CN113130900A - Vanadium pentoxide-coated high-nickel ternary lithium ion battery positive electrode material and preparation method thereof - Google Patents
Vanadium pentoxide-coated high-nickel ternary lithium ion battery positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a vanadium pentoxide coated high-nickel ternary lithium ion battery positive electrode material and a preparation method thereof. The preparation method comprises the following steps: (1) adding a nickel-cobalt-aluminum anode material into deionized water, stirring, washing, and drying to obtain a ternary anode material; (2) dissolving a vanadium source in a medium to form a solution, putting the ternary cathode material into the solution, uniformly mixing to obtain slurry, carrying out spray drying on the slurry to obtain dry powder, calcining the dry powder in an oxygen-filled atmosphere, cooling to room temperature, grinding and screening to obtain the vanadium pentoxide-coated high-nickel ternary lithium ion battery cathode material. The nickel-cobalt-aluminum cathode material prepared by the method provided by the invention has the advantages of narrow and uniform particle size distribution, simplicity in operation, easiness in condition control, good reproducibility, stable electrochemical performance and the like.
Description
The technical field is as follows:
the invention relates to the technical field of lithium ion batteries, in particular to a vanadium pentoxide coated high-nickel ternary lithium ion battery positive electrode material and a preparation method thereof.
Background art:
in order to increase the energy density of lithium ion batteries, higher capacity cathode materials are required. The ternary lithium ion battery is a battery which takes nickel-cobalt as a positive electrode material and takes manganese salt or aluminum salt to stabilize a chemical framework. The nickel-cobalt-manganese ternary positive electrode material is formed by combining nickel, cobalt and manganese according to a certain proportion, mainly comprises NCM111, NCM523, NCM622, NCM811 and the like, and has the advantages of good electrochemical performance, cycle performance, stable structure and the like; the nickel-cobalt-aluminum ternary positive electrode material (NCA) is made of nickel-cobalt-aluminum, has high gram capacity, high energy density and lower material cost, but has lower stability than NCM and is very sensitive to moisture environment. The two types of lithium ion batteries have relatively higher energy density and can balance endurance and stability, so that the two types of lithium ion batteries become the first choice of batteries of electric vehicles at present.
The specific capacity of the high-nickel ternary cathode material is higher. However, the problem of unstable material structure is caused along with the increasing of the nickel content in the system. At present, the size and the morphology of material particles are regulated and controlled mainly through bulk phase doping and surface coating modification of the material, the specific surface area of an electrode material is reduced, lattice distortion generated in the charge and discharge process of the material is inhibited, and side reactions between the surface of a positive electrode material and electrolyte are reduced, so that the circulation stability of the material is realized.
As the Ni content increases, a Residual Lithium Compound (RLC) inevitably exists in the Ni-rich ternary positive electrode material, and its content increases as the Ni content increases. RLC started with Li2O is in the form of O and is reacted with H in the air2O and CO2The reaction is gradually converted into LiOH and Li2CO3. And LiOH and LiPF in the electrolyte6Reaction to produce HF, and Li2CO3The resulting gas expansion during high temperature storage will seriously affect the electrochemical performance of the material and cause potential safety hazards. Therefore, before the material is coated and modified, the material is subjected to water washing pretreatment to reduce the residual alkali amount on the surface of the material. Meanwhile, the stability of the interface is effectively enhanced through surface coating, so that the material can bear Li under larger charge-discharge current+The ion extraction has the influence on the crystal structure of the material, or effectively inhibits the surface side reaction of the electrode, prevents the generation of particle cracks, thereby relieving irreversible structural degradation, optimizing the electron transmission path of the electrode/electrolyte interface and improving the electron conduction rate of the material.
