CN112054167B - Manufacturing method of positive electrode material for secondary battery - Google Patents
Manufacturing method of positive electrode material for secondary battery Download PDFInfo
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- CN112054167B CN112054167B CN201910491512.5A CN201910491512A CN112054167B CN 112054167 B CN112054167 B CN 112054167B CN 201910491512 A CN201910491512 A CN 201910491512A CN 112054167 B CN112054167 B CN 112054167B
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Abstract
本发明提供一种二次电池用正极材料的制造方法，以生产具碳包覆且含氟的二次电池用正极材料。制造方法包括步骤：(a)提供一具碳包覆的前驱物与一含碱金属的氟化物，形成一二次颗粒；(b)提供一密闭系统，具有一容置空间，且于容置空间内填入二次颗粒，其中二次颗粒于容置空间的体积填充率大于30％以上；以及(c)于一非氧化环境中，以300℃至900℃的温度进行热处理，以产生正极材料。透过密闭系统以体积填充率大于30％生产具碳包覆且含氟的二次电池用正极材料，可获致单一晶相，有助于提升产品转化率及生产效率，避免材料的浪费或造成环境污染的问题。
The present invention provides a method for producing a positive electrode material for a secondary battery, so as to produce a carbon-coated and fluorine-containing positive electrode material for a secondary battery. The manufacturing method includes the steps of: (a) providing a carbon-coated precursor and an alkali metal-containing fluoride to form a secondary particle; (b) providing a closed system with an accommodating space, and in the accommodating The space is filled with secondary particles, wherein the volume filling rate of the secondary particles in the accommodating space is greater than 30%; and (c) in a non-oxidizing environment, heat treatment at a temperature of 300° C. to 900° C. to produce a positive electrode Material. Through a closed system to produce a carbon-coated and fluorine-containing cathode material for secondary batteries with a volume filling rate of more than 30%, a single crystal phase can be obtained, which helps to improve product conversion rate and production efficiency, and avoid material waste or cause problem of environmental pollution.
Description
Technical Field
The present invention relates to a battery material, and more particularly to a method for manufacturing a cathode material for a secondary battery, so as to produce a cathode material for a secondary battery having a carbon coating and containing fluorine.
Background
The positive electrode material for secondary batteries is a main material that affects the performance of secondary batteries. Many different modifications have been proposed in the market for positive electrode materials for secondary batteries. With lithium vanadium fluorophosphate (LiVPO) 4 F) The material is exemplified by lithium vanadium fluoride phosphate (LiVPO) as a positive electrode material for a lithium secondary battery 4 F) The positive electrode material has high operating voltage characteristics, and is helpful for the lithium secondary battery to achieve high electric capacity, high discharge power, excellent long cycle life, and improved thermal stability and high temperature performance. In addition, lithium vanadium phosphate fluoride (LiVPO) 4 F) To further improve the lithium vanadium phosphate fluoride (LiVPO) 4 F) Characteristics of the positive electrode material.
However, in the actual production process, lithium vanadium fluoride phosphate (LiVPO) 4 F) Easily form other substances during carbon coating treatmentSuch as lithium vanadium phosphate (Li) 3 V 2 (PO 4 ) 3 ) So that a single pure phase of carbon-coated lithium vanadium phosphate (LiVPO) cannot be obtained 4 F/C) positive electrode material, which in turn affects the characteristics of subsequent battery applications.
In view of the above, it is desirable to provide a method for manufacturing a cathode material for a secondary battery, which is capable of producing a cathode material for a secondary battery having a carbon coating and containing fluorine, and solving the problems of the prior art.
Disclosure of Invention
The invention aims to provide a method for manufacturing a positive electrode material for a secondary battery, which is used for producing a positive electrode material for the secondary battery with carbon coating and fluorine. The positive electrode material for the secondary battery with carbon coating and fluorine is produced through a closed system, which is beneficial to improving the product conversion rate and the production efficiency and avoiding the problems of material waste or environmental pollution. The whole production process is simple in process and low in production cost. The obtained carbon-coated fluorine-containing cathode material for a secondary battery has a single crystal phase in X-ray diffraction analysis (XRD) analysis, and is helpful for achieving high electric capacity, high discharge power, excellent long cycle life of the secondary battery, and simultaneously improving thermal stability and high temperature performance.
