CN109216688B - Ternary lithium battery material, preparation method thereof and lithium ion battery - Google Patents
Ternary lithium battery material, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention provides a preparation method of a ternary lithium battery material, which comprises the following steps: A) performing ball milling activation on a nickel source, a cobalt source and a manganese source to obtain a mixed material; B) mixing the mixed material, a lithium source, a fluxing agent, a compound of M and polyvinyl alcohol, and pressing after spray drying to obtain a block; C) roasting and crushing the blocks to obtain a monocrystal-like ternary material; D) grinding and roasting the single-crystal-like ternary material and the coating source to obtain a ternary lithium battery material; the coating source is LiCO3And LiOH. H2One of O and Al2O3、ZrO2And TiO2One or more of (a). The application also provides the ternary lithium battery material and a lithium ion battery. According to the preparation method of the ternary lithium battery material, the raw materials are subjected to self-melting reaction to synthesize the single crystal-like ternary positive electrode material at one time, the particle size is large, the distribution is uniform, and the ternary positive electrode material serving as the positive electrode material is excellent in high-temperature storage performance and high-temperature cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrode materials, in particular to a ternary lithium battery material, a preparation method thereof and a lithium ion battery.
Background
In recent years, lithium ion batteries have been widely used in notebooks due to their high specific energy, small size, light weight, and long cycle performancePortable electronic devices such as computers, digital cameras, and mobile devices are increasingly being used in high-power devices such as electric vehicles, hybrid electric vehicles, and energy storage power supplies. In order to meet the requirements of high-power equipment, the development of a positive electrode material with high energy density, low cost and good high-voltage cycling stability becomes a research hotspot of a battery positive electrode material. Nickel cobalt lithium manganate (NCM) ternary positive electrode material (LiNi)xCoyMn1-x-yO2X is more than 0 and y is less than 1), has the advantages of high energy density, good safety performance and low cost, and becomes a new generation of lithium battery anode material.
The commercial NCM ternary cathode material is mostly used for a battery with a charging voltage of 4.2V, the specific capacitance ranges from 140 mAh/g to 200mAh/g, and the realization of higher utilization of the theoretical capacity (275mAh/g) of the ternary material by increasing the charging voltage (> 4.3V) is an effective means. At present, the factors influencing the cycle life of the ternary material are as follows: 1) reconstructing the surface crystal structure in the circulation process; 2) secondary particle fracture due to anisotropic volume expansion during cycling. Research shows that the particle-particle connection structure inside the secondary particles can cause local current density increase, so that great stress is generated, and the cycle performance of the material is influenced; meanwhile, there is a phenomenon in which the state of charge is not uniform among the respective portions inside the particles, which affects the electrochemical performance of the electrode.
In addition, when the lithium removal amount is large, the structure of the NCM ternary material becomes very fragile, active metal and oxygen in crystal lattices are displaced to reach a certain high temperature and high pressure, atom rearrangement and reconstruction are gradually intensified, and the crystal particle volume and the phase are greatly changed; on the other hand, the electrolyte reacts with the electrolyte chemically and electrochemically, so that the material is easy to deoxidize and the transition metal is dissolved, and the electrolyte is oxidized to generate H especially under high voltage+The acidity of the electrolyte is improved, so that the surface film of the electrode material is damaged by HF, the components and the structure of the interface are further changed, and the electrochemical performance and the cycle performance of the material are seriously influenced.
At present, the methods for preparing single crystal ternary materials generally comprise: firstly, preparing a nickel-cobalt-manganese hydroxide precursor or a nickel-cobalt-manganese oxalate precursor by using a nickel-cobalt-manganese sulfate through a coprecipitation method, and then adding a lithium source to roast to obtain the ternary cathode material.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a ternary lithium battery material, and the ternary lithium battery material prepared by the preparation method provided by the application has large particle size and uniform particle size distribution without micro powder, so that the ternary lithium battery material has excellent high-temperature storage performance and high-temperature cycle performance.