CN107394166A discloses a high-safety double-layer coated lithium nickel cobalt manganese oxide positive electrode material and a preparation method thereof, wherein the core of the positive electrode material is lithium nickel cobalt manganese oxide, and the inner layer is coated with a material V2O5The outer coating material is a high molecular conductive polymer. The technical proposal comprises (1) adopting a coprecipitation method to synthesize Ni0.5Co0.2Mn0.3(OH)2With Li2CO3Calcining to obtain a ternary cathode material (NCM); (2) reacting NCM with NH4VO3Mixing the aqueous solution, continuously stirring and evaporating to remove NH4VO3Coated NCM, followed by NH4VO3Placing the coated NCM into a muffle furnace, and roasting at 600 ℃ for 3h to obtain V2O5A coated NCM; (3) will V2O5The coated NCM, the conductive polymer monomer and the sodium p-toluenesulfonate are stirred and mixed uniformly in absolute ethyl alcohol, and FeCl is added3Continuously dropping the oxidant into the mixture, and continuously stirring the mixture under the ice-water bath condition to perform polymerization reaction; then the reaction product is filtered, washed and dried in vacuum to obtain the conducting polymer-VO-NCM. V2O5And LiOH and Li on the surface of NCM material2CO3React to form LiVO3And the reaction between the anode material and HF in the electrolyte is avoided. Meanwhile, the conductive high molecular polymer of the outer layer can play a role in improving the electronic conduction of the material. The method has complicated process, and the double-layer coating material, especially the conductive polymer, is inactive material and can be directly coatedDepending on the electrochemical capacity of the positive electrode material.
CN109546123A discloses a vanadium pentoxide coated core-shell structure gradient nickel-cobalt-manganese cathode material and a preparation method thereof. The preparation method comprises the following steps: (1) aging, filtering, washing and drying the precursor of the positive electrode material; (2) adding a lithium source, grinding, presintering and sintering; (3) ultrasonically mixing the vanadium source and the vanadium source in an alcohol solution for heating reaction; (4) and carrying out heat treatment in an oxygen-containing atmosphere to obtain the ternary cathode material. The coating layer of the vanadium pentoxide can provide a lithium ion channel in the charging and discharging process, so that the ionic conductivity is improved, and the coating layer can provide a protective shell to inhibit the structural change of materials in the charging and discharging process. At the same time, surface V2O5The coating layer has good stability in air and electrolyte, and can better isolate CO in the air2/H2And O and electrolyte greatly improve the air storage performance of the material and the electrochemical cycling stability of the material. In the method, a vanadium source and a positive electrode material are mixed in an alcohol solution, the mixture is stirred, heated and reacted until the mixture is evaporated to dryness to obtain mixed powder, and the appearance surface of secondary particle agglomeration is not smooth and the sphericity is not good.
CN109980204A discloses a method for preparing a vanadium pentoxide coated high-performance ternary cathode material by a surfactant-assisted hydrothermal method, the preparation method comprises: (1) dissolving a nickel-cobalt-manganese source, carbonate and a surfactant in distilled water, fully dissolving, transferring to a reaction kettle, and placing the reaction kettle in an oven to obtain a ternary precursor; (2) dissolving ammonium metavanadate in deionized water, stirring at constant temperature, stopping heating to obtain V2O5A solution; (3) adding a mixture obtained by grinding a precursor and a lithium source into V2O5Uniformly stirring and drying the solution, sintering the mixture step by step in a muffle furnace under the air atmosphere, and naturally cooling to room temperature to obtain LiNi1/3Co1/3Mn1/3O2/V2O5. The agglomeration phenomenon of the particles of the positive electrode material obtained by the method is serious, and the method has certain influence on the cycle performance of the electrode material.
All the above-mentioned patent applications make V on ternary or other positive electrode materials2O5And (4) coating modification. But the solution is directly evaporated by heating or a common drying mode is adopted, so that the agglomeration phenomenon of the coated material is easily caused, and the electrochemical performance of the electrode material is not favorably exerted; and the coating material, the precursor and the lithium source are directly mixed and calcined to obtain the cathode material with the coating layer. Residual lithium still exists on the surface of the cathode material obtained by adopting the coating mode, so that the coating effect cannot be expected, and the improvement of the performance of the cathode material is limited to a certain extent.
The invention content is as follows:
in order to solve the problems in the prior art, the invention provides a vanadium pentoxide-coated high-nickel ternary lithium ion battery positive electrode material and a preparation method thereof.
The invention aims to provide a preparation method of a vanadium pentoxide-coated high-nickel ternary lithium ion battery anode material, which comprises the following steps:
(1) according to the mass ratio of the nickel-cobalt-aluminum anode material to the deionized water of 1: adding a nickel-cobalt-aluminum anode material into deionized water by 20-30 parts, stirring and washing, and performing vacuum drying to obtain a washed ternary anode material;
(2) dissolving a vanadium source in a medium to form a solution, putting the ternary cathode material obtained in the step (1) into the solution, uniformly mixing to obtain slurry, carrying out spray drying on the slurry to obtain dry powder, calcining the dry powder at 500-700 ℃ in an oxygen-filled atmosphere, keeping the temperature for 2-5h, cooling to room temperature, and grinding and screening to obtain the vanadium pentoxide-coated high-nickel ternary lithium ion battery cathode material.
