CN115621450A - Composite coated modified cathode material and preparation method and application thereof - Google Patents
Composite coated modified cathode material and preparation method and application thereof Download PDFInfo
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a composite coated modified cathode material and a preparation method and application thereof, belonging to the technical field of battery materials. According to the preparation method, the doping type anode material is coated and modified by two coating agents respectively in an island in-situ coating mode and an ultrasonic atomization coating mode, the obtained product is uniform in coating effect and high in compactness, the interface stability and safety of the anode material are effectively improved, meanwhile, higher charging and discharging capacity can be maintained, and the commercialization value is high. The preparation method has simple operation steps and low requirements on production conditions, and can realize industrial mass production.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a composite coating modified positive electrode material and a preparation method and application thereof.
Background
With the rapid development of the lithium battery industry, the lithium battery and related products are gradually replacing traditional energy to become the main force of energy use in various industrial fields, and in the face of increasing use demands, how to improve the energy density of the battery gradually becomes the main research focus of the industry. The high nickel content, high voltage content and single crystallization of the lithium battery anode material can effectively improve the energy density of the battery, but the problem that the surface and the interface of the anode material are more easily reacted with electrolyte in the charging and discharging processes is accompanied, alkaline substances are easy to remain on the surface of the material, the risk of gas generation exists, and the stability and the safety need to be improved.
In the prior art, a doping and coating modification means is usually adopted to solve the problems, for example, a conductive polymer is adopted to carry out in-situ coating polymerization on the positive electrode material, or a metal salt is adopted to carry out doping on the positive electrode material, but the methods have multiple operation steps and higher requirements on production conditions, or the stability of the positive electrode material is improved on the premise of sacrificing the capacity of the positive electrode material, and the commercial value of the product is not high; meanwhile, the methods are difficult to ensure the uniformity of the modified part of the cathode material, but can cause local non-uniformity of the modified part of the product, so that safety accidents are more likely to happen.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide a preparation method of a composite coating modified cathode material, and the method is used for coating and modifying a doped cathode material by using two coating agents respectively in an island-shaped in-situ coating mode and an ultrasonic atomization coating mode, so that the obtained product has uniform coating effect and high compactness, the interface stability and safety of the cathode material are effectively improved, higher charge and discharge capacity can be maintained, and the commercialization value is high. The preparation method has simple operation steps and low requirements on production conditions, and can realize industrial mass production.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a composite coated modified cathode material comprises the following steps:
(1) Uniformly mixing the doped anode material and the coating agent A to obtain powder B; the coating agent A is at least one of oxide, hydroxide and salt of element N, wherein the element N is at least one of Ni, co, mn, zr, al, mg, ti, sr, W, Y, zn, la, ce, nb, sb, mo, ta, F and S;
(2) Putting the powder B into an ultrasonic atomizer, and uniformly mixing the powder B with liquid drop particles formed by ultrasonic atomization of the colloid coating agent C under a stirring state to obtain powder D; the colloid coating agent C is sol containing metal M, and the metal M is at least one of Al, ti, zr, Y and Si;
(3) Heating and preserving heat of the powder D in an oxygen-containing atmosphere, and sieving to obtain the composite coated modified cathode material;
the mass ratio of the coating agent A to the colloid coating agent C is (0.6-1.5): 1.
preferably, the working frequency of the ultrasonic atomizer during ultrasonic atomization is 2.2-2.5 Mhz.
