CN113066980A - Method for preparing phosphomolybdic acid modified high-nickel single crystal positive electrode material - Google Patents
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Abstract
The invention discloses a method for preparing a phosphomolybdic acid modified high-nickel single crystal anode material. The method comprises the following steps: mixing phosphomolybdic acid and ethanol to prepare phosphomolybdic acid ethanol solution; adding high-nickel single-crystal positive electrode material powder into the ethanol solution of phosphomolybdic acid, and stirring to volatilize ethanol; and calcining the mixture in an oxygen atmosphere to obtain the coated electrode material for the lithium ion secondary battery. The invention also provides the high-nickel single-crystal cathode material prepared by the method and application thereof in manufacturing a lithium ion secondary battery. The preparation method is simple and low in cost, and the prepared high-nickel single crystal positive electrode material has the advantages of high specific capacity, good conductivity, good cycling stability and the like.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a method for preparing a phosphomolybdic acid modified high-nickel single crystal anode material.
Background
Lithium ion batteries are widely used in the production and life of people due to their high energy density, no memory effect, and long cycle stability. Currently, to meet the long endurance demand, lithium ion batteries are being developed toward higher energy densities. The high nickel layered oxide has a high specific capacity and discharge voltage, and is considered to be the most promising positive electrode material for the next generation of high energy density lithium ion batteries. However, some problems with high nickel layered oxides have hindered their use in batteries.
During charge and discharge, lithium ion deintercalation tends to be accompanied by a volume change of the positive electrode material. The characteristic is more obvious in the ternary cathode material of a high nickel system. Particularly, when the Ni content is higher than 0.8, a new H2-H3 phase transition appears in the charge-discharge process of the cathode material. This phase change causes a large volume change and stress. In a common secondary particle high nickel cathode material, the random arrangement of the primary particles also causes the stress to be unevenly distributed inside the secondary particles, thereby causing the secondary particles to be broken. In addition, the surface of the high nickel positive electrode material is extremely unstable due to the disruption of the long-range order of the crystal. In the highly delithiated state, the surface lamellar phase will transform to the thermodynamically more stable rock salt phase. The phase transition process is accompanied by the release of active oxygen, which further catalyzes the decomposition of the electrolyte to form a thicker positive-electrolyte phase (CEI). The rock salt phase is a poor conductor of lithium ions, and a thicker CEI also inhibits diffusion of lithium ions into the electrode material. Thus, formation of the rock salt phase and CEI can lead to a decline in cell performance. High nickel single crystals have proven to be an effective strategy to inhibit secondary particle breakage. However, since the single crystal has a larger size and a smaller specific surface area, the current density of the single crystal positive electrode is higher, and surface phase transition and interfacial side reaction are more serious, thereby causing a large amount of active material to be deactivated. In addition, the high-nickel cathode material has poorer corrosion resistance to the electrolyte, and the dissolution of the transition metal is more obvious. Therefore, the regulation of the surface phase is an important part of the study of high nickel single crystals.
The regulation and control strategies of the surface phase of the anode material can be divided into two categories, one is to construct a thermodynamically stable electrochemical active phase on the surface, and the other is to construct an electrochemical inert phase on the surface. It is emphasized that the thermodynamic stability of the electrochemically active phase refers to the thermodynamic stability in a highly delithiated state, because the current density borne by the single crystal positive electrode is large, and the surface is in a highly delithiated state, and the main material capable of meeting the requirement is a positive electrode material showing a strict two-phase reaction behavior, such as lithium iron phosphate, high-pressure lithium nickel manganese oxide and lithium titanate. However, because of the low charge-discharge plateau of lithium iron phosphate and lithium titanate, the lithium ion conductor behaves in a manner of electrochemical inertia substantially within the electrochemical window range of the high-nickel anode. Therefore, the high-pressure lithium nickel manganese oxide may be the only electrochemical active phase meeting the thermodynamic stability requirement. The electrochemical inert phase mainly plays a role in forming a physical barrier between the electrolyte and the anode material, preventing the electrolyte from being corroded, and essentially has ion conduction and electron conduction capabilities. In addition, the newly constructed surface phase may be either a pure phase or a composite phase.
