CN111509209A - Positive electrode material coated with phosphorus-containing compound and preparation method thereof - Google Patents
Positive electrode material coated with phosphorus-containing compound and preparation method thereof Download PDFInfo
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a positive electrode material coated with a phosphorus-containing compound and a preparation method thereof, and relates to a positive electrode material of a lithium battery. The preparation method comprises the steps of coating a phosphorus-containing compound layer on the surface of a positive electrode material by an atomic layer deposition method; wherein the phosphorus-containing compound in the phosphorus-containing compound layer is one or more of phosphorus oxide, phosphorus nitride and phosphorus oxynitride. The atomic layer deposition can accurately control the coating thickness to form a uniform protective layer. The deposited phosphorus-containing compound reacts with the residual lithium on the surface of the anode material to generate a fast ion conductor substance, so that the residual lithium on the surface of the anode material is reduced, and the fast ion conductor containing phosphorus can reduce the interface impedance and improve the material performance.
Description
Technical Field
The invention relates to the field of positive electrode materials of lithium batteries, in particular to a positive electrode material coated with a phosphorus-containing compound and a preparation method thereof.
Background
The lithium ion battery is widely applied in the fields of mobile phones, notebook computers, electric tools, electric vehicles and the like, and with the development of science and technology, people put forward higher requirements on the energy density, the cycle performance and the safety performance of the lithium ion battery, the anode material of the lithium ion battery directly determines the energy density, the cycle performance and the like of the lithium ion battery to a certain extent.
At present, people generally adopt a surface coating modification method to relieve the degradation process of the anode material. The traditional coating method mainly comprises wet coating and high-temperature solid-phase synthesis. Chinese patent CN110010879A discloses a high-nickel anode material with a uniform coating layer and a preparation method thereof, wherein an ethanol solution containing a certain amount of phosphoric acid is added into the anode material, a mixed solution is obtained after stirring, and then the mixed solution is filtered, dried and finally sintered for 10 hours at 500 ℃. The purpose is to react phosphoric acid with residual lithium to generate lithium phosphate and reduce the residual lithium on the surface of the anode material. However, this method involves solid-liquid separation in actual production, and therefore, energy consumption is large, and uneven distribution of lithium remaining on the surface of the positive electrode material causes uneven distribution of lithium phosphate generated by the reaction, and a uniform coating film cannot be formed.
In addition, chinese patent CN104781960A proposes that after the cathode material is sintered once, a certain amount of solid boric acid is mixed and then high temperature solid phase synthesis is performed to reduce the residual lithium on the surface of the cathode material. However, first, such dry coating is not uniformly mixed. Secondly, the dry coating amount is not easy to control, and the addition amount is too large, so that a large amount of inactive substances are introduced into the positive electrode material due to too thick coating, and the capacity of the positive electrode material is further reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a positive electrode material coated with a phosphorus-containing compound, which has the characteristics of low energy consumption, low price of used materials, uniform formed coating layer and the like.
Another object of the present invention is to provide a positive electrode material coated with a phosphorus compound, which has low interfacial resistance and good cycle performance.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a preparation method of a positive electrode material coated with a phosphorus-containing compound, which comprises the following steps of coating a phosphorus-containing compound layer on the surface of the positive electrode material by an atomic layer deposition method; wherein the phosphorus-containing compound in the phosphorus-containing compound layer is one or more of phosphorus oxide, phosphorus nitride and phosphorus oxynitride.
Further, the thickness of the phosphorus compound layer is 0.1-1000 nm.
Further, the step of coating the surface of the positive electrode material with the phosphorus-containing compound layer by the atomic layer deposition method includes:
s1, placing the anode material in a reaction cavity of atomic layer deposition equipment, heating the reaction cavity to 25-450 ℃ and keeping the temperature for 0-5.0 h;
s2, introducing the precursor A into the reaction cavity, setting the pressure of the reaction cavity to be 0.1-100 torr, and setting the reaction time to be 1-3000S;
s3, introducing scavenging gas into the reaction chamber for removing redundant precursor A and byproducts;
s4, introducing a precursor B into the reaction cavity, wherein the reaction time is 1-3000S;
s5, introducing the scavenging gas into the reaction chamber for removing the redundant precursor B and byproducts;
s6, repeating the steps S2-S5 until the thickness of the coated phosphorus-containing compound layer reaches 0.1-1000 nm, and obtaining the positive electrode material coated with the phosphorus-containing compound.
