CN114156478B - Positive electrode material coated with co-embedded film, preparation method and lithium ion battery - Google Patents
Positive electrode material coated with co-embedded film, preparation method and lithium ion battery 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
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- 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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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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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Abstract
The invention provides a positive electrode material coated with a co-embedded film, a preparation method and a lithium ion battery. The co-embedded film includes an amorphous oxide layer of phosphorus and an amorphous oxide layer of titanium. The atomic layer deposition method can realize accurate regulation and control of element content and proportion, has low cost and short cladding period, the PO bond in the obtained co-embedded film with specific element proportion and content can prevent material structure collapse caused by material deoxidation, and the amorphous oxide layer of phosphorus can also form fast ion conductor lithium phosphate with residual lithium of the anode material, thereby reducing interface impedance. The amorphous oxide layer of titanium has the effect of blocking electrolyte attack. Therefore, the positive electrode material coated with the co-embedded film and the lithium ion battery assembled by the positive electrode material have higher capacity and cycle performance.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a positive electrode material coated with a co-embedded film, a preparation method and a lithium ion battery.
Background
Lithium ion batteries play an important role in energy storage and conversion. With the development of new energy automobiles and the increase of power battery demands, the delivery of lithium batteries in China is increased year by year. While lithium batteries are increasingly in demand, safety, cycling stability, energy density, and cost issues of lithium batteries are of great concern. In a lithium battery, the cost of the cathode material is 40% of the total battery cost, and determines the performance of 60% of the total lithium battery. Therefore, improving the cycle life of the positive electrode material, increasing the energy density, reducing the impedance, and reducing the production cost would be a problem to be solved currently. The high-nickel ternary positive electrode material has the characteristics of high specific capacity and low cost, but in the use process, when the high-nickel ternary positive electrode material is in a high-lithium removal state, phase change, lithium-nickel mixed discharge and the like are easy to occur, so that the material structure is collapsed, and the material capacity is lost. Therefore, it is a common goal of the industry to improve and make safe and stable positive electrode materials by improving the performance of high nickel positive electrode materials.
At present, lithium battery material manufacturers generally adopt modification methods such as doping or surface coating and the like to improve the cycle stability and capacity of the high-nickel ternary material. The traditional doping and coating mainly comprises solid phase doping, solid phase coating, liquid phase coating and the like. Chinese patent CN108878827a discloses a high nickel ternary positive electrode material coated by a dioxygen compound and a preparation method thereof, firstly adding the high nickel ternary material into absolute ethyl alcohol, then adding a titanium source and a silicon source into an ethanol solution to obtain a dispersion liquid, then adding the dispersion liquid into the absolute ethyl alcohol solution containing the high nickel ternary material, heating and stirring to obtain a coating material precursor, and finally sintering the precursor to obtain the double oxide composite coated high nickel ternary positive electrode material. The method relates to solid-liquid separation in actual production, and has the advantages of high energy consumption, difficult control of thickness uniformity of the coating material by a solution method, and influence on conductivity of the material due to the fact that silicon dioxide is non-conductive and too thick in coating.
In addition, chinese patent CN110492067a discloses a preparation method of an aluminum-titanium composite coated nickel-cobalt-manganese positive electrode material, which uses a vapor deposition method to coat, and the chemical deposition method controls the coating amount completely by controlling the reaction time, so that it is difficult to precisely control the thickness of the coating layer, not only the utilization rate is not high due to too much reactant passing, but also the three-dimensional powder particles are difficult to deposit by chemical vapor deposition, and even deposition is more difficult to be realized in the deposited powder. Therefore, chemical vapor deposition is not only consumed in a large amount, powder coating is not uniform, but also a large amount of inactive substances are introduced due to excessive coating, thereby further reducing the capacity of the cathode material.
Disclosure of Invention
The invention aims to provide a positive electrode material coated with a co-embedded film, which has higher capacity and cycle performance.
The invention further aims to provide a preparation method of the anode material of the coated co-embedded film, which not only can accurately regulate and control the content and proportion of elements by an atomic layer deposition method, but also has low cost and environmental friendliness, and is suitable for industrial mass production.
A third object of the present invention is to provide a lithium ion battery that is low in cost and superior in performance.