Another object of the present invention is to provide a method for manufacturing a positive electrode material for a secondary battery, which is capable of producing a positive electrode material for a secondary battery having a carbon coating and containing fluorine. When the closed system is subjected to heat treatment, the volume filling rate of the precursor with the carbon coating and the secondary particles of the fluoride containing the alkali metal is more than 30 percent, so that the positive electrode material for the secondary battery with the single pure phase, the carbon coating and the fluorine containing can be obtained, and the problems of material waste or environmental pollution are avoided. In addition, as the volume filling rate of the precursor with carbon coating and the secondary particles containing the fluoride of the alkali metal is increased, the positive electrode material for the secondary battery with carbon coating and fluorine, which can obtain a single pure phase, is ensured, the production efficiency is increased, and the production cost is effectively reduced.
It is still another object of the present invention to provide a method for manufacturing a positive electrode material for a secondary battery, which is capable of producing a positive electrode material for a secondary battery having a carbon coating and containing fluorine. When the carbon-coated precursor and the secondary particles of the fluoride containing the alkali metal are thermally treated in a closed system, the conversion rate and the production efficiency of the product can be improved by adding the fluorine-containing compound.
To achieve the above object, the present invention provides a method for producing a positive electrode material for a secondary battery, comprising: (a) providing a precursor with carbon coating and fluoride containing alkali metal to form a secondary particle; (b) providing a closed system which is provided with an accommodating space and is filled with the secondary particles, wherein the volume filling rate of the secondary particles in the accommodating space is more than 30%; and (c) performing heat treatment at a temperature of 300 ℃ to 900 ℃ in a non-oxidizing environment to produce the cathode material.
In one embodiment, the positive electrode material is selected from lithium vanadium phosphate with carbon coating (LiVPO) 4 F/C), lithium aluminum fluoride phosphate (LiAlPO) with carbon coating 4 F/C), lithium manganese fluoride phosphate (LiMnPO) with carbon coating 4 F/C), fluorine lithium titanium phosphate (LiTiPO) with carbon coating 4 F/C), lithium fluoride cobalt phosphate with carbon coating (LiCoPO) 4 F/C), fluorine lithium nickel phosphate (LiNiPO) with carbon coating 4 F/C), carbon-coated lithium zinc fluoride phosphate (LiZnPO) 4 F/C), lithium chromium fluoride phosphate with carbon coating (LiCrPO) 4 F/C), sodium vanadium fluoride phosphate with carbon coating (NaVPO) 4 F/C), sodium aluminum fluoride phosphate with carbon coating (NaAlPO) 4 F/C), carbon coated sodium fluoro manganese phosphate (NaMnPO) 4 F/C), fluorine sodium titanium phosphate (NaTiPO) with carbon coating 4 F/C), sodium fluorine cobalt phosphate with carbon coating (NaCoPO) 4 F/C), fluorine sodium nickel phosphate (NaNiPO) with carbon coating 4 F/C), sodium zinc fluophosphate (NaZnPO) with carbon coating 4 F/C), sodium chromium fluoride phosphate with carbon coating (NaCrPO) 4 F/C), carbon-coated potassium vanadium phosphate fluoride (KVPO) 4 F/C), potassium aluminum fluoride phosphate (KAlPO) with carbon coating 4 F/C), potassium manganese fluoride phosphate (KMnPO) with carbon coating 4 F/C), fluorine potassium titanium phosphate (KTiPO) with carbon coating 4 F/C), carbon-coated potassium cobalt fluoride phosphate (KCoPO) 4 F/C), fluorine potassium nickel phosphate (KNiPO) with carbon coating 4 F/C), potassium zinc phosphate fluoride (KZnPO) with carbon coating 4 F/C) and carbon-coated potassium chromium phosphate fluoride (KCrPO) 4 F/C) is selected from the group consisting of.
In one embodiment, the carbon-coated precursor is selected from the group consisting of carbon-coated Vanadium Phosphate (VPO) 4 C) aluminum phosphate with carbon coating (AlPO) 4 /C), manganese phosphate with carbon coating (MnPO) 4 C) carbon-coated titanium phosphate (TiPO) 4 C) carbon-coated cobalt phosphate (CoPO) 4 /C), nickel phosphate (NiPO) with carbon coating 4 /C), zinc phosphate (ZnPO) with carbon coating 4 C) and carbon-coated chromium phosphate (CrPO) 4 /C) one of the group.