In view of this, the present application provides a preparation method of a ternary lithium battery material, including the following steps:
A) performing ball milling activation on a nickel source, a cobalt source and a manganese source to obtain a mixed material;
B) mixing the mixed material, a lithium source, a fluxing agent, a compound of M and polyvinyl alcohol, and pressing after spray drying to obtain a block; m in the compound of M is selected from one or more of aluminum, magnesium, titanium, zirconium, iron, calcium, zinc, silicon, lanthanides and actinides;
C) roasting and crushing the blocks to obtain a monocrystal-like ternary material;
D) grinding and roasting the single-crystal-like ternary material and the coating source to obtain a ternary lithium battery material; the coating source is LiCO3And LiOH. H2One of O and Al2O3、ZrO2And TiO2One or more of;
the adding amount of the compounds of the nickel source, the cobalt source, the manganese source, the lithium source and the M is added according to the corresponding molar ratio of the compound shown in the formula (II),
LiNixCoyMnzMaO2 (Ⅱ)；
wherein x is more than or equal to 0.2 and less than or equal to 0.9, y is more than 0 and less than or equal to 0.4, z is more than or equal to 0.1 and less than or equal to 0.5, and a is more than 0 and less than or equal to 1-x-y-z and less than or equal to 0.05;
the lithium source is added according to the ratio of Li: (Ni + Co + Mn) is added in a molar ratio of 1.05-1.10: 1.
Preferably, the D50 particle size of the nickel source is 1-3 μm, the D50 particle size of the cobalt source is 5-20 μm, and the D50 particle size of the manganese source is 1-3 μm; the particle size of the mixed material is 5-20 mu m.
Preferably, in the step A), the rotation speed of the ball milling activation is 100-500 r/min, and the time is 1-3 h.
Preferably, the fluxing agent is one or more of polyethylene glycol, lithium borate and lithium phosphate, the polyvinyl alcohol is a polyvinyl alcohol solution with the concentration of 10%, and the polyvinyl alcohol is 10% -20% of the total mass of the nickel source, the cobalt source and the manganese source.
Preferably, in the step C), the roasting is carried out in the air or oxygen atmosphere, the roasting temperature is 850-950 ℃, and the roasting time is 12-15 hours.
Preferably, in the step D), the roasting temperature is 600-900 ℃ and the roasting time is 5-7 h.
Preferably, the nickel source is an oxide or carbonate of nickel, the cobalt source is an oxide or carbonate of cobalt, and the manganese source is an oxide or carbonate of manganese; the lithium source is lithium carbonate or lithium hydroxide; the compound of M is one or more of sulfate, nitrate, chloride and oxide of M.
The application also provides a ternary lithium battery material prepared by the preparation method, which consists of a nickel-cobalt-manganese multi-component material shown as a formula (I) and a coating layer N coated on the surface of the nickel-cobalt-manganese multi-component material;
LiNixCoyMnzMaO2 (Ⅰ)；
wherein x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0.1 and less than or equal to 0.5, and a is more than 0 and less than or equal to 1-x-y-z and less than or equal to 0.05;
m is selected from one or more of aluminum, magnesium, titanium, zirconium, iron, calcium, zinc, silicon, lanthanides and actinides;
the N cladding layer is selected from LiAlO2、Li2ZrO3、Li2TiO3One or more of (a).
Preferably, the particle size of the ternary lithium battery material is 5-20 mu m, and the compaction density is more than or equal to 3.6g/cm3。
The application also provides a lithium ion battery, which comprises an anode and a cathode, wherein the anode is made of the ternary lithium battery material prepared by the preparation method or the ternary lithium battery material prepared by the preparation method.
The application provides a preparation method of a ternary lithium battery material, which comprises the steps of mixing a nickel source, a cobalt source and a manganese source, performing ball milling activation to obtain a mixed material, mixing the mixed material, a lithium source, a compound of M and an auxiliary agent, pressing to obtain a block, roasting and crushing the block, and roasting the obtained monocrystal-like ternary material and a coating source to obtain the ternary lithium battery material. In the preparation process, firstly, the raw materials are refined by ball milling activation to be beneficial to controlling the particle size of the mixed materials, and then the contact area and the contact distance between the raw materials are increased by pressing treatment to be beneficial to increasing the heat conduction between the raw materials in the later sintering process and further promoting the self-fusion between the nickel, cobalt and manganese raw materials and the growth of particles; therefore, the new preparation method is adopted, and the particle size and distribution uniformity of the ternary lithium source material are improved. Further, the particle sizes of the nickel source, the cobalt source and the manganese source are preferably limited, so that the ternary lithium battery material with larger particle size can be prepared.