The formation of the surface phase is generally achieved by post-treatment of the anode material. The surface phase precursor is loaded on the surface of the anode material in a solid-phase mixing and liquid-phase coating mode. Solid phase mixing takes a short time and is efficient, but it is difficult to form a uniform surface phase. The liquid phase coating is usually water as a solvent, and although the liquid phase coating can form a uniform coating layer, it takes a long time, is inefficient, and causes damage to the active material of the positive electrode material. Therefore, it is necessary to develop an efficient liquid phase coating method to realize a surface phase having both high conductivity, stability and corrosion resistance.
Disclosure of Invention
The invention aims to reduce the corrosion of the electrolyte on the positive electrode material, improve the treatment efficiency of the positive electrode material and improve the conductivity of the battery.
In view of the above, according to the first aspect of the present invention, there is provided a method for preparing a high nickel single crystal positive electrode material with high cycling stability, wherein the general structural formula of the high nickel single crystal positive electrode material is LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.6 and less than 1, y is more than 0 and less than or equal to 0.2, and x + y is less than 1, the method comprises the following steps: mixing phosphomolybdic acid and ethanol to prepare phosphomolybdic acid ethanol solution; adding the high-nickel single-crystal positive electrode material into the phosphomolybdic acid ethanol solution to volatilize ethanol; and then calcined in an oxygen atmosphere to obtain a coated electrode material for a lithium ion secondary battery.
The inventor unexpectedly discovers that the lithium phosphomolybdate is dissolved firstly by using ethanol as a solvent to prepare a solution, and then the solution is coated, so that compared with the method of using water as a solvent, the residual lithium in the anode material is prevented from being dissolved by water, and lithium loss caused by the ion exchange reaction between H + in the water and lithium ions in the anode material is also prevented; meanwhile, the volatilization speed of the ethanol is higher, so that the time of the whole process is shortened.
Preferably, the method comprises the steps of:
1) mixing phosphomolybdic acid and ethanol to prepare phosphomolybdic acid ethanol solution;
2) adding the high-nickel single-crystal positive electrode material into the phosphomolybdic acid ethanol solution, stirring, and grinding to obtain powder after ethanol volatilizes;
3) and calcining the obtained powder in a tubular furnace in the atmosphere of oxygen at the temperature of 450-850 ℃ for 3-20 hours to obtain the coated electrode material for the lithium ion secondary battery.
Preferably, the concentration of the phosphomolybdic acid ethanol solution is 3-25 g/L.
Preferably, the temperature of step 3) is 550-.
Preferably, the calcination time of step 3) is 5 to 18 hours.
According to the second aspect of the invention, the preparation method of the high-nickel single crystal cathode material with high cycling stability is provided, and the structural general formula of the high-nickel single crystal cathode material is LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.6 and less than 1, y is more than 0 and less than or equal to 0.2, and x + y is less than 1, the method comprises the following steps: mixing phosphomolybdic acid, ethanol and polyvinylpyrrolidone to prepare a phosphomolybdic acid mixed solution; adding a high-nickel single-crystal positive electrode material into the phosphomolybdic acid mixed solution to volatilize ethanol; and then calcined in an oxygen atmosphere to obtain a coated electrode material for a lithium ion secondary battery.
Compared with the method without adding polyvinylpyrrolidone, the method has the advantages that phosphomolybdic acid, ethanol and high-molecular-weight polyvinylpyrrolidone are firstly mixed, so that phosphomolybdic acid is uniformly and stably coated on the surface of the positive electrode material, carbon dioxide generated by polyvinylpyrrolidone is volatilized after high-temperature calcination in an oxygen atmosphere, lithium molybdate and a small amount of lithium phosphomolybdate are mainly left on the surface, and the lithium molybdate is resistant to electrolyte corrosion and is an ion conductor and can conduct electricity, so that the corrosion resistance and the conductivity of the positive electrode material are improved.
Preferably, the method comprises the steps of:
(1) mixing phosphomolybdic acid with ethanol and polyvinylpyrrolidone to prepare a phosphomolybdic acid mixed solution;
(2) adding a high-nickel single-crystal positive electrode material into the phosphomolybdic acid mixed solution, and stirring to volatilize ethanol;
(3) and (3) calcining the product obtained in the step (2) in a tubular furnace at the atmosphere of oxygen and the temperature of 500-700 ℃ for 5-15 hours to obtain the coated electrode material I for the lithium ion secondary battery.
Preferably, phosphomolybdic acid: the mass ratio of the polyvinylpyrrolidone is (1-5): 1; more preferably, phosphomolybdic acid: the mass ratio of the polyvinylpyrrolidone is (2-4): 1.
preferably, the temperature in step (3) is 550-650 ℃.