The preparation method of the invention is realized by virtue of V in the shell2O5The coating layer stabilizes the crystal structure of the material, avoids the dissolution of transition metal ions in the long-term circulation process and achieves the aim of improving the electrochemical performance; meanwhile, the washing process before coating is favorable for improving the bonding strength of the coating layer and the coated material, thereby avoiding the coating layerPowdering and falling off.
Preferably, the nickel-cobalt-aluminum cathode material is LiNi0.88Co0.07Al0.05O2And (3) a positive electrode material.
Preferably, the step (1) of adding the nickel-cobalt-aluminum positive electrode material into deionized water, stirring and washing, and drying to obtain the washed nickel-cobalt-aluminum positive electrode material specifically comprises the following steps: adding the nickel-cobalt-aluminum cathode material into deionized water, magnetically stirring for 30min at room temperature, washing for a plurality of times, filtering, and drying in a vacuum drying oven at 80-100 ℃ for 12-24h to obtain the washed nickel-cobalt-aluminum cathode material.
Preferably, the specific steps of dissolving the vanadium source in the medium to form a solution are as follows: dissolving ammonium metavanadate in an aqueous solution at 50 ℃ to form an ammonium metavanadate aqueous solution, wherein the solid-to-liquid ratio of the ammonium metavanadate to water is 0.13-0.65:90 g/mL.
Preferably, the mass ratio of the vanadium source to the ternary cathode material in the step (2) is 0.013-0.065: 1.
Preferably, the specific conditions of the spray drying in the step (2) are that the inlet air temperature is 250 ℃, the outlet air temperature is 140 ℃, and the feeding rate is 300 mL/h.
The invention also protects the vanadium pentoxide coated high-nickel ternary lithium ion battery anode material prepared by the preparation method, and the chemical general formula of the vanadium pentoxide coated high-nickel ternary lithium ion battery anode material is LiNi0.88Co0.07Al0.05O2-xV2O5Wherein x is more than or equal to 1% and less than or equal to 5%.
The vanadium pentoxide-coated high-nickel ternary lithium ion battery positive electrode material prepared by the method has the advantages of narrow and uniform particle size distribution, low heat treatment temperature, easiness in operation, easiness in condition control, good reproducibility, stable electrochemical performance and the like.
The invention also protects a lithium ion battery, and the vanadium pentoxide-coated high-nickel ternary lithium ion battery anode material is used as the anode material.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the high nickel-cobalt-aluminum positive electrode material is washed, the residual lithium compound on the surface of the material is reduced, the positive electrode material coated with ammonium metavanadate is obtained in a spray drying mode, and the positive electrode material with a vanadium pentoxide coating layer is obtained after calcination.
2. The method proposed by the invention is based on V in the housing2O5The coating layer stabilizes the crystal structure of the material, avoids the dissolution of transition metal ions in the long-term circulation process and achieves the aim of improving the electrochemical performance. And meanwhile, the washing process before coating is favorable for improving the bonding strength of the coating layer and the coated material, so that the coating layer is prevented from being pulverized and falling off.
3. The nickel-cobalt-aluminum cathode material prepared by the method provided by the invention has the advantages of narrow and uniform particle size distribution, low heat treatment temperature, simple operation, easily controlled conditions, good reproducibility, stable electrochemical performance and the like.
Drawings
FIG. 1 is an XRD pattern of example 5 of the present invention and comparative example 2;
FIG. 2 is an SEM photograph of example 5 of the present invention;
FIG. 3 is an SEM photograph of comparative example 1 of the present invention;
FIG. 4 is an SEM photograph of comparative example 2 of the present invention;
FIG. 5 is a graph of cycle performance for examples 5, 12 and comparative examples 1-2.
The specific implementation mode is as follows:
the technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art. The room temperature proposed by the present invention means 25 ℃.
The chemical general formula of the vanadium pentoxide-coated high-nickel ternary lithium ion battery anode material is LiNi0.88Co0.07Al0.05O2-xV2O5Wherein x is more than or equal to 1% and less than or equal to 5%.