Further, after step S6, the method further includes:
and S7, carrying out post-treatment on the positive electrode material coated with the phosphorus-containing compound, wherein the post-treatment temperature is 300-700 ℃, and the post-treatment time is 0.1-12 h.
Further, before or after the step of coating the surface of the positive electrode material with the phosphorus compound layer by the atomic layer deposition method, the method further comprises the following steps:
and coating or doping elements on the surface of the positive electrode material or the phosphorus-containing compound layer by a mechanical stirring method, a mechanical fusion method or a solution chemical synthesis and then sintering method, wherein the elements comprise one or more of Al, Ti, Mg, Zr, Nb, F, B, W, Zn, V, Ta, L a and Hf.
Further, the precursor A is a precursor containing phosphorus elements, and comprises one or more of triethyl phosphate, trimethyl phosphate, tris (dimethylamino) phosphine, and diethyl phosphate.
Further, the precursor B is a precursor containing oxygen or nitrogen elements, and comprises one or more of water, oxygen, ozone, hydrogen peroxide, plasma oxygen atoms, ammonia gas, plasma nitrogen atoms, ethylene glycol and ethylenediamine.
Further, the purge gas is nitrogen or argon.
Further, the surface of the cathode material contains residual lithium in the form of lithium hydroxide or lithium carbonate; the residual lithium content is 0.1-50000 ppm.
The invention also provides a positive electrode material coated with the phosphorus-containing compound, which is prepared by the preparation method of the positive electrode material coated with the phosphorus-containing compound.
The positive electrode material coated with the phosphorus-containing compound and the preparation method thereof have the beneficial effects that:
the invention provides a method for coating a positive electrode material with a phosphorus-containing compound based on an atomic layer deposition technology. The atomic layer deposition is self-limiting saturated adsorption, so that the coating thickness can be accurately controlled by controlling the coating layer to form a uniform protective layer. The deposited phosphorus-containing compound reacts with residual lithium on the surface of the anode material and other surface metal elements to generate a fast ion conductor substance, so that the residual lithium content on the surface of the anode material is reduced, and on the other hand, the formed fast ion conductor containing phosphorus can effectively reduce the interface impedance, so that the performance of the anode material is improved. The coating method provided by the invention has the advantages of less used materials, low material cost, wide equipment operation window, dry operation and environmental friendliness.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a comparative graph of cycling performance of button cells provided in test example 1 of the present invention;
FIG. 2 is an SEM image of a high-nickel cathode material coated with a phosphorus-containing compound provided in example 1 of the present invention; wherein, fig. 2a is a schematic structural diagram of a high nickel cathode material coated with a phosphorus-containing compound; FIG. 2b is a schematic diagram of the structure of a phosphorus-containing compound layer under EDS-Mapping;
fig. 3 is a graph comparing the impedance performance of button cells of test example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The positive electrode material coated with a phosphorus compound and the method for producing the same according to the present invention will be specifically described below.
The invention provides a preparation method of a positive electrode material coated with a phosphorus-containing compound, which comprises the following steps of coating a phosphorus-containing compound layer on the surface of the positive electrode material by an atomic layer deposition method; wherein the phosphorus-containing compound in the phosphorus-containing compound layer is one or more of phosphorus oxide, phosphorus nitride and phosphorus oxynitride.
Further, the thickness of the phosphorus-containing compound layer is 0.1 to 1000 nm. The coated phosphorus compound layer is too thin to protect the positive electrode material. And the coated phosphorus-containing compound layer with too thick layer can increase polarization and reduce gram capacity of the lithium ion battery. Preferably, the thickness of the coated phosphorus compound layer is in the range of 0.1nm to 50 nm. The thickness of the coated phosphorus-containing compound layer can reach the specified coating thickness according to the adjustment of the reaction temperature, the reaction time and the number of the coating layers of a reaction cavity of the atomic layer deposition equipment. According to the invention, the uniform phosphorus-containing compound layer with controllable thickness is formed on the surface of the anode material, so that the anode material is protected, and the performance of the anode material can be optimized, thereby improving the performance of the lithium ion battery prepared by using the anode material.