In one embodiment, the alkali metal-containing fluoride is selected from one of the group consisting of lithium fluoride (LiF), sodium fluoride (NaF), and potassium fluoride (KF).
In one embodiment, the molar ratio of the carbon-coated precursor to the alkali metal-containing fluoride ranges from 1:1.0 to 1: 1.05.
In one embodiment, step (a) utilizes mixing, slurrying, and spray granulation to form secondary particles.
In one embodiment, the average size of the secondary particles is in the range of 5 μm to 30 μm.
In one embodiment, the step (b) further comprises the step (b1) of providing a fluorine-containing compound to fill the accommodating space.
In one embodiment, the fluorine-containing compound is one selected from the group consisting of polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE).
In one embodiment, the molar ratio of the fluorine-containing compound to the alkali metal-containing fluoride ranges from 0:1 to 0.1: 1.
In one embodiment, the non-oxidizing atmosphere is an argon atmosphere or a nitrogen atmosphere.
Drawings
Fig. 1 is a flowchart illustrating a method for manufacturing a positive electrode material for a secondary battery according to a first preferred embodiment of the present invention.
Fig. 2 is a schematic diagram of a closed system for containing secondary particles according to a first preferred embodiment of the present invention.
Fig. 3 shows the results of the particle size analysis of the secondary particles in the first example of the present invention.
Fig. 4 shows the XRD analysis result of the positive electrode material for a secondary battery having carbon coating and containing fluorine obtained in the first example of the present invention.
Fig. 5 shows the result of particle size analysis of secondary particles in a second example of the present invention.
Fig. 6 shows XRD analysis results of the positive electrode material for a secondary battery having carbon coating and containing fluorine obtained in the second example of the present invention.
Fig. 7 is a flowchart illustrating a method for manufacturing a positive electrode material for a secondary battery according to a second preferred embodiment of the present invention.
FIG. 8 is a schematic diagram of a closed system for containing secondary particles and fluorine-containing compound according to a second preferred embodiment of the present invention.
[ notation ] to show
10: secondary particles
11: carbon-coated precursor
12: fluoride containing alkali metals
2: closed system
20: containing space
30: fluorine-containing compound
S11-S13: step (ii) of
S21-S24: step (ii) of
Detailed Description
Some exemplary embodiments that embody features and advantages of the invention will be described in detail in the description that follows. As will be realized, the invention is capable of other and different forms without departing from the scope thereof, and the description and drawings are to be regarded as illustrative in nature, and not as restrictive.
Fig. 1 is a flowchart illustrating a method for manufacturing a positive electrode material for a secondary battery according to a first preferred embodiment of the present invention. Fig. 2 is a schematic diagram of a closed system for containing secondary particles according to a preferred embodiment of the invention. The method for producing a positive electrode material for a secondary battery according to the present invention is used for producing a positive electrode material for a secondary battery having a carbon coating and containing fluorine. Secondary batteries such as, but not limited toAn alkali metal secondary battery comprising a lithium secondary battery, a sodium secondary battery, a potassium secondary battery or an alloy thereof. In the present embodiment, the carbon-coated fluorine-containing cathode material for the secondary battery can be, for example, lithium vanadium phosphate (LiVPO) selected from the group consisting of carbon-coated lithium vanadium phosphate 4 F/C), lithium aluminum fluoride phosphate (LiAlPO) with carbon coating 4 F/C), lithium manganese fluoride phosphate (LiMnPO) with carbon coating 4 F/C), fluorine lithium titanium phosphate (LiTiPO) with carbon coating 4 F/C), lithium fluoride cobalt phosphate with carbon coating (LiCoPO) 4 F/C), fluorine lithium nickel phosphate (LiNiPO) with carbon coating 4 F/C), carbon-coated lithium zinc fluoride phosphate (LiZnPO) 4 F/C), lithium chromium fluoride phosphate with carbon coating (LiCrPO) 4 F/C), sodium vanadium fluoride phosphate with carbon coating (NaVPO) 4 F/C), sodium aluminum fluoride phosphate with carbon coating (NaAlPO) 4 F/C), carbon coated sodium fluoro manganese phosphate (NaMnPO) 4 F/C), fluorine sodium titanium phosphate (NaTiPO) with carbon coating 4 F/C), sodium fluorine cobalt phosphate with carbon coating (NaCoPO) 4 F/C), fluorine sodium nickel phosphate (NaNiPO) with carbon coating 4 F/C), sodium zinc fluophosphate (NaZnPO) with carbon coating 4 F/C), sodium chromium fluoride phosphate with carbon coating (NaCrPO) 4 F/C), carbon-coated potassium vanadium phosphate fluoride (KVPO) 4 F/C), potassium aluminum fluoride phosphate (KAlPO) with carbon coating 4 F/C), carbon-coated potassium manganese phosphate fluoride (KMnPO) 4 F/C), fluorine potassium titanium phosphate (KTiPO) with carbon coating 4 F/C), carbon-coated potassium cobalt fluoride phosphate (KCoPO) 4 F/C), fluorine potassium nickel phosphate (KNiPO) with carbon coating 4 F/C), potassium zinc phosphate fluoride (KZnPO) with carbon coating 4 F/C) and carbon-coated chromium potassium phosphate (KCrPO) 4 F/C) is selected from the group consisting of. The method for producing a positive electrode material for a secondary battery of the present invention comprises the following steps.