Preferably, the calcination time in step (3) is 6 to 13 hours.
Further preferably, the step (3) may be followed by the steps of:
(4) adding the electrode material I obtained in the step (3) into an ethanol solution of polyvinylpyrrolidone, stirring, and evaporating to remove ethanol;
(5) and (4) calcining the product obtained in the step (4) in a tubular furnace under an inert atmosphere to obtain the coated electrode material II for the lithium ion secondary battery.
Preferably, the calcination temperature in step (5) is 350-450 ℃ to prevent the carbon generated by calcination from reducing the metal in the cathode material. More preferably, the calcination temperature in step (5) is 400 ℃.
Preferably, in step (5), the calcination is carried out at a temperature of 350-450 ℃ for 3-8 hours.
Preferably, the mass ratio of the polyvinylpyrrolidone in the step (4) to the polyvinylpyrrolidone in the step (1) is 1: (2-5).
The inventors have unexpectedly found that the surface of the coated electrode material I for lithium ion secondary batteries can be further coated with dispersed carbon locally by further coating the coated electrode material I for lithium ion secondary batteries with polyvinylpyrrolidone, then calcining the coated electrode material I in an inert atmosphere, and controlling an appropriate temperature, and that the carbon coated on the surface improves the electronic conductivity of the electrode material and synergistically adds the ionic conductivity of the original electrode active material coated therein, thereby further improving the battery capacity, and at the same time, the carbon coated on the outermost layer also improves the stability of the battery.
According to a third aspect of the present invention, there is provided a high nickel single crystal positive electrode material prepared according to the above method, wherein the positive electrode material comprises Li modified by phosphomolybdic acid on the surface of the positive electrode material4MoO5An ion conductor coating.
Further, the positive electrode material is a nickel cobalt lithium manganate ternary material, and the structural formula of the positive electrode material is LiNixCoyMn1-x-yO2，0.6≤x is less than 1, y is more than 0 and less than or equal to 0.2, and x + y is less than 1. Specifically, the structural formula of the positive electrode material is LiNi0.6Co0.2Mn0.2O2、LiNi0.7Co0.2Mn0.1O2Or LiNi0.8Co0.1Mn0.1O2。
Preferably, the cathode material further comprises a carbon coating layer modified by polyvinylpyrrolidone and formed outside the coating layer modified by phosphomolybdic acid.
According to still another aspect of the present invention, there is provided a use of the high nickel single crystal positive electrode material prepared by the above method in manufacturing a high nickel lithium ion secondary battery.
The preparation method and the single crystal cathode material manufactured by the method have the following beneficial technical effects:
(1) by adopting phosphomolybdic acid for modification, Li with corrosion resistance and conductivity is formed on the surface of the positive electrode material4MoO5The ion conductor coating layer not only stabilizes the interface of the positive electrode and the electrolyte, but also constructs a surface phase with good stability and excellent conductivity;
(2) through double modification of phosphomolybdic acid and polyvinylpyrrolidone, a coating layer with good conductivity and corrosion resistance is formed on the surface of the anode electrode material, so that the service life of the electrode material is further prolonged;
(3) li formation by phosphomolybdic acid modification4MoO5The ion conductor layer and the carbon coating layer formed by polyvinylpyrrolidone modification are cooperatively interacted, so that the high-nickel single crystal cathode material disclosed by the invention has high specific capacity and cycling stability.
Drawings
Fig. 1 is an X-ray diffraction pattern (XRD) of the phosphomolybdic acid-modified high-nickel single-crystal positive electrode material in example 1.
Fig. 2 is a scanning electron microscope photograph of the phosphomolybdic acid-modified high-nickel single-crystal positive electrode material in example 1.
Fig. 3 is a charge-discharge curve diagram of the high nickel single crystal positive electrode materials in example 1 and comparative example 1 at a rate of 0.1C.
Fig. 4 is a cycle chart of the high nickel single crystal positive electrode materials of example 1 and comparative example 1 at a magnification of 0.5C.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
preparing a positive electrode material: preparing an absolute ethanol solution containing 6.2g/L phosphomolybdic acid at room temperature of 25 ℃, and taking 3ml for later use; weighing 2g of single crystal NCM811, dispersing in the 3ml of phosphomolybdic acid absolute ethanol solution, stirring in air until the ethanol naturally volatilizes, and grinding by using a mortar to obtain powder; placing the powder in a corundum box bowl, heating to 700 ℃ at a heating rate of 5 ℃/min in a tubular furnace under an oxygen atmosphere, calcining for 13h, naturally cooling to room temperature, and grinding by using a mortar to obtain the cathode material.