Further, in a preferred embodiment of the present invention, the surface of the positive electrode material may not have a coating, but the surface of the positive electrode material may contain residual lithium in the form of lithium hydroxide or lithium carbonate, the residual lithium may be obtained by overdesign during the synthesis of the positive electrode material, and the phosphorus-containing compound to be coated can react with the residual lithium in the positive electrode material to form a fast ion conductor such as lithium phosphate, L iPON, etc. this reduces the residual lithium content on the surface of the positive electrode material on one hand, and on the other hand, the formed fast ion conductor containing phosphorus can effectively reduce the interfacial resistance of the positive electrode material and improve the performance of the positive electrode material, wherein the residual lithium content is generally 0.1 to 50000ppm, more preferably 100to 10000ppm, and the formation of the fast ion conductor containing phosphorus on the coating surface of the positive electrode material is facilitated by designing an appropriate content of residual lithium on the surface of the positive electrode material.
Further, the step of coating the surface of the positive electrode material with the phosphorus-containing compound layer by the atomic layer deposition method includes:
s1, placing the anode material in a reaction cavity of the atomic layer deposition equipment, heating the reaction cavity to 25-450 ℃ and keeping the temperature for 0-5.0 h. Preferably, the temperature of the reaction cavity is 100-350 ℃ and kept for 0.5-4.5 h, so that the temperature of the positive electrode material is ensured to be stable at a temperature suitable for subsequent reaction.
S2, introducing the precursor A into the reaction cavity, setting the pressure of the reaction cavity to be 0.1-100 torr, and setting the reaction time to be 1-3000S. Preferably, the pressure of the reaction cavity is 0.1-20 torr, the reaction time is 1-250 s, the reaction time and the temperature of the reaction cavity are controlled, and the thickness of the coated phosphorus-containing compound layer can be controlled.
Further, the precursor a is a precursor containing phosphorus elements, and includes one or more of triethyl phosphate, trimethyl phosphate, tris (dimethylamino) phosphine, and diethyl phosphate. Preferably, the precursor A is trimethyl phosphate which is colorless transparent liquid, is easily dispersed in the reaction chamber after being heated, and easily forms a wrapping layer of the precursor A on the surface line of the anode material, so that the subsequent reaction is facilitated, and the price is low.
S3, a purge gas is introduced into the reaction chamber to remove excess precursor a and by-products.
Furthermore, the cleaning gas is nitrogen or argon, and inert gas is used for cleaning, so that on one hand, redundant precursor A and byproducts can be removed, on the other hand, the inert gas cannot react with the precursor A and the anode material, and the influence of other substances on the performance of the anode material is avoided.
And S4, introducing the precursor B into the reaction cavity, wherein the reaction time is 1-3000S. Preferably, the reaction time is 1-250 s, and enough time is ensured for the precursor B to react with the precursor A wrapped on the surface of the anode material to produce a corresponding phosphorus-containing compound layer, so that the phosphorus-containing compound reacts with residual lithium on the surface of the anode material to produce a phosphorus-containing fast ion conductor, and the performance of the anode material is improved.
Further, the precursor B is a precursor containing oxygen or nitrogen elements, and comprises one or more of water, oxygen, ozone, hydrogen peroxide, plasma oxygen atoms, ammonia gas, plasma nitrogen atoms, ethylene glycol and ethylenediamine. The precursor B is a substance with oxidation or nitridation performance, and can oxidize or nitrify the precursor A wrapped on the surface of the anode material into phosphorus oxide, phosphorus nitride or phosphorus oxynitride, so that a phosphorus-containing compound layer is formed, the anode material is protected, and the phosphorus-containing fast ion conductor can be generated by the reaction of the precursor B and residual lithium. Preferably, the precursor B is water, and the raw material is easily available and cheap.