First, in step S11, a carbon-coated precursor 11 and an alkali metal-containing fluoride 12 are provided to form a secondary particle 10. Wherein the precursor 11 with carbon coating can be selected from Vanadium Phosphate (VPO) with carbon coating 4 C) aluminum phosphate with carbon coating (AlPO) 4 /C), manganese phosphate with carbon coating (MnPO) 4 C) carbon-coated titanium phosphate (TiPO) 4 C), cobalt phosphate with carbon coating(CoPO 4 /C), nickel phosphate (NiPO) with carbon coating 4 /C), zinc phosphate (ZnPO) with carbon coating 4 C) and carbon-coated chromium phosphate (CrPO) 4 /C) one of the group. The carbon-coated precursor 11 can be synthesized by, for example, solid-phase synthesis (solid-phase synthesis), but the invention is not limited thereto. The fluoride 12 containing an alkali metal may be, for example, one selected from the group consisting of lithium fluoride (LiF), sodium fluoride (NaF), and potassium fluoride (KF). It should be noted that the sources of the carbon-coated precursor 11 and the alkali metal-containing fluoride 12 do not limit the formation of the secondary particles 10. In the embodiment, the molar ratio of the precursor 11 with carbon coating to the fluoride 12 containing alkali metal is in the range of 1:1.0 to 1: 1.05. The molar ratio of the precursor 11 with carbon coating and the fluoride 12 containing alkali metal is in the range of 1:1.0 to 1:1.05 according to the dosage ratio, and the secondary particles 10 can be formed by mixing, pulping and spray granulation. In the present embodiment, the average particle size of the secondary particles ranges from 5 μm to 30 μm.
Next, in step S12, a closed system 2 having a containing space 20 is provided, and the containing space 20 is filled with the secondary particles 10. The closed system 2 may be, for example, a closed tank, and the filling of the closed system 2 may be, for example, operated in a glove box in a non-oxidizing environment, which is not intended to limit the invention. The volume filling rate of the secondary particles 10 in the accommodating space 20 is greater than 30%, and as the volume filling rate of the secondary particles 10 with the carbon-coated precursor 11 and the alkali metal-containing fluoride 12 is increased, the production efficiency can be increased, and the production cost can be reduced.
Finally, in step S13, the closed system 2 is maintained in a non-oxidizing environment such as an argon atmosphere or a nitrogen atmosphere, and heat treatment is performed at a temperature of 300 ℃ to 900 ℃, so as to obtain a carbon-coated fluorine-containing cathode material for a secondary battery having a single pure phase. Because the closed system 2 is adopted for production, the product conversion rate and the production efficiency are improved, and the problems of material waste or environmental pollution can be avoided. In addition, as the volume filling rate of the secondary particles 10 of the carbon-coated precursor 11 and the alkali metal-containing fluoride 12 increases, the production efficiency is further increased, and the production cost is effectively reduced, in addition to ensuring that a single pure phase of the carbon-coated fluorine-containing cathode material for a secondary battery can be obtained.