Drawings
Fig. 1 is a scanning electron micrograph of a ternary lithium battery material prepared in example 1 of the present invention;
fig. 2 is a scanning electron micrograph of the ternary lithium battery material prepared in example 2 of the present invention;
fig. 3 is a scanning electron micrograph of the ternary lithium battery material prepared in example 3 of the present invention;
fig. 4 is a graph illustrating cycle performance of the ternary lithium battery material prepared according to the embodiment of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The invention provides a preparation method of a ternary lithium battery material, aiming at the problems that the ternary positive electrode material in the prior art is small in particle size and easy to generate micro powder to influence the cycling stability and safety of a battery, the ternary lithium battery material prepared by the method is large in particle size, uniform in distribution and free of micro powder, complete in structure and good in processing performance, and can be used as the positive electrode material without particle fragmentation in the cycling process, so that the direct contact between the surface of the material and an electrolyte, particularly the contact with HF in the electrolyte, is effectively prevented, the occurrence of side reaction is prevented, the crystal structure of the material is stabilized, and the ternary lithium battery material can be applied to a lithium ion battery, particularly a high-voltage power type lithium ion battery, and the high-temperature high-voltage cycling performance, particularly the high-temperature stability and the storage performance of the battery can. Specifically, the preparation method of the ternary lithium battery material specifically comprises the following steps:
A) performing ball milling activation on a nickel source, a cobalt source and a manganese source to obtain a mixed material;
B) mixing the mixed material, a lithium source, a fluxing agent, a compound of M and polyvinyl alcohol, and pressing after spray drying to obtain a block; m in the compound of M is selected from one or more of aluminum, magnesium, titanium, zirconium, iron, calcium, zinc, silicon, lanthanides and actinides;
C) roasting and crushing the blocks to obtain a monocrystal-like ternary material;
D) grinding and roasting the single-crystal-like ternary material and the coating source to obtain a ternary lithium battery material; the coating source is LiCO3And LiOH. H2One of O and Al2O3、ZrO2And TiO2One of (1);
the adding amount of the compounds of the nickel source, the cobalt source, the manganese source, the lithium source and the M is added according to the corresponding molar ratio of the compound shown in the formula (II),
LiNixCoyMnzMaO2 (Ⅱ)；
wherein x is more than or equal to 0.2 and less than or equal to 0.9, y is more than 0 and less than or equal to 0.4, z is more than or equal to 0.1 and less than or equal to 0.5, and a is more than 0 and less than or equal to 1-x-y-z and less than or equal to 0.05;
the lithium source is added according to the ratio of Li: (Ni + Co + Mn) is added in a molar ratio of 1.05-1.10: 1.
In the process of preparing the ternary lithium battery material, firstly, premixing raw materials, namely, performing ball milling activation on a nickel source, a cobalt source and a manganese source to form a mixed material; in the process, the D50 particle size of the nickel source is 1-3 μm, the D50 particle size of the cobalt source is 5-20 μm, and the D50 particle size of the manganese source is 1-3 μm; the particle size of the mixed material is 5-20 mu m. The particle size ranges of the nickel source, the cobalt source and the manganese source are prepared for the particle sizes of the cobalt source, the nickel source and the manganese source after self-fusion in the subsequent sintering stage; meanwhile, the particle size of the cobalt source is larger, the particle size of the nickel source and the particle size of the manganese source are smaller, so that the large-particle-size raw material is used as a core, the particle size range after sintering is determined, and in the sintering self-fusion process, the two small-particle-size raw materials are fused to the large-particle-size raw material, so that the required reaction power is smaller. The ball milling activation process is well known to those skilled in the art, and the specific operation means thereof is not particularly limited in the present application. The rotation speed of ball milling activation is 100-500 r/min, and the time is 1-3 h. For purposes of this application, the nickel, cobalt and manganese sources are all well known to those skilled in the art and are specifically oxides or carbonates of nickel, cobalt and manganese.