A preparation method of a vanadium pentoxide-coated high-nickel ternary lithium ion battery positive electrode material comprises the following steps:
(1) according to the mass ratio of the nickel-cobalt-aluminum anode material to the deionized water of 1: adding a nickel-cobalt-aluminum anode material into deionized water in an amount of 20-30, performing magnetic stirring at room temperature for 30min, washing for a plurality of times, filtering, and drying in a vacuum drying oven at 80-100 ℃ for 12-24h to obtain a washed ternary anode material;
(2) dissolving a vanadium source in a medium to form a solution, putting the ternary cathode material obtained in the step (1) into the solution, uniformly mixing to obtain slurry, carrying out spray drying on the slurry to obtain dry powder, calcining the dry powder at 500-700 ℃ in an oxygen-filled atmosphere, keeping the temperature for 2-5h, cooling to room temperature, and grinding and screening to obtain the vanadium pentoxide-coated high-nickel ternary lithium ion battery cathode material.
In the invention, the nickel-cobalt-aluminum cathode material is LiNi0.88Co0.07Al0.05O2And (3) a positive electrode material. The invention is directed to LiNi0.88Co0.07Al0.05O2The source of the positive electrode material is not particularly limited, and commercially available products or self-products known to those skilled in the art may be used.
In the invention, the dry powder in the step (2) is calcined at 500-700 ℃ in the atmosphere filled with oxygen and is kept for 2-5h, and the calcination at 600 ℃ is preferably carried out in the following embodiment and is kept for 2 h.
In the present invention, the source of vanadium is preferably ammonium metavanadate, and the source of ammonium metavanadate in the present invention is not particularly limited, and commercially available products or self-products known to those skilled in the art may be used. In the following examples, the preferable medium is water, the solid-to-liquid ratio of ammonium metavanadate to water is 0.13-0.65:90g/mL, and the mass ratio of the vanadium source to the ternary cathode material is 0.013-0.065: 1.
In the invention, the specific conditions of spray drying in the following examples are that the inlet air temperature is 250 ℃, the outlet air temperature is 140 ℃, and the feeding rate is 300 mL/h.
The following examples andthe anode material prepared by the comparative example is made into a 2032 button type simulation battery to test the electrochemical performance. The method comprises the following specific steps: (1) respectively weighing the positive electrode material, the conductive acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 80:10:10, firstly dissolving the PVDF in a proper amount of N-methyl pyrrolidone (NMP), then adding the uniformly mixed active substance and acetylene black powder into the NMP, and uniformly stirring to prepare slurry; (2) uniformly coating the slurry on an aluminum foil substrate, putting the wet electrode into a vacuum drying oven, drying at 80 ℃ for 12h, and cutting into positive plates; (3) in a dry vacuum glove box, a simulated cell was assembled. Taking the self-made positive plate as a positive electrode, a metal lithium plate as a negative electrode, a Celgard 2500 membrane as a diaphragm and 1mol/L LiPF6The electrochemical performance was tested using a solution of Ethylene Carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) (volume ratio 1:1:1) as the electrolyte.
Example 1
(1) In terms of LiNi0.88Co0.07Al0.05O2Materials: the mass ratio of the deionized water is 1: 25 adding LiNi to deionized water0.88Co0.07Al0.05O2Magnetically stirring the materials at room temperature for 30min, washing for 3 times, wherein the pH value of a washing solution is 11.55, filtering, drying for 24h at 80 ℃ in a vacuum drying oven, and grinding and screening to obtain a washed ternary cathode material;
(2) and (2) dissolving 3.25g of ammonium metavanadate in 450mL of 50 ℃ aqueous solution, fully dissolving to obtain an ammonium metavanadate aqueous solution, and putting 50.00g of the ternary cathode material obtained in the step (1) into the ammonium metavanadate aqueous solution to be uniformly mixed to obtain slurry. And (3) carrying out spray drying on the slurry under the set conditions of the air inlet temperature of 250 ℃, the air outlet temperature of 140 ℃ and the feeding rate of 300mL/h to obtain dry powder. 3.00g of dry powder is taken, calcined in an atmosphere furnace filled with oxygen at 600 ℃, kept warm for 2 hours and finally cooled to room temperature along with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-5％V2O5A ternary positive electrode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Example 2
Working examples1 spray drying to obtain 3.00g of dry powder, calcining at 600 ℃ in an atmosphere furnace filled with oxygen, keeping the temperature for 5 hours, and finally cooling to room temperature along with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-5％V2O5A ternary positive electrode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Example 3