Assembling the battery: mixing the prepared high-nickel single-crystal positive electrode material, conductive carbon (SP) and polyvinylidene fluoride (PVDF) according to a mass ratio of 90: 5: 5, mixing to prepare slurry, and uniformly coating the slurry on an aluminum foil current collector to obtain the anode membrane. Taking a metal lithium sheet as a negative electrode, a polypropylene microporous membrane (Celgard 2400) as a diaphragm, and 1mol/L LiPF6(the solvent is mixed solution of ethylene carbonate and dimethyl carbonate with the volume ratio of 1: 1) as electrolyte, and the button cell is assembled in a glove box protected by argon.
And (3) performance testing: and (3) carrying out constant-current charge and discharge test on the assembled battery on a blue charge and discharge tester, wherein the charge and discharge multiplying power is 0.1C (1C is 200mA/g), and the charge and discharge voltage interval is 3.0-4.3V. The 1 st circle of charge-discharge curve is shown in figure 3, and it can be seen that the discharge capacity of the high nickel single crystal anode material can reach 206 mAh/g. The charging and discharging voltage interval is 3.0-4.3V, and the capacity retention rate after 100 cycles at 0.5C multiplying power is 90% (as shown in figure 4), which shows that the high-nickel single crystal cathode material has outstanding cycling stability.
In addition, the crystal structure of the high nickel single crystal positive electrode material was analyzed by a powder X-ray diffractometer (D8 Advance, Bruke). The results are shown in FIG. 1. The figure shows that the prepared cathode material accords with the diffraction peak of the layered ternary material, and has no impurity peak, which indicates that the material purity is higher.
The morphology of the high-nickel single-crystal positive electrode material is characterized by a scanning electron microscope (JEOL-6700F), as shown in FIG. 2. As can be seen from FIG. 2, the surface-modified material maintains the morphology of the single crystal cathode material.
Example 2:
preparing an absolute ethanol solution containing 12.5g/L phosphomolybdic acid at room temperature of 25 ℃, and taking 3ml for later use; weighing 2g of single crystal NCM811, dispersing in the 3ml of absolute ethanol solution of phosphomolybdic acid, stirring in air until the ethanol naturally volatilizes, and grinding by using a mortar to obtain powder; placing the powder in a corundum box bowl, heating to 700 ℃ at a heating rate of 5 ℃/min in a tubular furnace under an oxygen atmosphere, calcining for 13h, naturally cooling to room temperature, and grinding by using a mortar to obtain the cathode material. The button cell was assembled using the same process as in example 1.
Example 3:
preparing an absolute ethanol solution containing 25g/L phosphomolybdic acid at room temperature of 25 ℃, and taking 3ml for later use; weighing 2g of single crystal NCM811, dispersing in the 3ml of absolute ethanol solution, stirring in air until the ethanol naturally volatilizes, and grinding by using a mortar to obtain powder; placing the powder in a corundum box bowl, heating to 700 ℃ at a heating rate of 5 ℃/min in a tubular furnace under an oxygen atmosphere, calcining for 13h, naturally cooling to room temperature, and grinding by using a mortar to obtain the cathode material. The button cell was assembled using the same process as in example 1.
Example 4:
preparing an absolute ethanol solution containing 37.5g/L phosphomolybdic acid at room temperature of 25 ℃, and taking 3ml for later use; weighing 2g of single crystal NCM811, dispersing in the 3ml of absolute ethanol solution, stirring in air until the ethanol naturally volatilizes, and grinding by using a mortar to obtain powder; placing the powder in a corundum box bowl, heating to 700 ℃ at a heating rate of 5 ℃/min in a tubular furnace under an oxygen atmosphere, calcining for 13h, naturally cooling to room temperature, and grinding by using a mortar to obtain the cathode material. The button cell was assembled using the same process as in example 1.
Example 5:
preparing an absolute ethanol solution containing 6.2g/L phosphomolybdic acid at room temperature of 25 ℃, and taking 3ml for later use; weighing 2g of single crystal NCM811, dispersing in the 3ml of absolute ethanol solution, stirring in air until the ethanol naturally volatilizes, and grinding by using a mortar to obtain powder; placing the powder in a corundum box bowl, heating to 500 ℃ at a heating rate of 5 ℃/min in a tubular furnace under an oxygen atmosphere, calcining for 13h, naturally cooling to room temperature, and grinding by using a mortar to obtain the cathode material. The button cell was assembled using the same process as in example 1.