The invention solves the technical problems by adopting the following technical scheme.
The invention provides a positive electrode material coated with a co-embedded film, which comprises a positive electrode material and a co-embedded film coated on the surface of the positive electrode material, wherein the co-embedded film comprises an amorphous oxide layer of phosphorus and an amorphous oxide layer of titanium.
The invention provides a preparation method of a positive electrode material coated with a co-embedded film, which comprises the following steps:
s1, placing the anode material into a reaction cavity of atomic layer deposition equipment, setting the pressure of the reaction cavity to be 0.001-1.0 torr, and keeping the temperature to be 25-400 ℃ for 1-5 h;
s2, introducing a precursor A into the reaction cavity, wherein the source time is 0.01-10S, the reaction time is 1-30S, the reaction times are 1-10 times, and then introducing a cleaning gas for purging redundant precursor A and byproducts;
s3, introducing a precursor B into the reaction cavity, wherein the source time is 0.01-10S, the reaction time is 1-30S, the reaction times are 1-10 times, and then introducing a cleaning gas for purging the redundant precursor B and byproducts;
s4, repeating the steps S2 and S3 for 0-4 times;
s5, introducing a precursor C into the reaction cavity, wherein the source time is 0.01-10S, the reaction time is 1-30S, the reaction times are 1-10 times, and then introducing a cleaning gas for purging redundant precursor C and byproducts;
s6, introducing a precursor B into the reaction cavity, wherein the source time is 0.01-10S, the reaction time is 1-30S, the reaction times are 1-10 times, and then introducing a cleaning gas for purging the redundant precursor B and byproducts;
s7, repeating the steps S2-S6 until the sum of the coating turns of the amorphous oxide layer of phosphorus and the amorphous oxide layer of titanium is 1-50 turns, and obtaining the anode material of the coating co-embedded film.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the positive electrode comprises the positive electrode material of the coated co-embedded film.
The positive electrode material of the coated co-embedded film, the preparation method and the lithium ion battery provided by the embodiment of the invention have the beneficial effects that:
1. the positive electrode material of the coated co-embedded film comprises a positive electrode material and the co-embedded film coated on the surface of the positive electrode material. The co-embedded film comprises an amorphous oxide layer of phosphorus (PO layer) and an amorphous oxide layer of titanium (TiO layer). The PO bond in the PO layer can solve the problem of stability of the material under high voltage and prevent the collapse of the material structure caused by deoxidization of the material. On the other hand, the PO layer can also form a fast ion conductor lithium phosphate with the residual lithium of the positive electrode material, so that the interface impedance is reduced. The TiO layer has the function of blocking electrolyte erosion. The invention selects specific active elements P and Ti which can react with the positive electrode material, and designates the thickness and the element proportion of the coating layer, and the obtained positive electrode material of the coated co-embedded film has higher capacity and cycle performance under a specific sintering process. In addition, the selected elements are low-cost and environment-friendly elements, and the coating doping requirements can be met by using a small amount of elements, so that the doping coating modification cost of enterprises can be greatly reduced.
2. The invention adopts atomic layer deposition technology to realize the precise regulation and control of element content and proportion. When the coating is carried out, only about 3 parts per million of coating amount is needed, the 0.1C discharge capacity can be improved by 8.11%, the 1C discharge capacity can be improved by 6.6%, and the cycle retention rate is improved from 31.42% to 95.27%. And the coating problem can be solved by adopting an atomic layer deposition method only by 5 cycle periods, and the method is suitable for industrialized mass production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing comparison of cycle performance of a button cell provided in test example 1 of the present invention;
fig. 2 is an SEM-mapping diagram of the positive electrode material of the coated co-embedded film of example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following describes the positive electrode material, the preparation method and the lithium ion battery of the coating co-embedded film in the embodiment of the invention.
The anode material coated with the co-embedded film comprises an anode material and the co-embedded film coated on the surface of the anode material, wherein the co-embedded film comprises an amorphous oxide layer of phosphorus and an amorphous oxide layer of titanium.