After the mixed material is obtained, mixing the mixed material with a lithium source, a fluxing agent, a compound of M and polyvinyl alcohol, and pressing after spray drying to obtain a block; wherein M is bulk doping element in the ternary cathode material. The fluxing agent is selected from one or more of polyethylene glycol, lithium borate and lithium phosphate, and fusion growth of raw material particles is facilitated; the polyvinyl alcohol is a polyvinyl alcohol solution with the concentration of 10 percent, and is 10 to 20 percent of the total mass of the nickel source, the cobalt source and the manganese source. M in the compound of M is specifically selected from one or more of aluminum, magnesium, titanium, zirconium, iron, calcium, zinc, silicon, lanthanides and actinides; more specifically one or more selected from the group consisting of aluminum, magnesium, titanium, zinc, and silicon; the chemical substance of M is one or more of sulfate, nitrate, chloride and oxide of M; the lithium source is lithium hydroxide or lithium carbonate. The pressing process increases the contact area and the contact distance between the raw materials, is beneficial to the heat conduction between the raw materials in the subsequent sintering and is beneficial to the growth of self-fused particles between the nickel, cobalt and manganese raw materials.
According to the invention, the obtained blocks are roasted and crushed to obtain the single crystal-like ternary material; the roasting is a process of fusing raw materials to form a solid solution, and a nickel source, a cobalt source, a manganese source and a lithium source are fused and reacted with each other at high temperature to form the solid solution; because the nickel source, the cobalt source, the manganese source and the lithium source are all non-agglomerated particles, the fused cathode material is all single crystal particles. The roasting is preferably carried out in the air or oxygen atmosphere, the roasting temperature is 850-950 ℃, and the roasting time is 12-15 hours.
Finally, grinding and roasting the monocrystal-like ternary positive electrode material and a coating source to obtain the ternary lithium battery material, wherein the coating source is LiCO3And LiOH. H2One of O and Al2O3、ZrO2And TiO2In the above-mentioned method, the coating source reacts during the firing process, thereby forming a coating layer which coats the surface of the mono-like ternary positive electrode material. The roasting temperature is 600-900 ℃, and the roasting time is 5-7 h.
The application also provides a ternary lithium battery material prepared by the scheme, which consists of a nickel-cobalt-manganese multicomponent material shown in a formula (I) and a coating layer N coated on the surface of the nickel-cobalt-manganese multicomponent material;
LiNixCoyMnzMaO2 (Ⅰ)；
wherein x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0.1 and less than or equal to 0.5, and a is more than 0 and less than or equal to 1-x-y-z and less than or equal to 0.05;
m is selected from one or more of aluminum, magnesium, titanium, zirconium, iron, calcium, zinc, silicon, lanthanides and actinides;
the N cladding layer is selected from LiAlO2、Li2ZrO3、Li2TiO3One or more of (a).
The ternary lithium battery material provided by the application is a composite material, and is prepared by a nickel-cobalt-manganese multi-component material and coating the nickel-cobalt-manganese multi-component materialA coating layer N of the surface; the N cladding layer is selected from LiAlO2、Li2ZrO3、Li2TiO3One or more of the nickel, cobalt and manganese composite materials are fast ion conductor materials, on one hand, the nickel, cobalt and manganese composite materials and the electrolyte are isolated, so that the electrolyte is prevented from being oxidized and decomposed on the surface of the anode material, on the other hand, the dynamic performance of the materials is improved, the charging voltage of the battery is more than or equal to 4.4V, and the battery has good high-temperature storage performance and high-voltage cycle performance.
The ternary lithium battery material has the average particle size of 5-20 mu m and the compacted density of more than or equal to 3.6g/cm3。
The application also provides a lithium ion battery, which comprises a positive electrode and a negative electrode, wherein the material of the positive electrode is the ternary lithium battery material.
Compared with the prior art, the invention synthesizes the single crystal-like ternary cathode material once through the self-fusion of the raw materials, does not need to prepare a precursor, has simple process, low cost and easy production, and has large product particle size (5-20 mu m) and compaction density of more than or equal to 3.6g/cm3The particle size distribution is uniform, no micro powder exists, and the high-temperature storage performance and the high-temperature cycle performance are excellent.
For further understanding of the present invention, the following examples are provided to illustrate the ternary lithium battery material and the preparation method thereof, and the scope of the present invention is not limited by the following examples.