In the preparation method of the composite coating modified anode material, in order to improve the stability of the doped anode material and not influence the charge and discharge capacity of a product, a metal coating agent rather than an organic polymer coating agent is used for modification, wherein the coating agent A is directly mixed with the doped anode material, then a colloid coating agent C is atomized into fine mist-shaped particles through an ultrasonic atomization effect by an ultrasonic atomizer, the particles are only 1-100 nm in size generally, and the service life is microsecond, so the mist-shaped particles can be rapidly collapsed after the atomization effect and form droplet particles which are dispersed to be in contact with powder B, the droplet particles still have higher speed and higher temperature at the moment of contact, the temperature can be rapidly reduced after the droplet particles are contacted, the droplet particles are tightly coated on the surface of the powder B through high kinetic energy transfer, the whole process is dispersed and mixed on the basis of a dry method, the pre-uniform coating tightness degree is high, and complicated wet method mixing steps such as water washing, drying and the like are not involved (some coating agents which are difficult to be uniformly dispersed on the surface of the doped anode material through the wet method), so that the coating agent is efficient, simple and convenient. In the technical scheme of the invention, as the atomized particles generated by ultrasonic atomization have higher temperature, the particles can partially change phase when being collapsed into liquid drop particles, so that the time for heat treatment of the subsequent powder D is shortened, and the possibility of oxygen loss is greatly reduced.
Further, the inventors have also noted that the ratio of the two coating agents to be added needs to be maintained in a moderate range depending on the kind of the coating agent and the coating form, and if the ratio is not proper, the charge/discharge capacity of the product is affected and becomes low.
Preferably, the molecular formula of the doped positive electrode material is LiNi x Co y Mn z R a O 2 Wherein the doping element R is at least one of Ni, co, mn, zr, al, mg, ti, sr, W, Y, zn, la, ce, nb, sb, mo, ta, F and S, 0<x is less than or equal to 1, y is less than or equal to 0.3, z is less than or equal to 0 and less than or equal to 0.6, a is less than or equal to 0.001 and less than or equal to 0.01, and x + y + z + a =1.
More preferably, the doping element R is at least one of Zr, mo, ce, Y and Sr.
The selected R element can form a strong chemical bonding effect with oxygen in the anode material, stabilize the lattice structure and improve the high-voltage performance of the doped anode material.
More preferably, the doped anode material is at least one of a polycrystalline type doped anode material, a single crystal type doped anode material and a single crystal type doped anode material.
More preferably, the preparation method of the doped positive electrode material comprises the following steps:
uniformly mixing a lithium source, a nickel source, a cobalt source, a manganese source and a compound containing a doping element R, heating and preserving heat in an oxygen-containing atmosphere, and crushing the obtained mixture to obtain the doped anode material.
More preferably, the lithium source is at least one of lithium hydroxide and lithium carbonate, and the temperature during heating and heat preservation is 750-1050 ℃.
Preferably, the coating agent A is an oxide of element N, and the element N is at least one of Ti, la, nb and Sb.
Because the coating agent A and the doped anode material are directly mixed and coated by the colloid coating agent C, the coating agent A exists in an island-shaped coating form in the heating and heat-preserving treatment process, and the reaction effect is optimal when the oxide form, particularly the oxides of the elements, are used as components.
Preferably, the colloid coating agent C is at least one of Al sol, ti sol, and Zr sol.
Among the above-mentioned several kinds of sols, the Al sol is mainly aluminium hydroxide sol, and under the high temperature that ultrasonic atomization process brought, it can take place the phase transition and turn into aluminium oxide to a certain extent, and on the same hand, the Ti sol that uses anatase's titanium dioxide as the main part can turn into rutile type titanium dioxide under high temperature, as above, this kind of partial phase transition can make the follow-up heating heat preservation of powder D handle the time shorten, has not only promoted the productivity, more can ensure that the product can not take place the oxygen loss phenomenon, ensures the normal cyclicity performance of product.
Preferably, the temperature of the heating and heat preservation treatment in the step (3) is 250-750 ℃, and the time is 1-10 h.
More preferably, the time for the heat-preservation treatment is 3 to 8 hours.
Due to the ultrasonic atomization treatment, the colloid coating agent C finishes a part of phase change conversion in advance, so that the time of heating and heat preservation treatment can be effectively shortened.
The invention also aims to provide the composite coated modified cathode material prepared by the preparation method of the composite coated modified cathode material.