The co-embedded film of the invention is a multielement active film. Due to the self-limiting nature of atomic layer deposition techniques, each powder surface has the same reactivity, and therefore a uniform adsorption layer can be formed on the powder surface. The adsorption layer is single-layer adsorption and has self-saturation property. PO bonds in the co-embedded film can solve the problem of stability of the material under high voltage and prevent collapse of the material structure caused by deoxidation of the material. On the other hand, the PO layer can also form a fast ion conductor lithium phosphate with the residual lithium of the positive electrode material, so that the interface impedance is reduced. The TiO layer has the function of blocking electrolyte erosion, so that the capacity and the cycle performance of the anode material can be improved.
Further, in a preferred embodiment of the present invention, the sum of the number of coating turns of the amorphous oxide layer of phosphorus and the amorphous oxide layer of titanium is 1to 50. The invention can realize the adjustment of the coating thickness by adjusting the coating turns. Too thick a coating layer is not chemically active, thus reducing the capacity of the lithium battery, and too thin a coating layer is not effective for protection. When the number of the growth turns is 1-50, the chemical activity of the coating layer can be ensured, and effective protection can be formed, so that the electrical property of the anode material can be improved.
Further, in the preferred embodiment of the present invention, the content of phosphorus and the content of titanium in the co-embedded film are both 10 to 2000ppm, the total content of amorphous oxide of phosphorus and amorphous oxide of titanium is 20 to 3000ppm, and the content ratio of phosphorus to titanium is 0.01to 100:1. the coating amount of PO and TiO, the content of P and Ti and the element ratio in the co-embedded film all have influence on the improvement of the performance. The positive electrode materials with different capacities and cycle performances can be obtained by adjusting the coating amount, the element content and the proportion. In a preferred embodiment of the present invention, the capacity and cycle performance of the cathode material coated with the co-embedded thin film having a P content of 185ppm, a Ti content of 130ppm, and an elemental content ratio of P/Ti of 1.42:1, and a total content of 315ppm are optimal.
Further, in a preferred embodiment of the present invention, the surface of the positive electrode material is alternately coated with the amorphous oxide layer of phosphorus and the amorphous oxide layer of titanium. In the optimal embodiment of the invention, two amorphous oxides alternately grow, namely, two PO layers are firstly grown, one TiO layer is further grown, and the process is repeated for 5 times, so that the anode material of the coated co-embedded film with the P content of 185ppm, the Ti content of 130ppm, the P/Ti element content ratio of 1.42:1 and the total content of 315ppm can be obtained. The positive electrode material is sintered in pure oxygen at 600 ℃ for 10 hours, and the positive electrode material of the coated semi-doped semi-coated co-embedded film can be obtained.
Further, in a preferred embodiment of the present invention, the surface of the positive electrode material is coated with the amorphous oxide layer of phosphorus and the amorphous oxide layer of titanium in order from inside to outside. According to the invention, the PO layer is grown to a certain thickness, and then the TiO layer is grown to a required thickness, so that the anode material which is sequentially coated with the PO layer and the TiO layer from inside to outside is obtained.
Further, in a preferred embodiment of the present invention, the surface of the positive electrode material is coated with the amorphous oxide layer of titanium and the amorphous oxide layer of phosphorus in order from inside to outside. The invention can also obtain the anode material which is coated with the TiO layer and the PO layer in turn from inside to outside by firstly growing the TiO layer to a certain thickness and then growing the PO layer to a required thickness.
The invention selects specific active elements P and Ti which can react with the positive electrode material, designates the thickness and the element proportion of the coating layer, and obtains the positive electrode material of the coated co-embedded film with higher capacity and cycle performance under a specific sintering process. The structure of the positive electrode material can be stabilized through the synergistic effect of P and Ti, the consumption of active lithium ions is reduced, and the capacity is improved. In addition, the selected elements are low-cost and environment-friendly elements, and the coating doping requirements can be met by using a small amount of elements, so that the doping coating modification cost of enterprises can be greatly reduced.