Example 1
(1) According to the proportion of Ni: co: weighing high-purity nickelous oxide, high-purity cobalt carbonate and high-purity manganese carbonate in a Mn stoichiometric ratio of 5:2:3, placing the nickelous oxide, the cobalt carbonate and the manganese carbonate into a ball mill, wherein a high-purity nickelous oxide material D50 is 3 microns, a high-purity cobalt carbonate material D50 is 8 microns, and a high-purity manganese carbonate material D50 is 3 microns, and performing ball milling activation for 1h at 150r/min to obtain a nickel-cobalt-manganese mixture A1 of which the D50 is about 6 microns;
(2) mixing the mixture A1 and Li2CO3、Al2O3According to Li: mixing Al (Ni + Co + Mn) in a molar ratio of 1.05:0.01:0.99, adding polyethylene glycol with the mass accounting for 0.95 percent of the total mass of the nickel, the cobalt and the manganese, and adding polyethylene with the mass concentration of 10 percentMixing and dispersing enol aqueous solution, wherein the mass of the enol aqueous solution is 15% of the total mass of nickel, cobalt and manganese in a water system for 3 hours, and pressing the mixture into a block B1 after spray drying treatment;
(3) placing the block B1 in a roasting furnace, introducing air atmosphere, roasting at 950 ℃ for 12h, discharging, cooling to 45-55 ℃, crushing, and sieving with a 200-mesh sieve to obtain a undersize product, namely the quasi-single crystal ternary positive electrode material C1 with the D50 being about 7 mu m;
(4) mixing Li in equal molar ratio2CO3Nano Al2O3Grinding and dispersing in an ethanol solution for 2h, then adding a monocrystal-like ternary positive electrode material C1, grinding and dispersing for 1h, placing the mixed material in a roasting furnace, sintering for 6h at 800 ℃, and obtaining the coated LiAlO according to a reaction equation2Like single crystal ternary positive electrode material D1, LiAlO2The mass of the ternary positive electrode material is 1.0 percent of the total mass of the active substance of the ternary positive electrode material, and the molecular formula of the active substance of the ternary positive electrode material is LiNi0.5Co0.2Mn0.3Al0.01O2；
Li2CO3+Al2O3＝2LiAlO2+CO2 ①。
Fig. 1 is a scanning electron micrograph of the single-crystal-like ternary cathode material prepared in this example.
Example 2
(1) According to the proportion of Ni: co: weighing high-purity nickelous trioxide, high-purity cobaltosic oxide and high-purity manganese dioxide in a Mn stoichiometric ratio of 6:2:2, placing the nickelous trioxide, the cobaltosic oxide and the manganese dioxide into a ball mill, wherein a high-purity nickelous trioxide material D50 is 5 microns, a high-purity cobaltosic oxide material D50 is 10 microns, and a high-purity manganese dioxide material D50 is 8 microns, and performing ball milling activation for 1.5 hours at 300r/min to obtain a nickel-cobalt-manganese mixture A2 of which D50 is about 7 microns;
(2) adding tetrabutyl titanate into isopropanol, preparing tetrabutyl titanate solution with the molar concentration of 1%, and stirring for 10min to obtain solution containing titanium element for later use; mixing the mixed material A2, LiOH and tetrabutyl titanate solution according to the proportion of Li: mixing Ti (Ni + Co + Mn) in the molar ratio of 1.08 to 0.015 to 0.985, and adding Li3BO3The mass of the material is 0.15 percent of the total mass of nickel, cobalt and manganese, and polyvinyl alcohol water solution with the mass concentration of 10 percent is addedMixing and dispersing the aqueous solution with the mass being 18% of the total mass of nickel, cobalt and manganese in a water system for 3 hours, and pressing the mixture into a block B2 after spray drying treatment;
(3) placing the block B2 in a roasting furnace, introducing oxygen atmosphere, roasting at 880 ℃ for 12h, discharging, cooling to 45-55 ℃, crushing, and sieving with a 200-mesh sieve to obtain a undersize product, namely the quasi-single crystal ternary positive electrode material C2 with the D50 being about 9 mu m;
(4) mixing LiOH and nano TiO2Grinding and dispersing in ethanol solution for 2h according to a molar ratio of 2:1, then adding a monocrystal-like ternary positive electrode material C2, grinding and dispersing for 1h, placing the mixed material in a roasting furnace for roasting at 780 ℃ for 6h, and obtaining the coated Li according to a reaction equation2TiO3Like single crystal ternary positive electrode material D2, Li2TiO3The mass of the ternary positive electrode material is 1.2 percent of the total mass of the active substance of the ternary positive electrode material, and the molecular formula of the active substance of the ternary positive electrode material is LiNi0.6Co0.2Mn0.2Ti0.015O2；
2LiOH+TiO2＝Li2TiO3+H2O ②。
Fig. 2 is a scanning electron micrograph of the single-crystal-like ternary cathode material prepared in this example.