Preferably, the general formula of the composite coating modified cathode material is LiNi x Co y Mn z R a O 2 @M b N c Wherein 0 is<x≤1，0≤y≤0.3，0≤z≤0.6，0.001≤a≤0.01，0＜b≤0.03，0＜c≤0.03，x+y+z+a＝1。
The preparation method of the invention adopts two different coating modes to compound the coating agent to dope the cathode material LiNi x Co y Mn z R a O 2 Performing coating modificationAfter the two coating agents generate synergistic action, the interface stability of the doped anode material can be effectively improved, the side reaction between the doped anode material and the electrolyte is inhibited, and the obtained product LiNi x Co y Mn z R a O 2 @M b N c The product has good safety performance and cycling stability, and due to the optimization of doping elements, the obtained product can also show good electrochemical activity in a high-voltage use environment, and the commercial use value is high.
The invention further aims to provide application of the composite coated modified cathode material in preparation of secondary batteries.
Preferably, the secondary battery includes a half battery and a full battery.
Preferably, the upper limit of the operating voltage of the secondary battery is 4.25 to 4.35V.
The composite coating modified anode material LiNi x Co y Mn z R a O 2 @M b N c The high-voltage electrochemical battery has good high-voltage electrochemical activity, high stability and safety, good storage and service performance even if being applied to the field of full batteries (such as soft package batteries), low storage gas production and wide application prospect.
The preparation method has the beneficial effects that the two coating agents are used for coating and modifying the doped positive electrode material in the modes of island-shaped in-situ coating and ultrasonic atomization coating respectively, the obtained product has uniform coating effect and high compactness, the interface stability and safety of the positive electrode material are effectively improved, high charge and discharge capacity can be maintained, and the commercialization value is high. The preparation method has simple operation steps and low requirements on production conditions, and can realize industrial mass production.
Drawings
Fig. 1 is a schematic flow chart of the preparation process of powder D in the composite coated modified cathode material of the present invention.
FIG. 2 is a graph showing the results of capacity retention rates of the products obtained in example 1 of the present invention and comparative example 1 when 100 charge/discharge cycle tests were performed.
FIG. 3 is a scanning electron micrograph of products obtained in example 1 (left) of the present invention and comparative example 1 (right).
Fig. 4 is a graph showing the results of stored gas production of the products obtained in example 2 of the present invention and comparative example 2 after the products are applied to the pouch battery.
Fig. 5 is a comparison graph of XRD results of the directly air-dried Al sol prepared in effect example 2 of the present invention and the Al sol after ultrasonic atomization treatment.
FIG. 6 is a graph showing a comparison of XRD results of the product obtained in example 1 of effect example 2 of the present invention and that of comparative example 1.
Fig. 7 is a graph showing the results of capacity retention ratio when the product obtained in example 1 of the present invention and the comparative product 1 were subjected to 100 charge and discharge cycle tests.
Detailed Description
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described below with reference to specific examples/comparative examples, which are intended to be a detailed understanding of the contents of the present invention, but are not intended to be limiting. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention. The experimental reagents, raw materials and instruments designed in the practice of the invention and the comparative examples are common reagents, raw materials and instruments unless otherwise specified. The Al sol, the Ti sol and the Zr sol used in the embodiment of the invention are all products produced by new crystal grain materials.