And S5, introducing a purge gas into the reaction chamber for removing the redundant precursor B and the by-products.
S6, repeating the steps S2-S5 until the thickness of the coated phosphorus compound layer reaches 0.1-50 nm, and obtaining the phosphorus compound coated positive electrode material. Wherein the growth rate of the coated phosphorus compound layer is 1 to 100 angstrom per cycle, and one cycle is defined as step S2 to step S5.
Further, after step S6, the method further includes:
s7, post-treating the positive electrode material coated with the phosphorus-containing compound at the temperature of 300-700 ℃ for 0.1-12 h. Preferably, the post-treatment temperature is 450-650 ℃, the time is 1-6 h, and the post-treatment step can ensure that a small amount of the phosphorus-containing compound coated on the surface of the positive electrode material permeates into the stable structure of the positive electrode material, so that the interface impedance of the coated phosphorus-containing compound layer and the positive electrode material is reduced, and the ionic conductivity is enhanced.
Further, before or after the step of coating the surface of the positive electrode material with the phosphorus compound layer by the atomic layer deposition method, the method further comprises the following steps:
the method comprises the steps of coating or doping elements on the surface of a positive electrode material or a phosphorus-containing compound layer by a mechanical stirring method, a mechanical fusion method or a solution chemical synthesis and then sintering method, wherein the elements comprise one or more of Al, Ti, Mg, Zr, Nb, F, B, W, Zn, V, L i, Ta, L a and Hf.
The invention also provides a positive electrode material coated with the phosphorus-containing compound, which is prepared by the preparation method of the positive electrode material coated with the phosphorus-containing compound. The surface of the anode material is coated with the phosphorus-containing compound, so that the residual lithium content on the surface of the anode material is reduced, the phosphorus-containing fast ion conductor is formed, the interface impedance of the anode material is reduced, and the cycle performance of the anode material is further improved.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
In this embodiment, a phosphorus oxide-coated high-nickel ternary material is taken as an example:
s1, placing the high-nickel ternary material into a reaction cavity of atomic layer deposition equipment, setting the reaction temperature to be 250 ℃ and keeping the reaction temperature for 2 hours;
s2, in the embodiment, trimethyl phosphate is used as a precursor A, trimethyl phosphate is introduced into the reaction cavity, the pressure is set to be 5torr, and the reaction time is 50S;
s3, introducing N2Purging excessive trimethyl phosphate and byproducts for 50 s;
s4, H in this example2O is used as a precursor B, and H is introduced into the reaction cavity2O, setting the pressure to be 5torr, and setting the reaction time to be 50 s;
s5, introducing N2Purging excess H2O and by-products, purge time 50 s;
s6, repeating the step S2-S550 times to obtain the anode material uniformly coated with 10nm of phosphorus oxide;
s7, the post-treatment temperature is 600 ℃, and the post-treatment time is 3 h.
Example 2
This example takes a phosphorus oxide-coated lithium cobaltate material as an example:
s1, placing the lithium cobaltate material into a reaction cavity of the atomic layer deposition equipment, setting the reaction temperature to 300 ℃ and keeping the reaction temperature for 2 hours;
s2, in the embodiment, trimethyl phosphate is used as a precursor A, trimethyl phosphate is introduced into the reaction cavity, the pressure is set to be 5torr, and the reaction time is 50S;
s3, introducing N2Purging excessive trimethyl phosphate and byproducts for 50 s;
s4, O in this example3Introducing O into the reaction cavity as a precursor B3Setting the pressure to be 5torr and the reaction time to be 50 s;
s5, introducing N2Purging excess O3And by-products, purge time 50 s;
s6, repeating the step S2-S550 times to obtain the anode material uniformly coated with 10nm of phosphorus oxide;
s7, the post-treatment temperature is 600 ℃, and the post-treatment time is 3 h.