In a first example, 1.0 mole of VPO is taken 4 and/C and 1.05 mol LiF, and forming the secondary particles 10 by mixing, pulping and spray granulation. Fig. 3 shows the results of the particle size analysis of the secondary particles in the first example of the present invention. In the present example, the secondary particles 10 have an average particle diameter of 27 μm and a tap density (tap density) of 1.3g/cm 3 . Wherein the secondary particles 10 have a surface area of 24m measured by BET 2 (ii) in terms of/g. Then, in an argon (Ar) atmosphere or nitrogen (N) gas, for example 2 ) The secondary particles 10 are filled into, for example, a can in a non-oxidizing atmosphere and the opening of the can is closed to form the closed system 2. In the accommodating space 20 of the closed system 2, the volume filling rate of the secondary particles 10 is 30%. The closed system 2 containing the secondary particles 10 is placed in a high-temperature furnace for heat treatment. In this example, the closed system 2 is maintained in a non-oxidizing environment, heated to 700 ℃ at a rate of 5 ℃ per minute, and then naturally cooled to room temperature after being maintained at 700 ℃ for 2 hours. The secondary particles 10 in the density system 2 form a carbon-coated fluorine-containing positive electrode material LiVPO for a secondary battery 4 F/C. Fig. 4 shows the XRD analysis result of the positive electrode material for a secondary battery having carbon coating and containing fluorine obtained in the first example of the present invention. Carbon-coated fluorine-containing positive electrode material LiVPO for secondary battery 4 F/C forms a single crystalline phase.
In a second example, 1.0 mole of VPO is taken 4 and/C and 1.0 mol LiF, and forming secondary particles by mixing, pulping and spray granulation. Fig. 5 shows the result of particle size analysis of secondary particles in a second example of the present invention. In the present example, the secondary particles 10 have an average particle diameter of 7 μm and a tap density (tap density) of 1.2g/cm 3 . Wherein the secondary particles 10 have a BET surface area of 19m 2 (ii) in terms of/g. Next, the secondary particles 10 are filled into a can, for example, in a non-oxidizing atmosphere such as an argon atmosphere or a nitrogen atmosphere, and then the opening of the can is closed to form the closed system 2. In the accommodating space 20 of the closed system 2, the volume filling rate of the secondary particles 10 is 30%. Will contain the secondary particles 10The closed system 2 is placed in a high temperature furnace for heat treatment. In this example, the temperature of the closed system 2 in the non-oxidizing environment is raised to 700 ℃ at a rate of 5 ℃ per minute, and the temperature is maintained at 700 ℃ for 2 hours, and then the furnace is cooled naturally. The secondary particles 10 in the density system 2 form a carbon-coated fluorine-containing positive electrode material LiVPO for a secondary battery 4 F/C. Fig. 6 shows XRD analysis results of the positive electrode material for a secondary battery having carbon coating and containing fluorine obtained in the second example of the present invention. Carbon-coated fluorine-containing positive electrode material LiVPO for secondary battery 4 F/C forms a single crystalline phase.
The series of table 1 shows another example of a positive electrode material for a carbon-coated fluorine-containing secondary battery obtained by heat-treating a carbon-coated precursor 11 and secondary particles 10 of an alkali metal-containing fluoride 12 at a temperature of 300 to 900 ℃ at a volume filling rate of more than 30%.
TABLE 1
It should be noted that, since the closed system 2 is used for the thermal treatment in the present invention, the intermediate product can be prevented from escaping to generate the impurity phase during the formation of the product of the carbon-coated precursor 11 and the secondary particles 10 of the alkali metal-containing fluoride 12. The positive electrode material LiVPO for the secondary battery having carbon coating and containing fluorine in the above exemplary list 4 F/C, for example, the closed system 2 may avoid, for example, Vanadium Fluoride (VF) 3 ) Gaseous intermediates escape, elimination of others such as lithium vanadium phosphate (Li) 3 V 2 (PO 4 ) 3 ) The formation of a heterogeneous phase. And as the volume filling rate of the carbon-coated precursor 11 and the secondary particles 10 of the fluoride 12 containing the alkali metal is increased, the single pure-phase positive electrode material for the carbon-coated fluorine-containing secondary battery is ensured, the production efficiency is further increased, and the production cost is effectively reduced.