The invention also provides a preparation method of the positive electrode material coated with the co-embedded film, which comprises the following steps:
s1, placing the anode material into a reaction cavity of atomic layer deposition equipment, setting the pressure of the reaction cavity to be 0.001-1.0 torr, and keeping the temperature to be 25-400 ℃ for 1-5 h;
s2, introducing a precursor A into the reaction cavity, wherein the source time is 0.01-10S, the reaction time is 1-30S, the reaction times are 1-10 times, and then introducing a cleaning gas for purging redundant precursor A and byproducts;
s3, introducing a precursor B into the reaction cavity, wherein the source time is 0.01-10S, the reaction time is 1-30S, the reaction times are 1-10 times, and then introducing a cleaning gas for purging the redundant precursor B and byproducts;
s4, repeating the steps S2 and S3 for 0-4 times;
s5, introducing a precursor C into the reaction cavity, wherein the source time is 0.01-10S, the reaction time is 1-30S, the reaction times are 1-10 times, and then introducing a cleaning gas for purging redundant precursor C and byproducts;
s6, introducing a precursor B into the reaction cavity, wherein the source time is 0.01-10S, the reaction time is 1-30S, the reaction times are 1-10 times, and then introducing a cleaning gas for purging the redundant precursor B and byproducts;
s7, repeating the steps S2-S6 until the sum of the coating turns of the amorphous oxide layer of phosphorus and the amorphous oxide layer of titanium is 1-50 turns, and obtaining the anode material of the coating co-embedded film.
The content of the added elements in the traditional solid-phase doping coating process is about 1 percent. At such high proportions not only an increase in the cost of the materials used but also failure to obtain maximum release of the activity of the positive electrode material can result. The liquid phase method doping coating process has the defects of high energy consumption, large coating amount and the like. The invention adopts atomic layer deposition technology to realize precise regulation and control of element content and proportion, and only about 3 parts per million of cladding amount is needed, so that the 0.1C discharge capacity is improved by 8.11%, the 1C discharge capacity is improved by 6.6%, and the cycle retention rate is improved from 31.42% to 95.27%. In addition, the conventional atomic layer deposition needs longer period and lower coating efficiency, and the invention can solve the coating problem by only carrying out 5 cycle periods, thereby being suitable for industrialized mass production.
Further, in a preferred embodiment of the present invention, the precursor a is an active precursor of phosphorus, including one or more of phosphoric acid, trimethyl phosphate, tri (dimethylamine) phosphorus, and trialkyl phosphorus oxide, the precursor B is an oxygen source precursor, including one or more of water, oxygen, and ozone, the precursor C includes one or more of titanium tetrachloride, titanium isopropoxide, titanium tetraethoxide, and titanium tetra (diethylamine), and the purge gas is nitrogen or argon.
Further, in a preferred embodiment of the present invention, after the step S7, the method further includes: and (3) carrying out post-treatment on the anode material coated with the co-embedded film, wherein the post-treatment temperature is 300-750 ℃, and the post-treatment time is 0.1-12 h. The semi-doped and semi-coated co-embedded film can be obtained by post-processing the positive electrode material coated with the co-embedded film, so that the performance of the positive electrode material can be improved. Preferably, the post-treatment temperature is 600 ℃, the post-treatment time is 10 hours, and the post-treatment gas atmosphere is pure oxygen. The PO/TO layer at about 600 ℃ can be subjected TO chemical reaction with residual lithium on the surface of the material, part of the residual lithium is consumed, a lithium phosphate and lithium titanate fast particle conductor layer is obtained, after long-term heat treatment for 10 hours, the coating layer is partially embedded into the material TO form shallow doping, and part of the coating layer is left on the surface TO form a coating layer. The performance of the positive electrode material of the coated co-embedded film obtained by post-treatment under the condition is optimal, and the effect of the assembled lithium ion battery is optimal.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the positive electrode comprises the positive electrode material of the coated co-embedded film. The positive electrode of the lithium ion battery is prepared from the positive electrode material of the coating co-embedded film, so that the capacity and the cycle performance of the lithium ion battery can be improved, and the adopted coating raw materials are low in price and environment-friendly, and are suitable for large-scale production.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a positive electrode material coated with a co-embedded film, which is prepared according to the following method:
(1) 10g of high-nickel ternary material 811 is weighed and placed into a reaction cavity of an atomic layer deposition device, and is vacuumized to 0.01torr, the reaction temperature is set to 250 ℃, and the holding time is set to 2.0h.