Example 3
This example takes phosphorus oxide coated high nickel ternary material as an example:
s1, selecting a high-nickel ternary material coated with Al by a mechanical fusion method, placing the high-nickel ternary material into a reaction cavity of atomic layer deposition equipment, setting the reaction temperature to be 200 ℃, and keeping the reaction temperature for 2.0 hours;
s2, in the embodiment, trimethyl phosphate is used as a precursor A, trimethyl phosphate is introduced into the reaction cavity, the pressure is set to be 5torr, and the reaction time is 50S;
s3, introducing N2Purging excessive trimethyl phosphate and byproducts for 50 s;
s4, O in this example3Introducing O into the reaction cavity as a precursor B3Setting the pressure to be 5torr and the reaction time to be 50 s;
s5, introducing N2Purging excess O3And by-products, purge time 50 s;
s6, repeating the step S2-S550 times to obtain the anode material uniformly coated with 10nm of phosphorus oxide;
s7, the post-treatment temperature is 450 ℃, and the post-treatment time is 3 h.
Test example 1: electrical Performance testing
The phosphorus compound-coated high-nickel cathode material provided in example 1 was assembled into a CR2032 button cell by methods well known in the art. The method comprises the following specific steps:
weighing a certain mass of high-nickel positive electrode material coated with a phosphorus-containing compound, a conductive agent and a binder according to a ratio of 90:5:5, uniformly mixing, adding a proper amount of NMP, stirring for 3.5h in a planetary ball mill to obtain uniformly dispersed slurry, coating the slurry on an aluminum foil, baking for 4h at 80 ℃ in a blower, rolling and slicing to obtain a positive electrode wafer, weighing, placing the positive electrode wafer in a vacuum drying box for baking for more than 120 h to remove water in the electrode wafer, quickly transferring the electrode wafer into a glove box after the temperature of the electrode wafer is reduced to room temperature, taking a lithium wafer as a negative electrode wafer, taking a 1 mol/L lithium hexafluorophosphate solution as an electrolyte, using a celgard2400 diaphragm, assembling a battery in the glove box, standing for 8h after the battery is assembled, and performing an electrical charge and discharge test, wherein the result is shown in.
The button cell assembled by the high-nickel positive electrode material coated with the phosphorus-containing compound provided by the embodiment 1 has the capacity retention rate of more than 98% after 100 cycles, and the battery assembled by the high-nickel positive electrode material not coated with the phosphorus-containing compound has the capacity retention rate of less than 94% after 100 cycles.
Test example 2: residual lithium test
The titration experiment of residual lithium of the positive electrode material provided in example 1 before and after coating with the phosphorus-containing compound was carried out according to the titration experiment, and the results of the experiment are shown in the following table. After the phosphorus-containing compound is coated, the total content of residual lithium can be reduced by about 1100ppm, the content of residual lithium in the positive electrode material is effectively reduced, and the pH value of the positive electrode material is reduced from 12.5 to 11.6. The reduction of the residual lithium and the PH can reduce the sensitivity of the anode material to moisture, thereby reducing the severe requirements on the environmental humidity in the processes of anode material storage and battery production and further reducing the production cost of enterprises.
| Sample (I) | LiOH(W)ppm | Li2CO3(W)ppm | Li+(W)ppm |
| Before coating | 6043 | 3133 | 2340 |
| After coating | 2997 | 2089 | 1261 |
Test example 3: SEM test
The high nickel cathode material coated with the phosphorus compound provided in example 1 was subjected to SEM test, and the results are shown in fig. 2. Fig. 2a is a schematic structural view of a high nickel cathode material coated with a phosphorous compound, and fig. 2b is a schematic structural view of a phosphorous compound layer under EDS-Mapping. In fig. 2b, it can be seen that the coating material is uniformly coated on the surface of the positive electrode material, and the original particle morphology of the surface of the positive electrode material is maintained without significant change. Further, it is demonstrated that the coating is very thin and very uniform. The traditional dry method is used for mixed coating, so that the coating amount is large and uneven; the invention can realize uniform and controllable coating layers on the surfaces of the anode material particles of the battery, which is incomparable with other coating layers. The coating thickness can be from 0.1nm to 1000nm to realize the coating with the specified thickness according to the requirement; the minimum coating source is used, and the coating efficiency is improved.