Example 6:
preparing an absolute ethanol solution containing 6.2g/L phosphomolybdic acid at room temperature of 25 ℃, and taking 3ml for later use; weighing 2g of single crystal NCM811, dispersing in the 3ml of absolute ethanol solution, stirring in air until the ethanol naturally volatilizes, and grinding by using a mortar to obtain powder; placing the powder in a corundum box bowl, heating to 700 ℃ at a heating rate of 5 ℃/min in a tubular furnace under an oxygen atmosphere, calcining for 8h, naturally cooling to room temperature, and grinding by using a mortar to obtain the cathode material. The button cell was assembled using the same process as in example 1.
Example 7:
preparing an absolute ethanol solution containing 6.2g/L phosphomolybdic acid at room temperature of 25 ℃, and taking 3ml for later use; weighing 2g of single crystal NCM811, dispersing in the 3ml of absolute ethanol solution, stirring in air until the ethanol naturally volatilizes, and grinding by using a mortar to obtain powder; placing the powder in a corundum box bowl, heating to 700 ℃ at a heating rate of 5 ℃/min in a tubular furnace under an oxygen atmosphere, calcining for 3h, naturally cooling to room temperature, and grinding by using a mortar to obtain the cathode material. The button cell was assembled using the same process as in example 1.
Example 8:
preparing an absolute ethanol solution containing 6.2g/L phosphomolybdic acid and 2.1g/L polyvinylpyrrolidone at room temperature of 25 ℃, and taking 3ml for later use; 2g of single crystal NCM811 is weighed and dispersed in the 3ml of absolute ethanol solution, and the mixture is stirred in the air to volatilize the ethanol; and (3) in an oxygen atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min in a tube furnace, calcining for 10h, naturally cooling to room temperature, and grinding by using a mortar to obtain the cathode material. The button cell was assembled using the same process as in example 1.
Example 9:
preparing an absolute ethanol solution containing 6.2g/L phosphomolybdic acid and 2.1g/L polyvinylpyrrolidone at room temperature of 25 ℃, and taking 3ml for later use; 2g of single crystal NCM811 is weighed and dispersed in the 3ml of absolute ethanol solution, and stirred in the air until the ethanol is volatilized to be dry; in the oxygen atmosphere, the temperature is raised to 600 ℃ at the heating rate of 5 ℃/min in a tube furnace and calcined for 10h, and the anode material I is obtained by grinding the anode material I by a mortar after the anode material is naturally cooled to the room temperature;
preparing an absolute ethyl alcohol solution of polyvinylpyrrolidone with the concentration of 0.5g/L, dispersing the positive electrode material I in 3ml of the absolute ethyl alcohol solution of polyvinylpyrrolidone with the concentration of 0.5g/L, stirring in the air, and evaporating to remove ethanol; and (3) in an argon atmosphere, heating to 400 ℃ at a heating rate of 5 ℃/min in a tube furnace, calcining for 6h, naturally cooling to room temperature, and grinding by using a mortar to obtain the final cathode material.
Example 10:
preparing an absolute ethanol solution containing 6.2g/L phosphomolybdic acid and 2.1g/L polyvinylpyrrolidone at room temperature of 25 ℃, and taking 3ml for later use; 2g of single crystal NCM811 is weighed and dispersed in the 3ml of absolute ethanol solution, and the mixture is stirred in the air to volatilize the ethanol; in the oxygen atmosphere, the temperature is raised to 600 ℃ at the heating rate of 5 ℃/min in a tube furnace and calcined for 10h, and the anode material I is obtained by grinding the anode material I by a mortar after the anode material is naturally cooled to the room temperature;
preparing an absolute ethyl alcohol solution of polyvinylpyrrolidone with the concentration of 1.0g/L, dispersing the positive electrode material I in 3ml of the absolute ethyl alcohol solution of polyvinylpyrrolidone with the concentration of 1.0g/L, stirring in the air, and evaporating to remove the ethanol; and (3) in an argon atmosphere, heating to 400 ℃ at a heating rate of 5 ℃/min in a tube furnace, calcining for 6h, naturally cooling to room temperature, and grinding by using a mortar to obtain the final cathode material.