Fig. 7 is a flowchart illustrating a method for manufacturing a positive electrode material for a secondary battery according to a second preferred embodiment of the present invention. FIG. 8 shows a second embodiment of the present inventionSchematic representation of subparticles and fluorochemicals. In the present embodiment, the closed system 2 and the secondary particle 10 are similar to the closed system 2 and the secondary particle 10 shown in fig. 1 to 2, and the same reference numerals denote the same components, structures and functions, which are not described herein again. First, in step S21, a carbon-coated precursor 11 and an alkali metal-containing fluoride 12 are provided to form a secondary particle 10. The carbon-coated precursor 11 can be synthesized by a solid phase method, but the invention is not limited thereto. Of course, the sources of the carbon-coated precursor 11 and the alkali metal-containing fluoride 12 do not limit the formation of the secondary particles 10. Unlike the closed system 2 and the secondary particles 10 shown in fig. 1 to 2, in the present embodiment, a fluorine-containing compound 30 is further provided in step S22. In the present embodiment, the fluorine-containing compound 30 may be, for example, one selected from the group consisting of polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE). Wherein the molar ratio of the fluorine-containing compound 30 to the alkali metal-containing fluoride 12 is in the range of 0:1 to 0.1: 1. Next, in step S23, a closed system 2 is provided, which has an accommodating space 20, and the accommodating space 20 is filled with the secondary particles 10 and the fluorine-containing compound 30, wherein the volume filling rate of the secondary particles 10 in the accommodating space 20 is greater than 30%. Finally, in step S24, the closed system 2 is heat-treated at a temperature of 300 ℃ to 900 ℃ in a non-oxidizing atmosphere such as an argon atmosphere or a nitrogen atmosphere, so as to obtain a carbon-coated fluorine-containing positive electrode material for a secondary battery having a single pure phase. The positive electrode material for the secondary battery with carbon coating and fluorine is produced by adopting the closed system 2, and the fluorine-containing compound 30 is added into the closed system 2 and filled into the accommodating space 20, so that the heat treatment of the closed system 2, such as Vanadium Fluoride (VF), is increased 3 ) The vapor pressure of the gas makes the reaction more favorable for forming the carbon-coated fluorine-containing cathode material LiVPO for the secondary battery with a single crystal phase 4 F/C. It should be noted that the addition of the fluorine-containing compound can be varied according to the actual application requirements, and in other embodiments, the fluorine-containing compound can be further added in the process of forming the secondary particles 10 from the precursor 11 with carbon coating and the fluoride 12 containing alkali metal, and the invention is not limited thereto and is not limited theretoThe above-mentioned processes are described.
In summary, the present invention provides a method for manufacturing a positive electrode material for a secondary battery, so as to produce a carbon-coated fluorine-containing positive electrode material for a secondary battery. The positive electrode material for the secondary battery with carbon coating and fluorine is produced through a closed system, which is beneficial to improving the product conversion rate and the production efficiency and avoiding the problems of material waste or environmental pollution. The whole production process is simple in process and low in production cost. The obtained carbon-coated fluorine-containing anode material for the secondary battery has a single crystal phase in XRD analysis, is favorable for achieving high electric capacity, high discharge power and excellent long cycle life of the secondary battery, and simultaneously improves thermal stability, high temperature performance and the like. In addition, when the closed system is subjected to heat treatment, the volume filling rate of the precursor with the carbon coating and the secondary particles of the fluoride containing the alkali metal is more than 30 percent, so that the positive electrode material for the secondary battery with the single pure phase, the carbon coating and the fluorine containing can be obtained, and the problems of material waste or environmental pollution are avoided. With the increase of the volume filling rate of the precursor with carbon coating and the secondary particles containing the fluoride of the alkali metal, the positive electrode material for the secondary battery with carbon coating and fluorine containing of a single pure phase can be obtained, the production efficiency is increased, and the production cost is effectively reduced. On the other hand, when the carbon-coated precursor and the secondary particles of the fluoride containing the alkali metal are thermally treated in the closed system, the conversion rate and the production efficiency of the product can be improved by adding the fluorine-containing compound.
The present invention may be modified in various ways by those skilled in the art without departing from the scope of the appended claims.
