CN113555538A - Carbon-free high-capacity positive electrode material and preparation method thereof - Google Patents
Carbon-free high-capacity positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of lithium ion battery materials, in particular to a carbon-free high-capacity positive electrode material and a preparation method thereof. The preparation method of the carbon-free high-capacity cathode material comprises the following steps: providing a raw material for synthesizing a lithium ion battery anode material; mixing a lithium supplement agent with the raw materials by a deposition method to obtain a precursor of the positive electrode material; and calcining the precursor of the positive electrode material to obtain the carbon-free high-capacity positive electrode material. According to the preparation method, no carbon material is added, and the lithium supplement agent and the raw materials of the positive electrode material are fully mixed by a deposition method, so that the adding amount of the lithium supplement agent can be controlled, and the finally obtained carbon-free high-capacity positive electrode material can be used for a lithium ion battery to improve the capacity and the cycle life of the battery.
Description
Technical Field
The application belongs to the technical field of lithium ion battery materials, and particularly relates to a carbon-free high-capacity positive electrode material and a preparation method thereof.
Background
With the application of lithium ion batteries in electric vehicles, battery cathode materials are more and more widely concerned, the performance of the cathode materials directly influences the popularization of the electric vehicles, and the development of high-capacity, high-safety, long-service life, low-cost and environment-friendly cathode materials is the main direction of future development.
At present, the electrochemical performance of the cathode material is generally improved by different forms of composite carbon materials, but the method has certain defects. For example, taking lithium iron phosphate (LFP) as an example, the following problems occur after LFP is compounded with a carbon material: firstly, the specific capacity is reduced to a certain extent; the tap density is reduced; thirdly, because the lithium iron phosphate generally needs to be nanocrystallized, the carbon coating is difficult to be uniform and stable, and the consistency of the product is difficult to control; the carbon coating increases the water absorption of the material, and brings more difficulty to the manufacturing process of the battery; the diffusion coefficient of lithium ions is reduced; sixthly, the synthesis condition is harsh; and the conductive carbon is not uniformly dispersed.
Disclosure of Invention
The application aims to provide a carbon-free high-capacity cathode material and a preparation method thereof, and aims to solve the technical problem that the electrochemical performance of the cathode material of a lithium ion battery can be improved on the premise of not using carbon material for compounding.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a carbon-free high-capacity cathode material, comprising the steps of:
providing a raw material for synthesizing a lithium ion battery anode material;
mixing a lithium supplement agent with the raw materials by a deposition method to obtain a precursor of the positive electrode material;
and calcining the precursor of the positive electrode material to obtain the carbon-free high-capacity positive electrode material.
The application provides a preparation method of a carbon-free high-capacity positive electrode material, which realizes pre-lithiation of the positive electrode material of a lithium ion battery through a deposition technology, and particularly, the preparation method mixes a lithium supplement agent with a raw material for synthesizing the positive electrode material of the lithium ion battery in advance through a deposition method and then obtains the lithium-rich carbon-free high-capacity positive electrode material through sintering. According to the preparation method, the carbon material is not added, the lithium supplement agent is fully mixed with the raw materials of the positive electrode material, the adding amount of the lithium supplement agent can be controlled through the condition of a deposition method, and the finally obtained carbon-free high-capacity positive electrode material can be used for the lithium ion battery, so that the capacity of the battery can be improved, and the cycle life of the battery can be prolonged.
In a second aspect, the present application provides a carbon-free high capacity positive electrode material prepared by the preparation method described herein.
The carbon-free high-capacity positive electrode material is prepared by the specific preparation method, and the carbon-free high-capacity positive electrode material rich in lithium is obtained by mixing a lithium supplement agent with raw materials for synthesizing the positive electrode material of the lithium ion battery in advance through a deposition method without adding a carbon material. The carbon-free high-capacity cathode material is used for the lithium ion battery, so that the capacity and the cycle life of the battery can be improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing a carbon-free high-capacity cathode material provided in an embodiment of the present application;
FIG. 2 is a schematic diagram of an apparatus for preparing a carbon-free high-capacity cathode material according to an embodiment of the present disclosure;
fig. 3 is an SEM image of a carbon-free high capacity positive electrode material provided by an example of the present application;
fig. 4 is a battery capacity performance diagram of the carbon-free high-capacity cathode material provided in the example of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "plural" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including single item or any combination of plural items. It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc. The room temperature in the present application means 25 to 27 ℃.