(2) Trimethyl phosphate is used as a precursor A, a source bottle is heated to 75-85 ℃, trimethyl phosphate is introduced into a reaction cavity, the introduction time is 2s, the reaction time is 10s, and the reaction times are 1 time.
(3) Ar gas is introduced to purge excess trimethyl phosphate and byproducts for 60 seconds and 2 times.
(4) By H 2 O is used as a precursor B, H is introduced into the reaction cavity 2 O, the charging time is 1s, the reaction time is 5s, and the reaction times are 1.
(5) Ar gas is introduced to purge excessive H 2 O and byproducts, purge time 60s, 2 times.
(6) Repeating the steps (2) - (5) for 2 times.
(7) Titanium tetrachloride is taken as a precursor C, a heating source bottle is heated to 75-85 ℃, titanium tetrachloride is introduced into a reaction cavity, the introduction time is 1.5s, the reaction time is 10s, and the reaction times are 1 time.
(8) Ar gas is introduced to purge excessive titanium tetrachloride and byproducts for 60 seconds for 2 times.
(9) By H 2 O is used as a precursor B, H is introduced into the reaction cavity 2 O, the charging time is 1s, the reaction time is 5s, and the reaction times are 1.
(10) Ar gas is introduced to purge excessive H 2 O and byproducts, purge time 60s, 2 times.
(11) Repeating the steps (2) - (10) for 5 times to obtain the anode material of the coated co-embedded film. The positive electrode material can be obtained through ICP test, the total amount of PO and TiO is 315ppm, and the P/Ti ratio is 1.42:1.
(12) And (3) carrying out post-treatment on the positive electrode material coated with the co-embedded film in pure oxygen atmosphere to obtain the positive electrode material coated with the semi-doped and semi-coated co-embedded film. Wherein the post-treatment temperature is 600 ℃, and the post-treatment time is 10 hours.
Example 2
The embodiment provides a positive electrode material coated with a co-embedded film, which is prepared according to the following method:
(1) 10g of high-nickel ternary material 811 is weighed and placed into a reaction cavity of an atomic layer deposition device, and is vacuumized to 0.01torr, the reaction temperature is set to 250 ℃, and the holding time is set to 2.0h.
(2) Trimethyl phosphate is used as a precursor A, a source bottle is heated to 75-85 ℃, trimethyl phosphate is introduced into a reaction cavity, the introduction time is 2s, the reaction time is 10s, and the reaction times are 1 time.
(3) Ar gas is introduced to purge excess trimethyl phosphate and byproducts for 60 seconds and 2 times.
(4) By H 2 O is used as a precursor B, H is introduced into the reaction cavity 2 O, the charging time is 1s, the reaction time is 5s, and the reaction times are 1.
(5) Ar gas is introduced to purge excessive H 2 O and byproducts, purge time 60s, 2 times.
(6) Titanium tetrachloride is taken as a precursor C, a heating source bottle is heated to 75-85 ℃, titanium tetrachloride is introduced into a reaction cavity for 1.5s, the reaction time is 10s, and the reaction times are 1 time
(7) Ar gas is introduced to purge excessive titanium tetrachloride and byproducts for 60 seconds for 2 times.
(8) By H 2 O is used as a precursor B, H is introduced into the reaction cavity 2 O, the charging time is 1s, the reaction time is 5s, and the reaction times are 1.
(9) Ar gas is introduced to purge excessive H 2 O and byproducts, purge time 60s, 2 times.
(10) Repeating the steps (2) - (9) for 6 times to obtain the anode material of the coated co-embedded film. The positive electrode material can be obtained through ICP test, the total amount of PO and TiO is 300ppm, and the P/Ti ratio is 1:1.
(11) And (3) carrying out post-treatment on the positive electrode material coated with the co-embedded film in pure oxygen atmosphere to obtain the positive electrode material coated with the semi-doped and semi-coated co-embedded film. Wherein the post-treatment temperature is 600 ℃, and the post-treatment time is 10 hours.
Example 3
The embodiment provides a positive electrode material coated with a co-embedded film, which is prepared according to the following method:
(1) 10g of high-nickel ternary material 811 is weighed and placed into a reaction cavity of an atomic layer deposition device, and is vacuumized to 0.01torr, the reaction temperature is set to 250 ℃, and the holding time is set to 2.0h.