Example 3
(1) According to the proportion of Ni: co: weighing high-purity nickelous trioxide, high-purity cobaltosic oxide and high-purity manganese dioxide in a Mn stoichiometric ratio of 8:1:1, placing the nickelous trioxide, the cobaltosic oxide and the manganese dioxide into a ball mill, wherein a high-purity nickelous trioxide material D50 is 8 microns, a high-purity cobaltosic oxide material D50 is 15 microns, and a high-purity manganese dioxide material D50 is 10 microns, and performing ball milling activation for 2 hours at 500r/min to obtain a nickel-cobalt-manganese mixture A3 of which the D50 is about 10 microns;
(2) adding tetrabutyl zirconate into isopropanol, preparing a tetrabutyl zirconate solution with the molar concentration of 1%, and stirring for 10min to obtain a solution containing a zirconium element for later use; mixing the mixture A3, LiOH and tetrabutyl zirconate solution according to the proportion of Li: zr (Ni + Co + Mn) 1.10:0.02:0.98, and Li is added3PO4The mass of the polyvinyl alcohol is 0.18 percent of the total mass of nickel, cobalt and manganese, a polyvinyl alcohol aqueous solution with the mass concentration of 10 percent is added, and the mass of the aqueous solution is 20 percent of the total mass of nickel, cobalt and manganeseMixing and dispersing in a water system for 3 hours, and pressing into a block B3 after spray drying treatment;
(3) placing the blocks in a roasting furnace, introducing oxygen atmosphere, roasting for 12h at 850 ℃, discharging, cooling to 45-55 ℃, crushing, and sieving with a 200-mesh sieve to obtain a undersize product, namely the D50-12 mu m monocrystal-like ternary positive electrode material C3;
(4) LiOH and nano ZrO2Grinding and dispersing in ethanol solution for 2h according to a molar ratio of 2:1, adding a mono-like ternary positive electrode material C3, grinding and dispersing for 1h, placing the mixed material in a roasting furnace for roasting at 750 ℃ for 6h, and obtaining the coated Li according to a reaction equation2ZrO3Like single crystal ternary positive electrode material D3, Li2ZrO3The mass of the ternary positive electrode material is 1.5 percent of the total mass of the active substance of the ternary positive electrode material, and the molecular formula of the active substance of the ternary positive electrode material is LiNi0.8Co0.1Mn0.1Zr0.02O2；
2LiOH+ZrO2＝Li2ZrO3+H2O ③。
Fig. 3 is a scanning electron micrograph of the single-crystal-like ternary cathode material prepared in this example.
Example 4
The method for preparing the full-electric of the secondary lithium ion battery by using the lithium ion battery ternary cathode material with the single-crystal-like laminated structure prepared in the embodiment 1-3 comprises the following steps:
preparing a positive electrode: adding the spherical or spheroidal lamellar structure lithium ion battery anode material, conductive carbon black (S.P) and a polyvinylidene fluoride (PVDF) adhesive into N-methylpyrrolidone (NMP) (the weight ratio of the lithium nickel cobalt manganese anode material to the NMP is 2.1:1) according to the weight ratio of 94:3:3, fully mixing, stirring to form uniform slurry, coating the uniform slurry on an aluminum foil current collector, drying and pressing to form a pole piece;
preparing a negative electrode: adding negative artificial graphite, conductive carbon black (S.P), carboxymethyl cellulose (CMC) and an adhesive (SBR) into sufficient pure water according to the weight ratio of 95:1:1:3, mixing, stirring to form uniform slurry, coating the uniform slurry on a copper foil current collector, drying and pressing to form a pole piece;
the diaphragm is a PP/PE composite film material, the positive and negative pole pieces after being pressed are spot-welded with a pole lug, the diaphragm is inserted, the positive and negative pole pieces are wound on a winding machine and then are put into a soft package clamp, top and side sealing is carried out, then the soft package clamp is put into an oven for baking, 9g of electrolyte is injected in the environment with the relative humidity less than 1.5%, and the electrolyte adopts the mass ratio EC of DEC to DMC of 1:1: 1, injecting a mixed solvent of 1M lithium hexafluorophosphate as an electrolyte, forming for 48 hours, and then vacuumizing and sealing; the cell model is 465473.