In a first aspect, an embodiment of the present application provides a method for preparing a carbon-free high-capacity cathode material, as shown in fig. 1, the method includes the following steps:
s01: providing a raw material for synthesizing a lithium ion battery anode material;
s02: mixing a lithium supplement agent with the raw materials by a deposition method to obtain a precursor of the positive electrode material;
s03: and calcining the precursor of the positive electrode material to obtain the carbon-free high-capacity positive electrode material.
According to the preparation method of the carbon-free high-capacity cathode material, the pre-lithiation of the lithium ion battery cathode material is realized through a deposition technology, and specifically, the preparation method mixes a lithium supplement agent with a raw material for synthesizing the lithium ion battery cathode material in advance through a deposition method, and then the lithium-rich carbon-free high-capacity cathode material is obtained through sintering. According to the preparation method, no carbon material is added, the lithium supplement agent is fully mixed with the raw materials of the positive electrode material, the adding amount of the lithium supplement agent can be controlled under the condition of a deposition method, and the finally obtained carbon-free high-capacity positive electrode material can be used for a lithium ion battery, so that the capacity of the battery can be improved, and the cycle life of the battery can be prolonged.
In the above step S01: the raw materials for synthesizing the lithium ion battery anode material can be common raw materials for synthesizing various types of anode materials at present, such as corresponding soluble salts. For example, the lithium ion battery anode material may be any one of lithium iron phosphate, lithium manganese iron phosphate, ternary materials (such as nickel-cobalt-manganese ternary material or nickel-cobalt-aluminum ternary material), and the like, and the raw material is a raw material for synthesizing the lithium ion battery anode material.
Specifically, if the lithium ion battery anode material is a lithium iron phosphate anode material, raw materials for synthesizing the lithium ion battery anode material comprise a phosphorus source, an iron source and a lithium source; specifically, the phosphorus source may be selected from at least one of diammonium hydrogen phosphate, ammonium phosphate, and phosphoric acid, the iron source may be a soluble ferrous salt, such as at least one selected from ferrous nitrate, ferrous chloride, ferrous acetate, and ferrous sulfate, and the lithium source may be a soluble lithium salt, such as at least one selected from lithium carbonate, lithium hydroxide, and lithium chloride.
Or, if the lithium ion battery anode material is a lithium iron manganese phosphate anode material, the raw materials for synthesizing the lithium ion battery anode material comprise a phosphorus source, a manganese source, an iron source and a lithium source; specifically, the phosphorus source may be selected from at least one of diammonium hydrogen phosphate, ammonium phosphate, and phosphoric acid, the manganese source may be selected from at least one of manganese acetate, manganese oxalate, manganese nitrate, manganese sulfate, and manganese phosphate, the iron source may be selected from at least one of ferrous nitrate, ferrous chloride, ferrous acetate, and ferrous sulfate, and the lithium source may be selected from at least one of lithium carbonate, lithium hydroxide, and lithium chloride.
Or, if the lithium ion battery anode material is a nickel-cobalt-aluminum ternary material, the raw materials for synthesizing the lithium ion battery anode material comprise a nickel source, a cobalt source, an aluminum source and a lithium source; or, if the lithium ion battery anode material is a nickel-cobalt-manganese ternary material, the raw materials for synthesizing the lithium ion battery anode material comprise a nickel source, a cobalt source, a manganese source and a lithium source.
In step S02, the raw material of the positive electrode material and the lithium supplement agent are fully mixed. Specifically, the deposition method for mixing the lithium supplement agent with the raw material may be a magnetron sputtering method, and the step of mixing the lithium supplement agent with the raw material by the magnetron sputtering method includes: when the raw material for synthesizing the lithium ion battery anode material is subjected to ball milling treatment, a lithium supplement agent is taken as a target material and is deposited in the raw material through magnetron sputtering. The raw materials for synthesizing the lithium ion battery anode material continuously move in the ball milling process, and the lithium supplement agent target material is deposited in the ball-milled raw materials through magnetron sputtering, so that the raw materials and the lithium supplement agent are mixed better and uniformly, and the uniformly dispersed anode material precursor is obtained.
Specifically, the lithium supplement agent is at least one selected from lithium ferrite, lithium nickelate, lithium nitride, lithium carbide, lithium sulfide and lithium fluoride. The lithium supplement agent can be well mixed with raw materials for synthesizing the lithium ion battery anode material.