Example 1
The invention discloses a composite coating modified cathode material and a preparation method and an embodiment of application thereof, wherein the preparation method comprises the following steps:
(1) Doped anode material LiNi x Co y Mn z R a O 2 Preparation of (R is Zr):
mixing Ni 0.55 Co 0.12 Mn 0.33 (OH) 2 Precursor and battery grade Li 2 CO 3 And ZrO 2 After being mixed uniformly, the mixture is heated and insulated at 950 ℃ in an oxygen-containing atmosphere (the volume concentration of oxygen is 22 percent). Wherein Ni 0.55 Co 0.12 Mn 0.33 (OH) 2 With Li 2 CO 3 Charging according to the molar ratio of Li/(Ni + Co + Mn) of 1.05, and ZrO 2 The amount of the added is 3000ppm (as ZrO) 2 Medium Zr accounts for the mass of the precursor). Carrying out coarse crushing pretreatment on a product obtained by sintering until the granularity D50 is 4.0 +/-0.3 mu m;
(2) Mixing the powder obtained after the crushing in the step (1) with a coating agent A in a mixer, then transferring the obtained powder B to the right below an ultrasonic atomizer, and spraying liquid drop particles formed by ultrasonic atomization of a colloid coating agent C at the working frequency of 2.4Mhz to be mixed with a mixed material in stirring to obtain powder D; wherein the colloid coating agent C is Al sol, and the coating agent A is TiO 2 The amounts of both added were 1000ppm and 1500ppm (Al (OH) 3 /TiO 2 The mass of the medium Al/Ti accounts for the mass of the powder obtained after the crushing in the step (1); the process is schematically shown in FIG. 1;
(3) Heating the powder D to 550 ℃ in an atmosphere with an oxygen concentration of 22%, preserving heat for 6h, and then sieving and deironing to obtain the composite coated modified cathode material LiNi x Co y Mn z Zr a O 2 @Al b Ti c 。
Example 2
The invention discloses a composite coating modified cathode material and a preparation method and an embodiment of application thereof, wherein the preparation method comprises the following steps:
(1) Doped positive electrode material LiNi x Co y Mn z R a O 2 Preparation of (R is Mo):
mix Ni 0.70 Co 0.10 Mn 0.20 (OH) 2 Precursor and battery grade LiOH and MoO 3 After being mixed evenly, the mixture is heated and insulated at 920 ℃ under the oxygen-containing atmosphere (the volume concentration of oxygen is 96 percent). Wherein Ni 0.70 Co 0.10 Mn 0.20 (OH) 2 Charging with LiOH according to the molar ratio of Li/(Ni + Co + Mn) of 1.04, moO 3 The amount of the additive is 2000ppm (in terms of MoO) 3 Medium Mo accounts for the mass of the precursor). Carrying out coarse crushing pretreatment on a product obtained by sintering until the granularity D50 is 4.0 +/-0.3 mu m;
(2) Mixing the powder obtained by crushing in the step (1) withMixing the coating agent A in a mixer, then transferring the obtained powder B to the right lower part of an ultrasonic atomizer, and spraying liquid drop particles formed by ultrasonic atomization of the colloid coating agent C at the working frequency of 2.4Mhz to be mixed with the mixed material in stirring to obtain powder D; wherein the coating agent A is La 2 O 3 The colloid coating agent C was Ti sol, and the addition amounts of the two were 1000ppm and 1500ppm (TiO) 2 Sol and La 2 O 3 The Ti/La accounts for the mass of the powder obtained after the crushing in the step (1);
(3) Heating the powder D to 450 ℃ in an atmosphere with an oxygen concentration of 96%, preserving heat for 8h, and then sieving and deironing to obtain the composite coated modified cathode material LiNi x Co y Mn z Mo a O 2 @Ti b La c 。
Example 3
The invention discloses a composite coating modified cathode material and a preparation method and an embodiment of application thereof, wherein the preparation method comprises the following steps:
(1) Doped anode material LiNi x Co y Mn z R a O 2 Preparation of (R is Mo):