The charge and discharge test of the secondary lithium ion experimental battery prepared by the invention is carried out on a Guangzhou Lanqi battery tester according to the test method of GB/T18287-2000. The test results are shown in fig. 4. Table 1 is a table of performance data of the single crystal-like ternary cathode materials prepared in examples 1 to 3;
TABLE 1 Performance data Table of quasi-single crystal ternary cathode material prepared by the inventive example
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A preparation method of a ternary lithium battery material comprises the following steps:
A) performing ball milling activation on a nickel source, a cobalt source and a manganese source to obtain a mixed material;
B) mixing the mixed material, a lithium source, a fluxing agent, a compound of M and polyvinyl alcohol, and pressing after spray drying to obtain a block; m in the compound of M is selected from one or more of aluminum, magnesium, titanium, zirconium, iron, calcium, zinc, silicon, lanthanides and actinides;
C) roasting and crushing the blocks to obtain a monocrystal-like ternary material;
D) grinding and roasting the single-crystal-like ternary material and the coating source to obtain a ternary lithium battery material; the coating source is LiCO3And LiOH. H2One of O and Al2O3、ZrO2And TiO2One or more of;
the adding amount of the compounds of the nickel source, the cobalt source, the manganese source, the lithium source and the M is added according to the corresponding molar ratio of the compound shown in the formula (II),
LiNixCoyMnzMaO2 （Ⅱ）；
wherein x is more than or equal to 0.2 and less than or equal to 0.9, y is more than 0 and less than or equal to 0.4, z is more than or equal to 0.1 and less than or equal to 0.5, and a = 0 and is more than 1-x-y-z and less than or equal to 0.05;
the lithium source is added according to the ratio of Li: (Ni + Co + Mn) = 1.05-1.10: 1 by mole;
the particle size of D50 of the nickel source is 1-3 mu m, the particle size of D50 of the cobalt source is 5-20 mu m, and the particle size of D50 of the manganese source is 1-3 mu m; the particle size of the mixed material is 5-20 microns;
the fluxing agent is selected from one or more of polyethylene glycol, lithium borate and lithium phosphate.
2. The preparation method of claim 1, wherein in the step A), the rotation speed of the ball milling activation is 100-500 r/min, and the time is 1-3 h.
3. The preparation method of claim 1, wherein the polyvinyl alcohol is a polyvinyl alcohol solution with a concentration of 10%, and the polyvinyl alcohol accounts for 10% -20% of the total mass of the nickel source, the cobalt source and the manganese source.
4. The preparation method of claim 1, wherein in the step C), the roasting is carried out in an air or oxygen atmosphere, the roasting temperature is 850-950 ℃, and the roasting time is 12-15 h.
5. The preparation method according to claim 1, wherein in the step D), the roasting temperature is 600-900 ℃ and the roasting time is 5-7 h.
6. The method according to claim 1, wherein the nickel source is an oxide or carbonate of nickel, the cobalt source is an oxide or carbonate of cobalt, and the manganese source is an oxide or carbonate of manganese; the lithium source is lithium carbonate or lithium hydroxide; the compound of M is one or more of sulfate, nitrate, chloride and oxide of M.
7. The ternary lithium battery material prepared by the preparation method of any one of claims 1 to 6, which consists of a nickel-cobalt-manganese multicomponent material shown in formula (I) and a coating layer N coated on the surface of the nickel-cobalt-manganese multicomponent material;
LiNixCoyMnzMaO2 （Ⅰ）；
wherein x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0.1 and less than or equal to 0.5, and a =1-x-y-z is more than or equal to 0.05;
m is selected from one or more of aluminum, magnesium, titanium, zirconium, iron, calcium, zinc, silicon, lanthanides and actinides;
the N cladding layer is selected from LiAlO2、Li2ZrO3、Li2TiO3One or more of (a).
8. The ternary lithium battery material according to claim 7, wherein the ternary lithium battery material has a particle size of 5-20 μm and a compacted density of 3.6g/cm or more3。
9. A lithium ion battery comprises a positive electrode and a negative electrode, and is characterized in that the material of the positive electrode is the ternary lithium battery material prepared by the preparation method of any one of claims 1 to 6 or the ternary lithium battery material of any one of claims 7 to 8.
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