Claims (10)
1. A method for producing a positive electrode material for a secondary battery, comprising:
(a) providing a precursor with carbon coating and fluoride containing alkali metal to form a secondary particle;
(b) providing a closed system which is provided with an accommodating space and filled with the secondary particles, wherein the volume filling rate of the secondary particles in the accommodating space is more than 30%;
(b1) providing a fluorine-containing compound, and filling the fluorine-containing compound into the accommodating space; and
(c) performing heat treatment at a temperature of 300-900 ℃ in a non-oxidizing environment to generate the cathode material.
2. The method for producing a positive electrode material for a secondary battery according to claim 1, wherein the positive electrode material is selected from the group consisting of lithium-vanadium-fluoride-phosphate with carbon coating, lithium-aluminum-fluoride-phosphate with carbon coating, lithium-manganese-fluoride-phosphate with carbon coating, lithium-titanium-fluoride-phosphate with carbon coating, lithium-cobalt-fluoride-phosphate with carbon coating, lithium-nickel-fluoride-phosphate with carbon coating, lithium-chromium-fluoride-phosphate with carbon coating, vanadium-sodium-fluoride-phosphate with carbon coating, aluminum-sodium-fluoride-phosphate with carbon coating, manganese-sodium-fluoride-phosphate with carbon coating, titanium-fluoride-phosphate with carbon coating, cobalt-sodium-fluoride-phosphate with carbon coating, nickel-fluorine-fluoride-phosphate with carbon coating, zinc-fluorine-sodium-phosphate with carbon coating, chromium-fluorine-sodium phosphate with carbon coating, vanadium-potassium-fluorine-potassium-phosphate with carbon coating, aluminum-potassium-fluorine-potassium-phosphate with carbon coating, manganese-fluorine-potassium-phosphate with carbon coating, potassium-fluoride-phosphate with carbon coating, titanium-fluoride-cobalt-coating, Carbon-coated nickel potassium fluoride phosphate, carbon-coated zinc potassium fluoride phosphate, and carbon-coated chromium potassium fluoride phosphate.
3. The method of claim 1, wherein the carbon-coated precursor is one selected from the group consisting of carbon-coated vanadium phosphate, carbon-coated aluminum phosphate, carbon-coated manganese phosphate, carbon-coated titanium phosphate, carbon-coated cobalt phosphate, carbon-coated nickel phosphate, carbon-coated zinc phosphate, and carbon-coated chromium phosphate.
4. The method for producing a positive electrode material for a secondary battery according to claim 1, wherein the fluoride containing an alkali metal is one selected from the group consisting of lithium fluoride, sodium fluoride and potassium fluoride.
5. The method of claim 1, wherein the molar ratio of the carbon-coated precursor to the alkali metal-containing fluoride ranges from 1:1.0 to 1: 1.05.
6. The method of manufacturing a positive electrode material for a secondary battery according to claim 1, wherein the step (a) forms the secondary particles by mixing, slurrying, and spray granulation.
7. The method for producing a positive electrode material for a secondary battery according to claim 1, wherein the secondary particles have an average particle diameter in a range of 5 μm to 30 μm.
8. The method for manufacturing a positive electrode material for a secondary battery according to claim 1, wherein the fluorine-containing compound is one selected from the group consisting of polyvinylidene fluoride and polytetrafluoroethylene.
9. The method for producing a positive electrode material for a secondary battery according to claim 1, wherein the molar ratio of the fluorine-containing compound to the alkali metal-containing fluoride ranges from 0:1 to 0.1: 1.
10. The method for producing a positive electrode material for a secondary battery according to claim 1, wherein the non-oxidizing atmosphere is an argon atmosphere or a nitrogen atmosphere.
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| WO2014051020A1 (en) * | 2012-09-28 | 2014-04-03 | Tdk株式会社 | Lithium ion secondary battery |
| CN109755514A (en) * | 2018-12-27 | 2019-05-14 | 大连博融新材料有限公司 | A kind of carbon coating lithium vanadium fluorophosphates lithium ionic cell anode material and preparation method thereof |
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| WO2014051020A1 (en) * | 2012-09-28 | 2014-04-03 | Tdk株式会社 | Lithium ion secondary battery |
| CN109755514A (en) * | 2018-12-27 | 2019-05-14 | 大连博融新材料有限公司 | A kind of carbon coating lithium vanadium fluorophosphates lithium ionic cell anode material and preparation method thereof |
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