mix Ni 0.83 Co 0.06 Mn 0.11 (OH) 2 Precursor and micro-powder grade LiOH and CeO 2 After being mixed uniformly, the mixture is heated and insulated at 870 ℃ in an oxygen-containing atmosphere (the volume concentration of oxygen is 97 percent). Wherein Ni 0.83 Co 0.06 Mn 0.11 (OH) 2 Charging with LiOH according to the molar ratio of Li/(Ni + Co + Mn) of 1.02, and adding CeO 2 The amount of the additive was 2500ppm (as CeO) 2 Middle Ce accounts for the mass of the precursor). Carrying out coarse crushing pretreatment on a product obtained by sintering until the granularity D50 is 10 +/-0.5 mu m;
(2) Mixing the powder obtained after the crushing in the step (1) with a coating agent A in a mixer, then transferring the obtained powder B to the right below an ultrasonic atomizer, and spraying liquid drop particles formed by ultrasonic atomization of a colloid coating agent C at the working frequency of 2.4Mhz to be mixed with a mixed material in stirring to obtain powder D; wherein the coating agent A is Nb 2 O 5 The colloid coating agent C is Zr sol, and the addition amounts of the Zr sol and the Zr sol are 1500ppm and 1800ppm respectivelyppm(ZrO 2 Sol and Nb 2 O 5 The medium Zr/Nb accounts for the mass of the powder obtained after the crushing in the step (1);
(3) Heating the powder D to 250 ℃ in an atmosphere with the oxygen concentration of 97%, preserving the heat for 10 hours, and then sieving and deironing to obtain the composite coated modified cathode material LiNi x Co y Mn z Ce a O 2 @Al b Nb c 。
Example 4
The invention discloses a composite coating modified cathode material and a preparation method and an embodiment of application thereof, wherein the preparation method comprises the following steps:
(1) Doped anode material LiNi x Co y Mn z R a O 2 Preparation of (R is Y and Sr):
mixing Ni 0.95 Co 0.03 Mn 0.02 (OH) 2 Precursor and micro-powder level LiOH and Y 2 O 3 And heating and preserving heat at 855 ℃ in an oxygen-containing atmosphere (the volume concentration of oxygen is 98%) after the SrO is uniformly mixed. Wherein Ni 0.95 Co 0.03 Mn 0.02 (OH) 2 Charging with LiOH according to the molar ratio of Li/(Ni + Co + Mn) of 1.01, Y 2 O 3 And SrO in an amount of 2000ppm and 1500ppm (as Y) 2 O 3 Y/Sr in the SrO accounts for the mass of the precursor). Carrying out coarse crushing pretreatment on a product obtained by sintering until the granularity D50 is 3.3 +/-0.3 mu m;
(2) Mixing the powder obtained after the crushing in the step (1) with a coating agent A in a mixer, then transferring the obtained powder B to the right below an ultrasonic atomizer, and spraying liquid drop particles formed by ultrasonic atomization of a colloid coating agent C at the working frequency of 2.4Mhz to be mixed with a mixed material in stirring to obtain powder D; wherein the cladding agent A is Sb 2 O 5 The colloidal coating agent C was Zr sol, and the amounts of both added were 1500ppm and 1800ppm (ZrO) 2 Sol and Sb 2 O 5 The mass of medium Zr/Sb accounts for the mass of the powder obtained after the crushing in the step (1);
(3) Heating the powder D to 360 ℃ in an atmosphere with the oxygen concentration of 97%, preserving the heat for 10 hours, and then sieving and deironing to obtain the compoundComposite coated modified positive electrode material LiNi x Co y Mn z Y/Sr a O 2 @Zr b Sb c 。
Comparative example 1
A composite coating modified cathode material and a preparation method thereof are different from those of the embodiment 1 only in that the preparation method comprises the following steps: and (2) directly mixing the powder obtained after the crushing in the step (1) with a coating agent A and a colloid coating agent C to prepare powder D.
Comparative example 2
The difference between the composite coating modified cathode material and the preparation method thereof and the embodiment 2 is that the preparation method comprises the following steps: and (2) directly mixing the powder obtained after the crushing in the step (1) with a coating agent A and a colloid coating agent C to prepare powder D.
Comparative example 3
The difference between the composite coating modified anode material and the preparation method thereof and the embodiment 1 is that the coating agent A is TiO 2 The colloid coating agent C was Al sol, and the amounts of the both added were 500ppm and 2000ppm, respectively.