Further, when the raw materials for synthesizing the lithium ion battery anode material are subjected to ball milling treatment, the rotating speed of the ball milling treatment is 200r/min-500 r/min. The raw materials are subjected to ball milling under the condition, so that the ball milling is more uniform, and the raw materials can be more fully mixed with the lithium supplement agent of magnetron sputtering to obtain the uniformly dispersed precursor of the positive electrode material containing the lithium supplement agent.
Further, in the step of depositing the lithium supplement agent on the raw material through magnetron sputtering, the sputtering power of magnetron sputtering is 1 KW-20 KW; the sputtering temperature of the magnetron sputtering is 80-100 ℃. Under the conditions, the magnetron sputtering deposition effect of the lithium supplement target is better.
Further, according to the mass ratio of the lithium supplement agent to the lithium ion battery anode material (2-6): (94-98), mixing the lithium supplement with the raw materials. Under the condition of the mass ratio, the lithium-rich effect of the cathode material can be better.
Further, after the lithium supplement agent is uniformly mixed with the raw materials by a magnetron sputtering method to obtain a precursor of the anode material, the precursor is directly calcined at the temperature of 600-900 ℃, so that the carbon-free high-capacity anode material is obtained.
In one embodiment, the present application provides an apparatus for implementing the above-described method for preparing a carbon-free high capacity positive electrode material, as shown in fig. 2: the device comprises a sputtering chamber (used for realizing the magnetron sputtering process of a lithium supplement target material), a target material (namely a lithium supplement agent) at the upper end of the sputtering chamber, a ball milling device (used for realizing the ball milling process of a raw material for synthesizing a lithium ion battery anode material) at the lower end of the sputtering chamber and sputtering conditionsThe control panel of (1). The target material is arranged opposite to the ball milling device, the distance between the target material and the upper end face of the ball milling device is 10cm-50cm, so that sputtered materials can fall into the ball milling device completely and are uniformly mixed with the raw materials in the ball milling device, and the ball milling speed is set to be 200r/min-500r/min in order to be fully mixed with received lithium supplement materials. And sputtering a lithium supplement target material into a ball milling device, obtaining a precursor mixed with the lithium supplement agent by ball milling raw materials of a positive electrode material in the ball milling device, closing a vacuum pump after sputtering is finished, replacing inert gas, continuing ball milling, and taking out the precursor for sintering after the temperature is reduced, wherein the sintering temperature is 600-900 ℃. The magnetron sputtering conditions can be set as follows: vacuum degree of 1X10-7And the sputtering power is 1-20 KW below Pa, and the amount of the lithium supplement agent is controlled by controlling the time and the rate of magnetron sputtering.
The second aspect of the embodiments of the present application also provides a carbon-free high-capacity cathode material, which is prepared by the preparation method described above.
The carbon-free high-capacity positive electrode material is prepared by the specific preparation method, and the carbon-free high-capacity positive electrode material rich in lithium is obtained by mixing a lithium supplement agent with raw materials for synthesizing the positive electrode material of the lithium ion battery in advance through a deposition method without adding a carbon material. The carbon-free high-capacity cathode material is used for the lithium ion battery, so that the capacity and the cycle life of the battery can be improved.
Specifically, the carbon-free high-capacity positive electrode material of the present application is a lithium-rich carbon-free lithium ion battery positive electrode material, and may be any one of a lithium-rich carbon-free lithium iron phosphate positive electrode material, a lithium-rich carbon-free lithium manganese iron phosphate positive electrode material, a lithium-rich carbon-free nickel cobalt aluminum ternary material, a lithium-rich carbon-free nickel cobalt manganese ternary material, and the like. The capacity of the carbon-free high-capacity cathode material of the present application is brought to a theoretical capacity of the non-prelithiated cathode material by fully mixing the lithium supplement agent with the raw material of the cathode material without adding the carbon material.
The carbon-free high-capacity positive electrode material is used for preparing a positive electrode plate, and then is assembled with a negative electrode plate, a diaphragm and electrolyte to form the lithium ion battery. In the embodiment, the mass ratio of the lithium supplement agent to the synthesized lithium ion battery anode material is (2-6): (94-98), mixing according to the preparation method to prepare the positive electrode material of the lithium ion battery, then preparing a positive plate, and further assembling to obtain the lithium ion secondary battery.