Example 11:
preparing an absolute ethanol solution containing 6.2g/L phosphomolybdic acid and 2.1g/L polyvinylpyrrolidone at room temperature of 25 ℃, and taking 3ml for later use; 2g of single crystal NCM811 is weighed and dispersed in the 3ml of absolute ethanol solution, and the mixture is stirred in the air to volatilize the ethanol; in the oxygen atmosphere, the temperature is raised to 600 ℃ at the heating rate of 5 ℃/min in a tube furnace and calcined for 10h, and the anode material I is obtained by grinding the anode material I by a mortar after the anode material is naturally cooled to the room temperature;
preparing an absolute ethyl alcohol solution of polyvinylpyrrolidone with the concentration of 3.5g/L, dispersing the positive electrode material I in 3ml of the absolute ethyl alcohol solution of polyvinylpyrrolidone with the concentration of 3.5g/L, stirring in the air, and evaporating to remove ethanol; and (3) in an argon atmosphere, heating to 400 ℃ at a heating rate of 5 ℃/min in a tube furnace, calcining for 6h, naturally cooling to room temperature, and grinding by using a mortar to obtain the cathode material II.
Comparative example 1:
the rest is the same as example 1, except that: the high-nickel single-crystal cathode material is not modified by phosphomolybdic acid. The button cell was then assembled using the same process as in example 1.
Comparative example 2:
the rest is the same as example 1, except that: the high-nickel anode material is mixed with phosphomolybdic acid without adopting wet coating, is subjected to ball milling in a certain ball milling medium for a period of time, and is then placed in a muffle furnace for calcination.
The button cell was then assembled using the same process as in example 1.
The button cells assembled in the above examples and comparative examples were measured for discharge capacity and capacity retention after 100 cycles by the measurement method in example 1, and the results are shown in the following table 1:
| discharge capacity (mAh/g) | Capacity retention (%) | |
| Example 1 | 206 | 90 |
| Example 2 | 203.5 | 87 |
| Example 3 | 203 | 86 |
| Example 4 | 172 | 80 |
| Example 5 | 200 | 88 |
| Example 6 | 198 | 87 |
| Example 7 | 196 | 82 |
| Example 8 | 215 | 87 |
| Example 9 | 219 | 94 |
| Example 10 | 217 | 92 |
| Example 11 | 181 | 87 |
| Comparative example 1 | 200 | 14 |
| Comparative example 2 | 204 | 11 |
Compared with the comparative example 1, the coating layer formed by phosphomolybdic acid modification can obviously improve the cycle stability of the single crystal cathode material without sacrificing the theoretical capacity of the single crystal cathode material. The reason for this is probably that hydrogen ions in phosphomolybdic acid undergo ion exchange with lithium ions of the positive electrode material, and become a rock salt phase during calcination, stabilizing the interface between the positive electrode and the electrolyte. Meanwhile, in the calcining process, phosphorus and molybdenum are respectively converted into lithium phosphate and lithium molybdate ion conductors, so that the lithium phosphate and lithium molybdate ion conductors can be used as ion conductors while electrolyte is prevented from being dissolved in the positive electrode, and the charge transfer resistance is reduced, thereby improving the specific capacity and improving the cycling stability.
As can be seen from comparison of example 1 with comparative example 2, liquid phase coating is superior to solid phase coating because liquid phase coating can form a uniform coating layer on a uniform nanometer scale on the surface of a single crystal. And because the solid phase coating is slow in ion diffusion, a uniform coating layer is difficult to form on the surface of the single crystal, so that the improvement of the cycle performance of the lithium battery by solid phase mixing is limited.
According to examples 1 to 4, it was found that the discharge capacity decreased and the cycle stability became poor as the amount of phosphomolybdic acid used was increased. This may be due to the limited solubility of molybdenum in the layered oxide, which is associated with the formation of unstable hetero-phases due to excessive amounts.
According to examples 1 and 5, it can be found that the reduction of the calcination temperature leads to the reduction of the discharge capacity of the prepared electrode material and the reduction of the capacity retention rate, which may be caused by the lower calcination temperature, so that the Mo ions are difficult to diffuse into the crystal lattice to form a hetero phase on the surface, thereby leading to the limited improvement of the cycle performance of the material.
In addition, according to examples 1 and 6 to 7, it can be found that the specific capacity of the electrode material is reduced and the capacity retention rate is also reduced as the calcination time is shortened, and the reason for this is probably that the calcination time is shorter, so that the Mo ions diffused into the crystal lattice are less and the improvement of the cycle performance of the material is limited.