Comparative example 4
The difference between the composite coating modified anode material and the preparation method thereof and the embodiment 1 is that the coating agent A is TiO 2 The colloid coating agent C was Al sol, and the amounts of addition of the both were 2000ppm and 500ppm, respectively.
Effect example 1
In order to verify the performance effect of the composite coating modified cathode material, the products obtained in the examples 1-4 and the comparative examples 1-2 are subjected to charge-discharge cycle test, and the test method specifically comprises the following steps: n-methyl pyrrolidone is used as a solvent, and the mass ratio of N-methyl pyrrolidone to N-methyl pyrrolidone is 9.2:0.5:0.3 respectively and uniformly mixing the products obtained in the embodiments and the comparative examples, acetylene black and PVDF to form slurry, coating the slurry on an aluminum foil, drying by blowing at 80 ℃ for 8h, and drying at 120 ℃ for 12h in vacuum to obtain a positive electrode for testing, and assembling the battery in an argon-protected glove box, wherein the negative electrode is a metal lithium sheet, the diaphragm is a polypropylene film, the electrolyte is 1MLiPF6-EC/DMC (1: 1, v/v), and a 2032 type button battery case is adopted during battery assembly. And (3) carrying out electrochemical performance detection on the obtained button cell, carrying out 0.1C rate activation for one cycle under a specific cut-off voltage, then carrying out 1C/1C rate cycle 100 times under the same cut-off voltage, and recording the cycle capacity retention rate after 100 times, wherein the calculation method of the capacity retention rate comprises the following steps: the ratio of the specific capacity of gram charged at the N-th cycle to the specific capacity of gram charged at the first cycle is multiplied by 100 percent. The test results are shown in table 1.
TABLE 1
It can be seen from table 1 that the products prepared in the embodiments have good charge and discharge activity and cycle stability, the first discharge specific capacity at 0.1C reaches 180mAh/g and the highest 230mAh/g under the working voltage of 2.8-4.25/4.35V, and still reaches 175-225 mAh/g under the magnification of 1C, and the capacity retention rate after 100 cycles is more than 90%, which indicates that the products prepared by the preparation method of the invention are not only unaffected in capacity, but also significantly improved in stability after being coated and modified by two special coating agents in a special way, and the products of comparative examples 1 and 2 are only coated in an island form by directly mixing the coating agents in a conventional way, so that the inhibition effect on the interface reaction of the positive electrode material is very limited, and the electrochemical performance, particularly the cycle performance is inferior to the products of the embodiments, as shown in fig. 2. When the products obtained by the preparation methods of example 1 and comparative example 1 are observed by a scanning electron microscope, as shown in fig. 3, it can be seen that the product of comparative example 1 obtained by the conventional mixed coating method is only island-shaped coated, while the product obtained by example 1 is obviously better in coating effect and more compact in coating degree. In addition, the same tests as described above were performed on the products obtained in comparative examples 3 and 4, and the results are shown in Table 2.
TABLE 2
| Product(s) | 0.1C specific discharge capacity (mAh/g) | Capacity retention ratio (%) at 100 cycles |
| Comparative example 3 | 178 | 95.4 |
| Comparative example 4 | 176 | 95.2 |
It can be seen that the product prepared by using the non-preferred proportion of the coating agent has little influence on the cycle stability, but the specific discharge capacity of the product is greatly influenced, and the initial specific discharge capacity can be close to 10mAh/g.
Further, in order to verify the safety of the product of the invention, the product obtained in example 2 and the product obtained in comparative example 2 are used for preparing a soft package battery and storing the detection result of gas generation at 70 ℃ in a full charge state, and the specific flow is as follows:
pulping, coating, rolling, winding, packaging, injecting liquid, forming and testing.