(2) Trimethyl phosphate is used as a precursor A, a source bottle is heated to 75-85 ℃, trimethyl phosphate is introduced into a reaction cavity, the introduction time is 2s, the reaction time is 10s, and the reaction times are 1 time.
(3) Ar gas is introduced to purge excess trimethyl phosphate and byproducts for 60 seconds and 2 times.
(4) By H 2 O is used as a precursor B, H is introduced into the reaction cavity 2 O, the charging time is 1s, the reaction time is 5s, and the reaction times are 1.
(5) Ar gas is introduced to purge excessive H 2 O and byproducts, purge time 60s, 2 times.
(6) Repeating the steps (2) - (5) for 2 times.
(7) Titanium tetrachloride is taken as a precursor C, a heating source bottle is heated to 75-85 ℃, titanium tetrachloride is introduced into a reaction cavity, the introduction time is 1.5s, the reaction time is 10s, and the reaction times are 1 time.
(8) Ar gas is introduced to purge excessive titanium tetrachloride and byproducts for 60 seconds for 2 times.
(9) By H 2 O is used as a precursor B, H is introduced into the reaction cavity 2 O, the charging time is 1s, the reaction time is 5s, and the reaction times are 1.
(10) Ar gas is introduced to purge excessive H 2 O and byproducts, purge time 60s, 2 times.
(11) Repeating the steps (2) - (10) for 10 times to obtain the anode material of the coated co-embedded film. The positive electrode material can be obtained through ICP test, the total amount of PO and TiO is 630ppm, and the P/Ti ratio is 1.42:1.
(12) And (3) carrying out post-treatment on the positive electrode material coated with the co-embedded film in pure oxygen atmosphere to obtain the positive electrode material coated with the semi-doped and semi-coated co-embedded film. Wherein the post-treatment temperature is 600 ℃, and the post-treatment time is 10 hours.
Example 4
The embodiment provides a positive electrode material coated with a co-embedded film, which is prepared according to the following method:
(1) 10g of high-nickel ternary material 811 is weighed and placed into a reaction cavity of an atomic layer deposition device, and is vacuumized to 0.01torr, the reaction temperature is set to 250 ℃, and the holding time is set to 2.0h.
(2) Trimethyl phosphate is used as a precursor A, a source bottle is heated to 75-85 ℃, trimethyl phosphate is introduced into a reaction cavity, the introduction time is 2s, the reaction time is 10s, and the reaction times are 1 time.
(3) Ar gas is introduced to purge excess trimethyl phosphate and byproducts for 60 seconds and 2 times.
(4) By H 2 O is used as a precursor B, H is introduced into the reaction cavity 2 O, the charging time is 1s, the reaction time is 5s, and the reaction times are 1.
(5) Ar gas is introduced to purge excessive H 2 O and byproducts, purge time 60s, 2 times.
(6) Repeating the steps (2) - (5) for 3 times.
(7) Titanium tetrachloride is taken as a precursor C, a heating source bottle is heated to 75-85 ℃, titanium tetrachloride is introduced into a reaction cavity, the introduction time is 1.5s, the reaction time is 10s, and the reaction times are 1 time.
(8) Ar gas is introduced to purge excessive titanium tetrachloride and byproducts for 60 seconds for 2 times.
(9) By H 2 O is used as a precursor B, H is introduced into the reaction cavity 2 O, the charging time is 1s, the reaction time is 5s, and the reaction times are 1.
(10) Ar gas is introduced to purge excessive H 2 O and byproducts, purge time 60s, 2 times.
(11) Repeating the steps (2) - (10) for 5 times to obtain the anode material of the coated co-embedded film. The positive electrode material can be obtained through ICP test, the total amount of PO and TiO is 350ppm, and the P/Ti ratio is 2:1.
(12) And (3) carrying out post-treatment on the positive electrode material coated with the co-embedded film in pure oxygen atmosphere to obtain the positive electrode material coated with the semi-doped and semi-coated co-embedded film. Wherein the post-treatment temperature is 600 ℃, and the post-treatment time is 10 hours.
