickel anode slurry on the surface of a current collector, enabling the magnetic material to be directionally arranged in the high-nickel anode slurry through alternate loading and magnetic field removal, preparing a thick polar plate with a graded multidimensional through channel by utilizing an ice crystal effect, and recovering the magnetic material in the thick polar plate by adopting a magnetic recovery device to prepare the lithium ion battery anode plate, wherein the Ni content in the high-nickel anode material is more than or equal to 80wt%, and the magnetic material is iron-doped gadolinium gallium garnet magnetic nanoparticles.
2. The preparation method of the positive plate of the lithium ion battery according to claim 1, comprising the following specific steps:
step S1: gd is mixed with2O3And Ga2O3Uniformly mixing with a nitric acid solution, condensing and refluxing to obtain a gadolinium-gallium mixed nitrate solution, adding a ferric nitrate solution, adjusting the pH value of a mixed system to 2.5-3.0 by using concentrated ammonia water, then using an ammonium bicarbonate solution as a precipitator, controlling the pH value of the mixed system to 7.5-8.0 after titration, standing and aging, transferring the dried precipitate to a muffle furnace for calcining at 800-950 ℃ to obtain iron-doped gadolinium-gallium garnet magnetic nanoparticles, adding a surfactant, stirring by an oil bath at 80 ℃, cooling to room temperature, separating a magnetic nanoparticle crude product from the solution by adopting magnetic field separation, alternately washing for several times by using ethanol and deionized water, and drying to obtain superfine iron-doped gallium-garnet magnetic nanoparticles;
step S2: according to the high nickel anode material: binder PVDF: respectively weighing raw materials according to the mass ratio of 90% to 5% of the conductive agent SP, dispersing a high-nickel anode material into an ethanol solution to obtain a suspension containing the high-nickel anode material, adding the ultrafine iron-doped gadolinium gallium garnet magnetic nanoparticles prepared in the step S1 into the suspension containing the high-nickel anode material, uniformly mixing, and uniformly mixing with the binder PVDF, the conductive agent SP, acetic acid and the solvent NMP to obtain high-nickel anode slurry;
step S3: adjusting the coating thickness to be 100-1000 mu m by a scraper, and coating the high-nickel anode slurry prepared in the step S2 in a mold with an aluminum foil placed at the bottom;
step S4: placing the die in the step S3 in a sealed drying chamber, alternately loading and removing the magnetic field, regulating and controlling the magnetic field strength to be 6-8T, loading the magnetic field for 0.5-1.5 min, removing the magnetic field for 2-4 min, and circulating for 3-5 times, and then transferring the electrode to a low-temperature low-pressure chamber to stand to obtain a thick electrode with a hierarchical multidimensional through channel;
step S5: and (4) adopting a magnetic recovery device, setting the magnetic field intensity to be 2-4T, and recovering and recycling the magnetic nanoparticles in the thick electrode prepared in the step S4 to finally prepare the lithium ion battery positive plate.
3. The method for preparing the positive plate of the lithium ion battery according to claim 2, wherein the method comprises the following steps: in step S1, the surfactant is sodium stearate, potassium stearate, sodium oleate, potassium oleate, sodium laurate or potassium laurate.
4. The method for preparing the positive plate of the lithium ion battery according to claim 2, wherein the method comprises the following steps: the high-nickel positive electrode material in the step S2 is an NCM811 high-nickel ternary positive electrode material.
5. The method for preparing the positive plate of the lithium ion battery according to claim 2, wherein the method comprises the following steps: in the step S2, the mass ratio of the ultrafine iron-doped gadolinium gallium garnet magnetic nanoparticles to the high-nickel positive electrode material is 0.1-0.5%, the mass ratio of the acetic acid to the high-nickel positive electrode material is 0.02-0.05%, and the viscosity of the high-nickel positive electrode slurry is 4000-9000 mPa & S.
6. The method for preparing the positive plate of the lithium ion battery according to claim 2, wherein the method comprises the following steps: in step S3, the coating thickness is adjusted to 250 to 350 μm by a doctor blade.
7. The method for preparing the positive plate of the lithium ion battery according to claim 2, wherein the method comprises the following steps: in the step S4, the low-temperature low-pressure indoor temperature is-5 to-10 ℃, and the low pressure is 1 to 2 Pa.
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