Wherein, the positive electrode material slurry was prepared according to example 2/comparative example 2: PVDF: the SP mass ratio is 96:2:2, stirring the slurry, wherein the addition amount of NMP is 0.8 times of the mass of the anode material, and stirring the slurry for 8 hours at the speed of 2000r/min to ensure that the viscosity of the slurry is more than 4000mPa & S;
the negative electrode slurry was prepared according to graphite: SBR: CMC: the SP mass ratio is 90:1:4:5, preparing materials, adding deionized water with the mass 1.5 times of that of the graphite, and stirring for 6 hours at the speed of 2000r/min during stirring;
coating process control of positive electrode surface densityThe degree is 1.6g/dm 2 The surface density of the negative electrode was 1.1g/dm 2 (ii) a Controlling the surface density of the positive electrode to be 3.9g/cc and the surface density of the negative electrode to be 1.6g/cc in the rolling process;
after the components are finished, the positive pole piece, the negative pole piece and the diaphragm are wound into a bare cell through an automatic winding machine, and the deviation between the positive pole piece and the negative pole is avoided in the process. And packaging the naked battery cell into an aluminum plastic film for top side sealing, and drying for 12h at 90 ℃ in vacuum drying to remove excessive moisture in the battery cell. Then 5g of commercial electrolyte was injected, and the cell was evacuated and pre-packaged.
And (3) carrying out aging treatment on the battery cell at 45 ℃: and standing the prepared battery cell for 2 hours, charging to 3.4V at 0.02C according to a constant current, standing for 5min, charging to 3.75V at 0.33C according to a constant current, standing for 5min, and continuously charging to 4.4V at 0.33C according to a constant current.
And (4) mounting the soft package battery on a test cabinet, and setting a charging system according to the test steps. The storage gas production of the soft package battery is measured according to the once-for-5-day test frequency and the gas volume by a drainage method. The test results are shown in fig. 4.
As can be seen from the figure, the gas production of the pouch battery prepared from the product obtained in example 2 is significantly reduced, and particularly after 30 days, the gas production of the pouch battery prepared from the product of comparative example 2 is significantly improved, compared with the product of comparative example 2 prepared by a conventional coating method.
Effect example 2
In order to investigate the phase transition preference of the colloid coating agent in the preparation method of the present invention, the Al sol used in example 1 was directly air-dried and XRD-detected, and at the same time, the Al sol was subjected to the same ultrasonic atomization treatment as in example 1 and XRD-detected by collecting particles, and as shown in fig. 5, it can be seen that the Al sol which was not subjected to the ultrasonic atomization treatment was mainly AlOOH, and the diffraction peak thereof exhibited a significant broadening effect, while the sol which was subjected to the ultrasonic atomization was partially phase-transformed and transformed into alumina, but the diffraction peak thereof was not sharp, indicating that the transformation degree thereof was not complete. Subsequently, a product was prepared in the same manner as in example 1 except that the heat-retention time in step (3) was extended to 7 hours to obtain a control 1, and XRD tests were carried out on the product of example 1 and the control 1, respectively, as shown in FIG. 6, whereby it was found that the peak shapes were substantially the same, but the peak intensity ratio of I (003)/I (104) was slightly decreased with the extension of the heat-retention time, indicating that the degree of cationic shuffling was slightly increased. The control 1 is subjected to the cycle test with the same effect as that of the example 1, and the result is shown in fig. 7, it can be seen that the initial charge-discharge performance of the control 1 is similar to that of the product in the example 1, but the cycle performance is obviously poor, and the capacity retention rate after 100 cycles is less than 90%, which indicates that the preparation method of the invention not only can shorten the calcination and sintering time, improve the productivity, but also can avoid the electrochemical stability of the product from being weakened due to overburning.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the composite coating modified cathode material is characterized by comprising the following steps:
(1) Uniformly mixing the doped anode material and the coating agent A to obtain powder B; the coating agent A is at least one of oxide, hydroxide and salt of element N, wherein the element N is at least one of Ni, co, mn, zr, al, mg, ti, sr, W, Y, zn, la, ce, nb, sb, mo, ta, F and S;
(2) Putting the powder B into an ultrasonic atomizer, and uniformly mixing the powder B with liquid drop particles formed by ultrasonic atomization of the colloid coating agent C under a stirring state to obtain powder D; the colloid coating agent C is sol containing metal M, and the metal M is at least one of Al, ti, zr, Y and Si;
(3) Heating and preserving heat of the powder D in an oxygen-containing atmosphere, and sieving to obtain the composite coated modified cathode material;
the mass ratio of the coating agent A to the colloid coating agent C is (0.6-1.5): 1.