Example 5
The embodiment provides a positive electrode material coated with a co-embedded film, which is prepared according to the following method:
(1) 10g of high-nickel ternary material 811 is weighed and placed into a reaction cavity of an atomic layer deposition device, and is vacuumized to 0.01torr, the reaction temperature is set to 250 ℃, and the holding time is set to 2.0h.
(2) Trimethyl phosphate is used as a precursor A, a source bottle is heated to 75-85 ℃, trimethyl phosphate is introduced into a reaction cavity, the introduction time is 2s, the reaction time is 10s, and the reaction times are 1 time.
(3) Ar gas is introduced to purge excess trimethyl phosphate and byproducts for 60 seconds and 2 times.
(4) By H 2 O is used as a precursor B, H is introduced into the reaction cavity 2 O, the charging time is 1s, the reaction time is 5s, and the reaction times are 1.
(5) Ar gas is introduced to purge excessive H 2 O and byproducts, purge time 60s, 2 times.
(6) Repeating the steps (2) - (5) for 2 times.
(7) Titanium tetrachloride is taken as a precursor C, a heating source bottle is heated to 75-85 ℃, titanium tetrachloride is introduced into a reaction cavity, the introduction time is 1.5s, the reaction time is 10s, and the reaction times are 1 time.
(8) Ar gas is introduced to purge excessive titanium tetrachloride and byproducts for 60 seconds for 2 times.
(9) By H 2 O is used as a precursor B, H is introduced into the reaction cavity 2 O, the charging time is 1s, the reaction time is 5s, and the reaction times are 1.
(10) Ar gas is introduced to purge excessive H 2 O and byproducts, purge time 60s, 2 times.
(11) Repeating the steps (2) - (10) for 5 times to obtain the anode material of the coated co-embedded film. The positive electrode material can be obtained through ICP test, the total amount of PO and TiO is 315ppm, and the P/Ti ratio is 1.42:1.
(12) And (3) carrying out post-treatment on the positive electrode material coated with the co-embedded film in pure oxygen atmosphere to obtain the positive electrode material coated with the semi-doped and semi-coated co-embedded film. Wherein the post-treatment temperature is 450 ℃, and the post-treatment time is 10 hours.
Comparative example 1
This comparative example provides a high nickel ternary cathode material that is an uncoated high nickel ternary material 811.
Test example 1
And (3) testing electrical properties: the cathode materials of the coated co-embedded films of examples 1to 5 and the uncoated high-nickel ternary cathode material of comparative example 1 were assembled into CR2032 button cells, respectively. The method comprises the following specific steps:
the positive electrode materials of the coated co-embedded films of examples 1to 5 and the uncoated high-nickel ternary material 811 of comparative example 1 were weighed with a conductive agent and a binder in a ratio of 90:5:5, and after uniform mixing, an appropriate amount of NMP was added and stirred in a planetary ball mill for 3.5 hours to obtain a slurry which was uniformly dispersed. The slurry is coated on aluminum foil, baked for 4 hours at 80 ℃ in a blower, rolled and sliced to obtain the anode wafer. And weighing the anode wafer, and then placing the anode wafer in a vacuum drying oven to bake for more than 4 hours at 120 ℃ to remove the moisture in the pole piece. After the pole piece is cooled to room temperature, the pole piece is quickly transferred into a glove box, then a lithium piece is used as a negative pole piece, a 1mol/L lithium hexafluorophosphate solution is used as an electrolyte, a celgard2400 diaphragm is used, and the assembly of the button cell is carried out in the glove box. And after the battery is assembled, the battery is stationary for 8 hours for charge and discharge testing, namely, the battery is charged and discharged for 2 times at 0.1C, and then the 1C cycle performance testing is carried out.
Fig. 1 is a graph showing the cycle performance of the button cell provided in test example 1. As can be seen from fig. 1, the battery assembled with the non-coated high-nickel ternary positive electrode material provided in comparative example 1 decays rapidly, while the battery assembled with the positive electrode material coated with the co-embedded film of example 1 has the highest capacity. Compared with a battery assembled by uncoated high-nickel ternary cathode materials, the 0.1C discharge capacity of the battery assembled by the coated co-embedded film high-nickel ternary cathode materials in the embodiment 1 is improved from 203.6mAh/g to 220.15mAh/g, 8.12% is improved, and 7.13% is improved. The assembled battery of uncoated high nickel ternary positive electrode material decayed rapidly after 60 cycles with a capacity retention of only 31.42%, while the assembled battery of coated co-embedded thin film high nickel ternary positive electrode material of example 1 still had a capacity retention of 95.27% after 100 cycles.