In addition, according to examples 8 to 11, it can be found that the coating layer formed by co-modifying phosphomolybdic acid and polyvinylpyrrolidone significantly improves the discharge capacity and the cycle performance of the electrode material. The reason for this may be that there is a certain synergistic effect between the lithium molybdate layer formed by phosphomolybdic acid modification and the carbon layer formed by polyvinylpyrrolidone modification, which makes the finally formed electrode material further improve the cycling stability and conductivity.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Various alternatives, modifications and combinations of the features of the invention can be made without departing from the spirit and nature of the invention as claimed, and such simple variations and combinations should also be considered as disclosed in the present application, all falling within the scope of the invention.
Claims (10)
1. A preparation method of a high-nickel single crystal anode material with high cycling stability is provided, and the structural general formula of the high-nickel single crystal anode material is LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.6 and less than 1, y is more than 0 and less than or equal to 0.2, and x + y is less than 1, and the method is characterized by comprising the following steps:
1) mixing phosphomolybdic acid and ethanol to prepare phosphomolybdic acid ethanol solution;
2) adding high-nickel single-crystal positive electrode material powder into the ethanol solution of phosphomolybdic acid, and stirring to volatilize ethanol;
3) and calcining the mixture in an oxygen atmosphere to obtain the coated electrode material for the lithium ion secondary battery.
2. The method according to claim 1, wherein in step 3), the temperature is 450-850 ℃, preferably, the temperature in step 3) is 550-750 ℃; and the calcination time is 3 to 20 hours, and preferably, the calcination time of step 3) is 5 to 18 hours.
3. The process according to claim 1, wherein the concentration of the phosphomolybdic acid ethanol solution in step 1) is 3-25 g/L.
4. A preparation method of a high-nickel single crystal anode material with high cycling stability is provided, and the structural general formula of the high-nickel single crystal anode material is LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.6 and less than 1, y is more than 0 and less than or equal to 0.2, and x + y is less than 1, and the method is characterized by comprising the following steps:
(1) mixing phosphomolybdic acid, ethanol and polyvinylpyrrolidone to prepare a phosphomolybdic acid mixed solution;
(2) adding a high-nickel single-crystal positive electrode material into the phosphomolybdic acid mixed solution, and stirring to volatilize ethanol;
(3) and then calcined in an oxygen atmosphere to obtain a coated electrode material for a lithium ion secondary battery.
5. The process according to claim 5, wherein in step (1), phosphomolybdic acid: the mass ratio of the polyvinylpyrrolidone is (1-5): 1; more preferably, phosphomolybdic acid: the mass ratio of the polyvinylpyrrolidone is (2-4): 1.
6. the method as claimed in claim 5, wherein in step (3), the product obtained in step (2) is calcined in a tube furnace at a temperature of 500-.
7. The method of claim 6, further comprising, after step (3), the steps of:
(4) adding the electrode material I obtained in the step (3) into an ethanol solution of polyvinylpyrrolidone, stirring, and evaporating to remove ethanol;
(5) and (4) calcining the product obtained in the step (4) in a tubular furnace under an inert atmosphere to obtain the coated electrode material II for the lithium ion secondary battery.
8. The method as claimed in claim 7, wherein the calcination temperature in step (5) is 350-450 ℃; and the calcination time is 3-8 hours.
9. A high-nickel single-crystal positive electrode material prepared according to the method of any one of claims 1 to 8, wherein the positive electrode material comprises Li modified with phosphomolybdic acid on the surface thereof4MoO5An ion conductor coating.