2. the method for preparing the composite coated modified cathode material according to claim 1, wherein the molecular formula of the doped cathode material is LiNi x Co y Mn z R a O 2 Wherein the doping element R is at least one of Ni, co, mn, zr, al, mg, ti, sr, W, Y, zn, la, ce, nb, sb, mo, ta, F and S, 0<x is less than or equal to 1, y is less than or equal to 0.3, z is less than or equal to 0 and less than or equal to 0.6, a is less than or equal to 0.001 and less than or equal to 0.01, and x + y + z + a =1;
preferably, the doping element R is at least one of Zr, mo, ce, Y and Sr.
3. The method for preparing the composite coated modified cathode material according to claim 1, wherein the doped cathode material is at least one of a polycrystalline doped cathode material, a quasi-single crystal doped cathode material and a single crystal doped cathode material;
the preparation method of the doped anode material comprises the following steps:
uniformly mixing a lithium source, a nickel source, a cobalt source, a manganese source and a compound containing a doping element R, heating and preserving heat in an oxygen-containing atmosphere, and crushing the obtained mixture to obtain the doped anode material.
4. The method for preparing the composite coated modified cathode material according to claim 1, wherein the coating agent A is an oxide of an element N, and the element N is at least one of Ti, la, nb and Sb.
5. The method for preparing the composite coated modified cathode material according to claim 1, wherein the colloid coating agent C is at least one of Al sol, ti sol, and Zr sol.
6. The preparation method of the composite coated modified cathode material according to claim 1, wherein the temperature of the heat preservation treatment in the step (3) is 250 to 750 ℃ and the time is 1 to 10 hours;
preferably, the time for the heat preservation treatment is 3-8 h.
7. The composite coated modified cathode material prepared by the method for preparing the composite coated modified cathode material according to any one of claims 1 to 6.
8. The composite coated modified cathode material according to claim 7, wherein the general formula of the composite coated modified cathode material is LiNi x Co y Mn z R a O 2 @M b N c Wherein 0 is<x≤1，0≤y≤0.3，0≤z≤0.6，0.001≤a≤0.01，0＜b≤0.03，0＜c≤0.03，x+y+z+a＝1。
9. Use of the composite coated modified cathode material according to claim 7 or 8 in the preparation of a secondary battery.
10. The use according to claim 9, wherein the secondary battery includes a half cell and a full cell; preferably, the upper limit of the operating voltage of the secondary battery is 4.25 to 4.35V.
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| PCT/CN2023/079175 WO2024093074A1 (en) | 2022-11-02 | 2023-03-02 | Composite-coated modified positive electrode material, preparation method therefor and use thereof |
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| CN116093309A (en) * | 2023-03-07 | 2023-05-09 | 中南大学 | Antimony-modified high-nickel ternary layered composite positive electrode material, and preparation method and application thereof |
| WO2024093074A1 (en) * | 2022-11-02 | 2024-05-10 | 广东邦普循环科技有限公司 | Composite-coated modified positive electrode material, preparation method therefor and use thereof |
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| CN114566636B (en) * | 2021-12-29 | 2023-11-17 | 中国科学院过程工程研究所 | Lithium-rich manganese-based positive electrode material and preparation method and application thereof |
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