The following description will be given with reference to specific examples.
Example 1
A preparation method of a carbon-free high-capacity positive electrode material, namely a lithium iron phosphate lithium-rich material, comprises the following steps:
preparing lithium ferrite as a target material, vacuumizing a sputtering chamber in a magnetic control device, connecting the sputtering chamber with a ball milling device, and adding ammonium dihydrogen phosphate, lithium carbonate and ferrous nitrate into the ball milling device according to the mol ratio of Li: fe: p is 1: 1: 1, the sputtering power is 5KW, the temperature in the sputtering chamber is 80 ℃, and the ball milling speed is 500 r/min. Firstly, starting sputtering of a lithium ferrite target material, simultaneously controlling a ball milling device to perform ball milling mixing for 4 hours, closing sputtering of lithium ferrite, replacing with inert gas, continuing ball milling for 10 hours, slowly reducing the temperature to room temperature to obtain a precursor, sintering the precursor at 600 ℃, and finally obtaining a carbon-free high-capacity positive electrode material, namely a lithium iron phosphate lithium-rich material (an SEM image is shown in figure 3).
Example 2
A preparation method of a carbon-free high-capacity positive electrode material, namely a lithium iron manganese phosphate lithium-rich material, comprises the following steps:
preparing lithium nickelate as a target material, vacuumizing a sputtering chamber in magnetic control equipment, connecting the sputtering chamber with a ball milling device, and putting ammonium phosphate, manganese acetate, lithium chloride and ferrous acetate into the ball milling device according to the mol ratio of Li: fe: mn: p is 1: 0.2: mixing at the ratio of 1:0.8, wherein the sputtering power is 10KW, the temperature in a sputtering chamber is 100 ℃, and the ball milling speed is 400 r/min. Firstly, starting sputtering of a lithium nickelate target material, simultaneously controlling a ball milling device to perform ball milling mixing for 4 hours, closing the sputtering of the lithium nickelate, replacing inert gas, continuing ball milling for 10 hours, slowly reducing the temperature to room temperature to obtain a precursor, and sintering the precursor at 700 ℃ to obtain a carbon-free high-capacity positive electrode material, namely the lithium iron manganese phosphate lithium-rich material.
Example 3
A method for preparing a carbon-free high-capacity positive electrode material, namely a nickel-cobalt-manganese lithium-rich material, comprises the following steps:
preparing lithium nitride as a target material, vacuumizing a sputtering chamber in a magnetic control device, connecting the sputtering chamber with a ball milling device, and putting lithium oxalate, nickel sulfate, cobalt sulfate and manganese sulfate into the ball milling device according to the mol ratio of Li: ni: co: mn ═ 1.05: 0.5: 0.3: 0.2, the sputtering power is 20KW, the temperature in the sputtering chamber is 100 ℃, and the ball milling speed is 400 r/min. Firstly, starting sputtering of a lithium nitride target material, simultaneously controlling a ball milling device to perform ball milling mixing for 4 hours, closing the sputtering of the lithium nitride, replacing with inert gas, continuing ball milling for 10 hours, simultaneously slowly reducing the temperature to room temperature to obtain a precursor, and sintering the precursor at 900 ℃ to obtain the carbon-free high-capacity positive electrode material, namely the nickel-cobalt-manganese lithium-rich material.
Comparative example 1
The preparation method of the carbon-coated lithium iron phosphate composite material comprises the following steps:
s1: preparing a conductive carbon dispersion liquid;
s2: taking a phosphorus source, an iron source and a lithium source according to the proportion of the ball-milled lithium iron phosphate raw material in the embodiment 1 to prepare a lithium iron phosphate precursor solution;
s3: and uniformly stirring and mixing the conductive carbon dispersion liquid and the lithium iron phosphate precursor solution, drying, and sintering to obtain the carbon-coated lithium iron phosphate composite material.
Comparative example 2
The preparation method of the carbon-coated lithium iron phosphate composite material comprises the following steps:
taking a phosphorus source, an iron source and a lithium source according to the proportion of the ball-milled lithium iron phosphate raw material in the embodiment 1 to prepare a lithium iron phosphate precursor solution; and drying and sintering, and performing vapor deposition on a carbon material in the sintering process to obtain the carbon-coated lithium iron phosphate composite material.