Table 1 shows the capacity and cycle data table of this test example. As can be seen from Table 1, the P/Ti ratio of 1.42:1, total content of 315ppm, sintering temperature of 600℃and the performance of the assembled battery of the positive electrode material of the coated co-embedded film obtained after sintering under pure oxygen atmosphere for 10 hours were optimal. In examples 2 to 5, the final capacity and cycle result of the assembled battery of the obtained positive electrode material coated with the co-embedded film were not improved to the maximum extent due to the change of the P/Ti ratio, the total coating amount or the sintering time.
TABLE 1 Capacity and cycle data Table
Test example 2
Fig. 2 is an SEM-mapping diagram of the positive electrode material of the coated co-embedded film of example 1. It can be seen from FIG. 2 that the P/Ti forms a uniform coating on the surface of the high nickel ternary material.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the 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 made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (3)
1. The positive electrode material coated with the co-embedded film is characterized by comprising a positive electrode material and the co-embedded film coated on the surface of the positive electrode material, wherein the co-embedded film comprises an amorphous oxide layer of phosphorus and an amorphous oxide layer of titanium; the sum of the wrapping turns of the amorphous oxide layer of phosphorus and the amorphous oxide layer of titanium is 1-50 turns; in the co-embedded film, the content ratio of the phosphorus to the titanium is 0.01-100: 1, a step of;
the preparation method of the positive electrode material of the coated co-embedded film comprises the following steps:
s1, placing the anode material into a reaction cavity of atomic layer deposition equipment, setting the pressure of the reaction cavity to be 0.001-1.0 torr, and keeping the temperature to be 25-400 ℃ for 1-5 hours;
s2, introducing a precursor A into the reaction cavity, wherein the source time is 0.01-10S, the reaction time is 1-30S, the reaction times are 1-10 times, and then introducing a cleaning gas for purging redundant precursor A and byproducts;
s3, introducing a precursor B into the reaction cavity, wherein the source time is 0.01-10S, the reaction time is 1-30S, the reaction times are 1-10 times, and then introducing a cleaning gas for purging the redundant precursor B and byproducts;
s4, repeating the steps S2 and S3 for 0-4 times;
s5, introducing a precursor C into the reaction cavity, wherein the source time is 0.01-10S, the reaction time is 1-30S, the reaction times are 1-10 times, and then introducing a cleaning gas for purging redundant precursor C and byproducts;
s6, introducing a precursor B into the reaction cavity, wherein the source time is 0.01-10S, the reaction time is 1-30S, the reaction times are 1-10 times, and then introducing a cleaning gas for purging the redundant precursor B and byproducts;
s7, repeating the steps S2-S6 until the sum of the coating turns of the amorphous oxide layer of phosphorus and the amorphous oxide layer of titanium is 1-50 turns, so as to obtain the anode material of the coating co-embedded film; then post-treating the positive electrode material of the coated co-embedded film at the post-treatment temperature of 300-750 ℃ for 0.1-12 h;
the precursor A is an active precursor of phosphorus and comprises one or more of phosphoric acid, trimethyl phosphate, tri (dimethylamine) phosphorus and trialkyl phosphorus oxide, the precursor B is an oxygen source precursor and comprises one or more of water, oxygen and ozone, the precursor C comprises one or more of titanium tetrachloride, titanium isopropoxide, tetraethoxy titanium and tetra (diethylamine) titanium, and the sweeping gas is nitrogen or argon.
2. The positive electrode material coated with the co-embedded film according to claim 1, wherein the surface of the positive electrode material is coated with the amorphous oxide layer of phosphorus and the amorphous oxide layer of titanium in sequence from inside to outside.
3. A lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises the positive electrode material of the coated co-embedded film according to any one of claims 1to 2.
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