3.00g of the dried powder obtained by spray drying in example 1 was calcined in an atmosphere furnace charged with oxygen at 700 ℃ for 2 hours, and finally cooled to room temperature with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-5％V2O5A ternary positive electrode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Example 4
0.65g of ammonium metavanadate is dissolved in 450mL of aqueous solution at 50 ℃, ammonium metavanadate aqueous solution is obtained after full dissolution, and 50.00g of the ternary cathode material obtained in the step (1) in the example 1 is put into the ammonium metavanadate aqueous solution and mixed uniformly to obtain slurry. And (3) carrying out spray drying on the slurry under the set conditions of the air inlet temperature of 250 ℃, the air outlet temperature of 140 ℃ and the feeding rate of 300 mL/h. 3.00g of dry powder is taken, calcined in an atmosphere furnace filled with oxygen at 600 ℃, kept warm for 2 hours and finally cooled to room temperature along with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-1％V2O5A ternary positive electrode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Example 5
3.00g of the dried powder obtained by spray drying in example 4 was calcined in an atmosphere furnace charged with oxygen at 600 ℃ for 5 hours, and finally cooled to room temperature with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-1％V2O5A ternary positive electrode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Example 6
The dry powder 3 obtained in example 4 by spray drying was taken00g, calcining at 500 ℃ in an atmosphere furnace filled with oxygen, preserving heat for 5 hours, and finally cooling to room temperature along with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-1％V2O5A ternary positive electrode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Example 7
3.00g of the dried powder obtained by spray drying in example 4 was calcined in an atmosphere furnace charged with oxygen at 550 ℃ for 5 hours, and finally cooled to room temperature with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-1％V2O5A ternary positive electrode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Example 8
3.00g of the dried powder obtained by spray drying in example 4 was calcined in an atmosphere furnace charged with oxygen at 650 ℃ for 5 hours, and finally cooled to room temperature with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-1％V2O5A ternary positive electrode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Example 9
3.00g of the dried powder obtained by spray drying in example 4 was calcined in an atmosphere furnace charged with oxygen at 700 ℃ for 5 hours, and finally cooled to room temperature with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-1％V2O5A ternary positive electrode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Example 10
Dissolving 1.30g of ammonium metavanadate in 450mL of 50 ℃ aqueous solution, fully dissolving to obtain an ammonium metavanadate aqueous solution, putting 50.00g of the ternary cathode material obtained in the step (1) in the example 1 into the ammonium metavanadate aqueous solution, and carrying out spray drying on the slurry under the set conditions of the air inlet temperature of 250 ℃, the air outlet temperature of 140 ℃ and the feeding rate of 300mL/h to obtain dry powder. Taking 3.00g of dry powder, and placing in an atmosphere furnace filled with oxygenCalcining at 500 ℃, preserving heat for 5 hours, and finally cooling to room temperature along with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-2％V2O5A ternary positive electrode material. Using LiNi0.88Co0.07Al0.05O2-2％V2O5The test results of button cell made of ternary positive electrode material are shown in table 1.
Example 11
3.00g of the dried powder obtained by spray drying in example 10 was calcined in an atmosphere furnace charged with oxygen at 550 ℃ for 5 hours, and finally cooled to room temperature with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-2％V2O5A ternary positive electrode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Example 12
3.00g of the dried powder obtained by spray drying in example 10 was calcined in an atmosphere furnace charged with oxygen at 600 ℃ for 5 hours, and finally cooled to room temperature with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-2％V2O5A ternary positive electrode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Example 13
3.00g of the dried powder obtained by spray drying in example 10 was calcined in an atmosphere furnace charged with oxygen at 650 ℃ for 5 hours, and finally cooled to room temperature with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-2％V2O5A ternary positive electrode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Example 14
3.00g of the dried powder obtained by spray drying in example 10 was calcined in an atmosphere furnace charged with oxygen at 700 ℃ for 5 hours, and finally cooled to room temperature with the furnace. Grinding and sieving to obtain LiNi0.88Co0.07Al0.05O2-2％V2O5A ternary positive electrode material. Button made of ternary anode materialThe test results for the cells are shown in table 1.