10. Use of the high nickel single crystal positive electrode material prepared according to the method of any one of claims 1 to 8 in the manufacture of a high nickel lithium ion secondary battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113479944A (en) * | 2021-09-07 | 2021-10-08 | 中南大学 | Preparation method of modified high-nickel ternary cathode material |
| CN114551869A (en) * | 2022-02-15 | 2022-05-27 | 山东泰一新能源股份有限公司 | Lithium phosphomolybdate nanorod lithium battery positive electrode material and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011003354A (en) * | 2009-06-17 | 2011-01-06 | Sony Corp | Positive electrode active material, method of manufacturing the same, and nonaqueous electrolyte battery |
| US20120321911A1 (en) * | 2009-06-17 | 2012-12-20 | Sony Corporation | Non-aqueous electrolyte battery, non-aqueous electrolyte battery positive electrode, non-aqueous electrolyte battery negative electrode, non-aqueous electrolyte battery separator, electrolyte for non-aqueous electrolyte, and method of manufacturing non-aqeuous electrolyte battery separator |
| CN104638245A (en) * | 2015-02-13 | 2015-05-20 | 江苏科技大学 | Keggin type phosphomolybdate-graphene composite material for lithium ion battery and preparation method thereof |
| US20150162599A1 (en) * | 2013-12-09 | 2015-06-11 | Samsung Sdi Co., Ltd. | Positive electrode for rechargeable lithium battery, preparing same, and rechargeable lithium battery |
| CN108110248A (en) * | 2017-12-27 | 2018-06-01 | 深圳市比克动力电池有限公司 | A kind of cobalt acid lithium anode material for lithium-ion batteries and preparation method thereof |
| CN108306014A (en) * | 2017-12-26 | 2018-07-20 | 深圳市德方纳米科技股份有限公司 | A kind of monocrystalline nickel-cobalt lithium manganate cathode material and its preparation method and application |
| CN109920993A (en) * | 2019-03-12 | 2019-06-21 | 四川纳创时代新能源科技有限公司 | A kind of surface modifying method of nickelic ternary material nickle cobalt lithium manganate |
| CN110581269A (en) * | 2019-10-09 | 2019-12-17 | 济南大学 | Lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material and preparation method thereof |
| CN111370684A (en) * | 2020-03-27 | 2020-07-03 | 天目湖先进储能技术研究院有限公司 | Method for reducing residual alkali content on surface of high-nickel cathode material of lithium ion battery |
-
2021
- 2021-03-19 CN CN202110293646.3A patent/CN113066980B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011003354A (en) * | 2009-06-17 | 2011-01-06 | Sony Corp | Positive electrode active material, method of manufacturing the same, and nonaqueous electrolyte battery |
| US20120321911A1 (en) * | 2009-06-17 | 2012-12-20 | Sony Corporation | Non-aqueous electrolyte battery, non-aqueous electrolyte battery positive electrode, non-aqueous electrolyte battery negative electrode, non-aqueous electrolyte battery separator, electrolyte for non-aqueous electrolyte, and method of manufacturing non-aqeuous electrolyte battery separator |
| US20150162599A1 (en) * | 2013-12-09 | 2015-06-11 | Samsung Sdi Co., Ltd. | Positive electrode for rechargeable lithium battery, preparing same, and rechargeable lithium battery |
| CN104638245A (en) * | 2015-02-13 | 2015-05-20 | 江苏科技大学 | Keggin type phosphomolybdate-graphene composite material for lithium ion battery and preparation method thereof |
| CN108306014A (en) * | 2017-12-26 | 2018-07-20 | 深圳市德方纳米科技股份有限公司 | A kind of monocrystalline nickel-cobalt lithium manganate cathode material and its preparation method and application |
| CN108110248A (en) * | 2017-12-27 | 2018-06-01 | 深圳市比克动力电池有限公司 | A kind of cobalt acid lithium anode material for lithium-ion batteries and preparation method thereof |
| CN109920993A (en) * | 2019-03-12 | 2019-06-21 | 四川纳创时代新能源科技有限公司 | A kind of surface modifying method of nickelic ternary material nickle cobalt lithium manganate |
| CN110581269A (en) * | 2019-10-09 | 2019-12-17 | 济南大学 | Lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material and preparation method thereof |
| CN111370684A (en) * | 2020-03-27 | 2020-07-03 | 天目湖先进储能技术研究院有限公司 | Method for reducing residual alkali content on surface of high-nickel cathode material of lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| XIANXIANG ZENG等: "Raising the capacity of lithium vanadium phosphate via anion and cation co-substitution", 《SCIENCE CHINA CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113479944A (en) * | 2021-09-07 | 2021-10-08 | 中南大学 | Preparation method of modified high-nickel ternary cathode material |
| CN114551869A (en) * | 2022-02-15 | 2022-05-27 | 山东泰一新能源股份有限公司 | Lithium phosphomolybdate nanorod lithium battery positive electrode material and preparation method and application thereof |
| CN114551869B (en) * | 2022-02-15 | 2023-10-27 | 山东泰一新能源股份有限公司 | Lithium phosphomolybdate nanorod lithium battery positive electrode material, and preparation method and application thereof |
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