Test example 4: impedance testing
The assembly procedure of the button cell assembled from the high nickel cathode material coated with the phosphorus-containing compound provided in example 1 is shown in fig. 3, where the assembly procedure is as in test example 1, and then an ac impedance test is performed.
The results show that the impedance of the battery assembled from the material provided in example 1 is significantly lower than the battery assembled from the positive electrode material not coated with the phosphorus-containing compound. It is shown again that the coating method provided by the invention can effectively reduce the surface impedance of the anode material, and the traditional coating method can improve the impedance of the material due to too thick and uneven coating of the coating layer. The coating method of the invention coats the fast ion conductor with nanometer thickness, effectively reduces the impedance of the material and further improves the performance of the material.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a positive electrode material coated with a phosphorus-containing compound is characterized in that a phosphorus-containing compound layer is coated on the surface of the positive electrode material by an atomic layer deposition method; wherein the phosphorus-containing compound in the phosphorus-containing compound layer is one or more of phosphorus oxide, phosphorus nitride and phosphorus oxynitride.
2. The method for producing the phosphorus compound-coated positive electrode material according to claim 1, wherein the thickness of the phosphorus compound layer is 0.1 to 1000 nm.
3. The method for producing the phosphorus compound-coated positive electrode material according to claim 1, wherein the step of coating the surface of the positive electrode material with the phosphorus compound layer by an atomic layer deposition method comprises:
s1, placing the anode material in a reaction cavity of atomic layer deposition equipment, heating the reaction cavity to 25-450 ℃ and keeping the temperature for 0-5.0 h;
s2, introducing the precursor A into the reaction cavity, setting the pressure of the reaction cavity to be 0.1-100 torr, and setting the reaction time to be 1-3000S;
s3, introducing scavenging gas into the reaction chamber for removing redundant precursor A and byproducts;
s4, introducing a precursor B into the reaction cavity, wherein the reaction time is 1-3000S;
s5, introducing the scavenging gas into the reaction chamber for removing the redundant precursor B and byproducts;
s6, repeating the steps S2-S5 until the thickness of the coated phosphorus-containing compound layer reaches 0.1-1000 nm, and obtaining the positive electrode material coated with the phosphorus-containing compound.
4. The method for producing the phosphorus compound-coated positive electrode material according to claim 3, further comprising, after step S6:
and S7, carrying out post-treatment on the positive electrode material coated with the phosphorus-containing compound, wherein the post-treatment temperature is 300-700 ℃, and the post-treatment time is 0.1-12 h.
5. The method for producing the phosphorus compound-coated positive electrode material according to claim 3, further comprising, before or after the step of coating a phosphorus compound layer on the surface of the positive electrode material by an atomic layer deposition method:
and coating or doping elements on the surface of the positive electrode material or the phosphorus-containing compound layer by a mechanical stirring method, a mechanical fusion method or a solution chemical synthesis and then sintering method, wherein the elements comprise one or more of Al, Ti, Mg, Zr, Nb, F, B, W, Zn, V, L i, Ta, L a and Hf.
6. The method according to claim 3, wherein the precursor A is a precursor containing phosphorus element, and comprises one or more of triethyl phosphate, trimethyl phosphate, tris (dimethylamino) phosphine, and diethyl phosphate.
7. The preparation method of the phosphorus compound-coated positive electrode material according to claim 3, wherein the precursor B is a precursor containing oxygen or nitrogen, and comprises one or more of water, oxygen, ozone, hydrogen peroxide, plasma oxygen atoms, ammonia gas, plasma nitrogen atoms, ethylene glycol and ethylenediamine.
8. The method according to claim 3, wherein the purge gas is nitrogen or argon.
9. The method for producing the phosphorus compound-coated positive electrode material according to claim 1, wherein the surface of the positive electrode material contains residual lithium in the form of lithium hydroxide or lithium carbonate; the residual lithium content is 0.1-50000 ppm.
10. A positive electrode material coated with a phosphorus compound, characterized by being produced by the method for producing a positive electrode material coated with a phosphorus compound according to any one of claims 1 to 9.
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