Example 15
(1) According to the mass ratio of the nickel-cobalt-aluminum anode material to the deionized water of 1: 20 to deionized Water0.88Co0.07Al0.05O2Magnetically stirring the material at room temperature for 30min, washing for 3 times, wherein the pH value is 11.55, filtering, and drying at 90 ℃ for 18h in a vacuum drying oven to obtain a ternary cathode material;
(2) dissolving 1.30g of ammonium metavanadate in 450mL of 50 ℃ aqueous solution, fully dissolving to obtain an ammonium metavanadate aqueous solution, putting 50.00g of the ternary positive electrode material obtained in the step (1) into the ammonium metavanadate aqueous solution, uniformly mixing to obtain slurry, carrying out spray drying on the slurry under the set conditions of the air inlet temperature of 250 ℃, the air outlet temperature of 140 ℃ and the feeding rate of 300mL/h to obtain dry powder, calcining 3.00g of the dry powder at 600 ℃ in an oxygen-filled atmosphere, preserving heat for 5h, cooling to room temperature, grinding and screening to obtain the vanadium pentoxide-coated high-nickel ternary lithium ion battery positive electrode material.
Example 16
(1) According to the mass ratio of the nickel-cobalt-aluminum anode material to the deionized water of 1: 30 to deionized Water0.88Co0.07Al0.05O2Magnetically stirring the material at room temperature for 30min, washing for 3 times, wherein the pH value is 11.55, filtering, and drying in a vacuum drying oven at 100 ℃ for 12h to obtain a ternary cathode material;
(2) dissolving 1.30g of ammonium metavanadate in 450mL of 50 ℃ aqueous solution, fully dissolving to obtain an ammonium metavanadate aqueous solution, putting 50.00g of the ternary positive electrode material obtained in the step (1) into the ammonium metavanadate aqueous solution, uniformly mixing to obtain slurry, carrying out spray drying on the slurry under the set conditions of the air inlet temperature of 250 ℃, the air outlet temperature of 140 ℃ and the feeding rate of 300mL/h to obtain dry powder, calcining 3.00g of the dry powder at 600 ℃ in an oxygen-filled atmosphere, preserving heat for 5h, cooling to room temperature, grinding and screening to obtain the vanadium pentoxide-coated high-nickel ternary lithium ion battery positive electrode material.
Comparative example 1
100.00g of LiNi was taken0.88Co0.07Al0.05O2Material, according to LiNi0.88Co0.07Al0.05O2Materials: the mass ratio of the deionized water is 1: 25 adding LiNi to deionized water0.88Co0.07Al0.05O2And magnetically stirring the materials at room temperature for 30min, washing for 3 times, wherein the pH value of a washing solution is 11.55, filtering, drying for 24h at 80 ℃ in a vacuum drying oven, and grinding and screening to obtain the washed ternary cathode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Comparative example 2
100.00g of LiNi was taken0.88Co0.07Al0.05O2Material, according to LiNi0.88Co0.07Al0.05O2Materials: the mass ratio of the deionized water is 1: and 25, magnetically stirring for 30min at room temperature, washing for 3 times, wherein the pH value is 11.55, filtering, drying for 24h at 80 ℃ in a vacuum drying oven, and grinding and screening to obtain the washed cathode material. And 3.00g of the washed anode material is taken, calcined in an atmosphere furnace filled with oxygen at 600 ℃, kept warm for 2h, and finally cooled to room temperature along with the furnace. And grinding and screening to obtain the ternary cathode material. The test results for button cells made with the ternary positive electrode material are shown in table 1.
Button cells were fabricated using the positive electrode materials of examples 1-14 and comparative examples 1-2 and tested for electrochemical performance, as shown in table 1.
TABLE 1 electrochemical Properties of cathode materials of examples 1-14 and comparative examples 1-2
As shown in Table 1, the first discharge specific capacity of 0.2 of the material of example 5 was 209.2mAh/g, and the first charge-discharge efficiency was 83.0%. After the material is circulated for 100 weeks at the multiplying power of 1C, the discharge specific capacity still has 147.5mAh/g, the capacity retention rate reaches 78.5 percent, and the material is stable in circulationThe qualitative performance is better than that of comparative example 2, and the first discharge specific capacity of 0.2C is much higher than that of comparative example 1. The material of example 5 is shown to avoid irreversible capacity caused by side reaction due to direct contact of the active material with the electrolyte by means of a vanadium pentoxide coating layer. Meanwhile, the calcination process decomposes ammonium metavanadate into oxides on one hand, and aggravates Ni for water washing on the other hand3+Reduced Ni2+Is oxidized again to Ni3+. In addition, example 12 is superior to comparative example 2 in electrochemical capacity and cycle stability. As seen from FIG. 1, the positive electrode materials before and after the vanadium pentoxide coating all exhibited LiNiO2Typical structural characteristics of the anode material are that the diffraction peak is alpha-NaFeO2The characteristic peak of the layered structure belongs to a hexagonal system, R-3m space group. (006) The two pairs of diffraction peaks of (012) and (018)/(110) are clearly split and the lamellar structure develops completely. The diffraction peaks of the materials before and after coating have no significant change and no impurity peaks. As can be seen from fig. 2 to 4, the positive electrode materials of example 5 and comparative examples 1 and 2 are composed of primary particles agglomerated to form secondary particles having a particle size of about 10 to 15 μm. Wherein the particle surfaces of the materials of example 5 and comparative example 2 were very smooth compared to comparative example 1. Fig. 5 shows the trend of the capacity of the positive electrode material before and after the coating modification as the process of lithium intercalation and deintercalation of the electrode material continues. The method shows that the proper vanadium pentoxide coating amount can effectively improve the cycling stability of the material.