Comparative example 3
Preparation method of lithium iron phosphate coated lithium iron phosphate composite material
S1: adding the ferrous sulfate solution, the lithium hydroxide solution, the ammonium monohydrogen phosphate solution and the titanyl sulfate solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction under the stirring condition to obtain the slurry.
S2: adding a dispersing agent into the slurry obtained in the step S1, stirring for 20min to obtain a base solution, then preparing a ferric chloride solution, an ammonium bicarbonate solution and a lithium hydroxide solution, adding the ferric chloride solution, the ammonium bicarbonate solution and the lithium hydroxide solution into the base solution in a parallel flow manner under the stirring condition, maintaining the pH value of the feeding process to be 7.5, the temperature to be 50 ℃, the feeding time to be 3h, introducing carbon dioxide after the feeding is finished, continuing to react for 1.5h to ensure that the lithium content in the supernatant is lower than 0.2g/L, then filtering, heating the filter residue to be washed by pure water, and drying, screening and removing iron to obtain a precursor;
s3: and (4) calcining the precursor obtained in the step (S2) in an inert atmosphere, and carrying out jet milling, screening and iron removal on the calcined material to obtain the lithium iron phosphate composite material coated by the lithium ferrite.
And (3) performance testing:
the above examples and comparative examples were subjected to performance tests:
the battery capacity development graph of example 1 is shown in fig. 4, and the carbon-free high capacity cathode material prepared in this example: the lithium supplementing agent lithium phosphate (LFO) and lithium iron phosphate (LFP) are prepared in a compounding way according to the ratio of 0.2:0.98, the capacity is exerted to 171mAh/g, the single lithium iron phosphate is generally charged to 3.7V, the capacity is exerted to 160mAh/g, and the capacity of the composite material obtained in the comparative examples 1-3 is exerted to 160 mAh/g; therefore, the carbon-free high-capacity cathode material prepared by the embodiment of the application exceeds the theoretical capacity of lithium iron phosphate.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a carbon-free high-capacity cathode material is characterized by comprising the following steps:
providing a raw material for synthesizing a lithium ion battery anode material;
mixing a lithium supplement agent with the raw materials by a deposition method to obtain a precursor of the positive electrode material;
and calcining the precursor of the positive electrode material to obtain the carbon-free high-capacity positive electrode material.
2. The method of preparing a carbon-free high capacity positive electrode material according to claim 1, wherein the step of mixing a lithium supplement agent with the raw material by a deposition method comprises: and when the raw materials are subjected to ball milling treatment, the lithium supplement agent is taken as a target material and is deposited in the raw materials through magnetron sputtering.
3. The method for preparing a carbon-free high-capacity cathode material according to claim 2, wherein the rotation speed of the ball milling treatment is 200r/min to 500 r/min.
4. The method for preparing a carbon-free high-capacity cathode material according to claim 2, wherein the sputtering power of the magnetron sputtering is 1KW to 20 KW; and/or the presence of a gas in the gas,
the sputtering temperature of the magnetron sputtering is 80-100 ℃.
5. The preparation method of the carbon-free high-capacity cathode material according to claim 1, wherein the mass ratio of the lithium supplement agent to the lithium ion battery cathode material is (2-6): (94-98) mixing the lithium supplement agent with the raw material.
6. The method of preparing a carbon-free high capacity positive electrode material according to claim 1, wherein the lithium supplement agent is at least one selected from the group consisting of lithium ferrite, lithium nickelate, lithium nitride, lithium carbide, lithium sulfide and lithium fluoride.
7. The method for preparing a carbon-free high-capacity cathode material according to any one of claims 1 to 6, wherein the lithium ion battery cathode material is selected from at least one of lithium iron phosphate, lithium manganese iron phosphate, and a ternary material.
8. The method for producing a carbon-free high-capacity positive electrode material according to any one of claims 1 to 6, wherein the temperature of the calcination treatment is 600 to 900 ℃.
9. A carbon-free high-capacity positive electrode material, characterized in that it is produced by the production method according to any one of claims 1 to 8.
10. The carbon-free high capacity positive electrode material according to claim 9, wherein the carbon-free high capacity positive electrode material is a lithium-rich carbon-free lithium ion battery positive electrode material.
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Cited By (3)
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|---|---|---|---|---|
| CN114804211A (en) * | 2022-05-20 | 2022-07-29 | 洛阳师范学院 | High-first-efficiency lithium ferrate negative electrode material for lithium ion battery and preparation method thereof |
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