The above embodiments are only for the purpose of helping understanding the technical solution of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (8)
1. A preparation method of a vanadium pentoxide-coated high-nickel ternary lithium ion battery positive electrode material is characterized by comprising the following steps:
(1) according to the mass ratio of the nickel-cobalt-aluminum anode material to the deionized water of 1: adding a nickel-cobalt-aluminum anode material into deionized water by 20-30 parts, stirring and washing, and drying to obtain a washed ternary anode material;
(2) dissolving a vanadium source in a medium to form a solution, putting the ternary cathode material obtained in the step (1) into the solution, uniformly mixing to obtain slurry, carrying out spray drying on the slurry to obtain dry powder, calcining the dry powder at 500-700 ℃ in an oxygen-filled atmosphere, keeping the temperature for 2-5h, cooling to room temperature, and grinding and screening to obtain the vanadium pentoxide-coated high-nickel ternary lithium ion battery cathode material.
2. The method for preparing the vanadium pentoxide coated high-nickel ternary lithium ion battery cathode material according to claim 1, wherein the nickel-cobalt-aluminum cathode material is LiNi0.88Co0.07Al0.05O2And (3) a positive electrode material.
3. The method for preparing the vanadium pentoxide coated high-nickel ternary lithium ion battery cathode material according to claim 1, wherein the step (1) of adding the nickel-cobalt-aluminum cathode material into deionized water, stirring and washing the mixture, and drying the mixture to obtain the washed nickel-cobalt-aluminum cathode material comprises the following specific steps: adding the nickel-cobalt-aluminum cathode material into deionized water, magnetically stirring for 30min at room temperature, washing for a plurality of times, filtering, and drying in a vacuum drying oven at 80-100 ℃ for 12-24h to obtain the washed nickel-cobalt-aluminum cathode material.
4. The method for preparing the vanadium pentoxide coated high-nickel ternary lithium ion battery positive electrode material according to claim 1, wherein the specific steps of dissolving a vanadium source in a medium to form a solution are as follows: dissolving ammonium metavanadate in an aqueous solution at 50 ℃ to form an ammonium metavanadate aqueous solution, wherein the solid-to-liquid ratio of the ammonium metavanadate to water is 0.13-0.65:90 g/mL.
5. The method for preparing the vanadium pentoxide coated high-nickel ternary lithium ion battery cathode material as claimed in claim 1, wherein the mass ratio of the vanadium source to the ternary cathode material in the step (2) is 0.013-0.065: 1.
6. The preparation method of the vanadium pentoxide coated high-nickel ternary lithium ion battery cathode material according to claim 1, wherein the specific conditions of the spray drying in the step (2) are that the air inlet temperature is 250 ℃, the air outlet temperature is 140 ℃, and the feeding rate is 300 mL/h.
7. The vanadium pentoxide coated high-nickel ternary lithium ion battery positive electrode material prepared by the preparation method of the vanadium pentoxide coated high-nickel ternary lithium ion battery positive electrode material of claim 2, wherein the chemical general formula of the vanadium pentoxide coated high-nickel ternary lithium ion battery positive electrode material is LiNi0.88Co0.07Al0.05O2-xV2O5Wherein x is more than or equal to 1% and less than or equal to 5%.
8. A lithium ion battery is characterized in that the vanadium pentoxide-coated high-nickel ternary lithium ion battery positive electrode material of claim 7 is adopted as the positive electrode material.
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