CN114057233B - Lithium cobalt oxide positive electrode target material for preparing thin film lithium battery and preparation method thereof - Google Patents
Lithium cobalt oxide positive electrode target material for preparing thin film lithium battery and preparation method thereof Download PDFInfo
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- CN114057233B CN114057233B CN202111361724.5A CN202111361724A CN114057233B CN 114057233 B CN114057233 B CN 114057233B CN 202111361724 A CN202111361724 A CN 202111361724A CN 114057233 B CN114057233 B CN 114057233B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- Y02E60/10—Energy storage using batteries
Abstract
A lithium cobalt oxide positive electrode target material for preparing a thin film lithium battery and a preparation method thereof. The preparation method comprises the following steps: a premixing step, a ball milling step, a sieving step, a pressing step, a sintering step and a cooling step. The lithium cobalt oxide positive electrode target and the preparation method thereof can be specially suitable for a scheme for preparing the all-solid-state thin film lithium battery by adopting a magnetron sputtering coating mode, and solve the problem of 'no available proper target' in the process of preparing the all-solid-state thin film lithium battery by adopting the magnetron sputtering coating mode. The contact surface resistance of the prepared all-solid-state thin-film lithium battery is obviously reduced and the performance of the battery is obviously improved based on the lithium cobalt oxide positive electrode target material and the magnetron sputtering coating technology.
Description
Technical Field
The application relates to the field of large-scale energy storage and power energy, in particular to a lithium cobalt oxide positive electrode target material for preparing a thin film lithium battery and a preparation method thereof.
Background
All-solid-state lithium batteries, also known as all-solid-state lithium secondary batteries, are battery cells, and include lithium secondary batteries in which all of the positive and negative electrodes and the electrolyte are solid materials. The structure of the all-solid-state lithium battery is simpler than that of the traditional lithium ion battery, and the solid electrolyte plays the role of a diaphragm besides conducting lithium ions, and has the advantages of high mechanical strength, no inflammability, no volatile component, no hidden trouble of liquid leakage, good temperature resistance and the like. The all-solid-state lithium battery can be made of inorganic materials, is easy to realize large-scale preparation to meet the requirement of large-size batteries, and has simpler structural composition.
However, the solid materials have certain rigidity and strength, so that when the battery is formed, the contact surfaces of different solid materials cannot be completely and closely attached completely, so that the contact surface resistance of the all-solid-state lithium battery is very high, the performance of the battery is obviously reduced, the energy density, specific energy, specific power, energy efficiency and energy retention rate of the all-solid-state battery are limited, the current application is mainly limited to a power supply of a small-sized system, and the current application cannot be applied to a large-capacity energy storage system, and the difficult problem which is difficult to overcome in the manufacturing of the all-solid-state battery is solved.
The inventors have realized that the introduction of thin film fabrication techniques into all-solid-state lithium batteries, which are formed as thin films, completely avoids the problem of interfacial contact within the battery. The all-solid-state battery is prepared by adopting a magnetron sputtering coating mode, so that the problem of high contact surface resistance can be effectively solved, however, the magnetron sputtering coating needs a proper target material. How to prepare the positive electrode target material is a technical problem to be solved by the technicians in the field.
The above information disclosed in this background section is only for enhancement of understanding of the background section of the application and therefore it may not form the prior art that is already known to those of ordinary skill in the art.
Disclosure of Invention
An object of the present application is to provide a lithium cobaltate positive electrode target for producing a thin film lithium battery and a method for producing the same, which at least partially solve the above-mentioned problems.
The application further aims at providing a brand new lithium cobalt oxide positive electrode target material and a preparation method thereof, which are specially aimed at the scheme of preparing an all-solid-state thin film lithium battery by adopting a magnetron sputtering coating mode.
In particular, according to an aspect of the present application, there is provided a method for preparing a lithium cobaltate cathode target for preparing a thin film lithium battery, comprising
A premixing step of mixing lithium salt powder and cobaltosic oxide powder according to a preset proportion to obtain premixed powder, wherein the lithium salt powder is selected from a substance group formed by lithium oxide, lithium carbonate and lithium nitrate;
a ball milling step, namely mixing the premixed powder with zirconia balls with preset particle size in a ball milling tank, adding a dispersing agent, performing ball milling according to a preset first rotating speed and a first time length, performing ball milling according to a preset second rotating speed and a second time length, adding a preset weight of binder, and performing ball milling according to a preset third rotating speed and a third time length to obtain synthetic powder;
sieving, namely sieving the synthetic powder;
pressing, namely vibrating and pressurizing the screened synthetic powder, and then pressurizing the powder in a cold isostatic pressing mode to obtain a blank;
sintering the blank according to a preset heating program to obtain a sintered material, wherein the heating program comprises a plurality of groups of temperature control temperatures and temperature control durations which are in one-to-one correspondence, and each group of temperature control temperatures and temperature control durations is provided with a suitable sintering atmosphere respectively;
and a cooling step, wherein the sintered material is cooled to obtain the lithium cobalt oxide positive electrode target.
Optionally, in the ball milling step, the zirconia balls have a particle size of 0.5mm to 6mm, a ratio of a total volume to a volume of the ball milling tank is not more than one third, and a ratio of a total volume of the premixed powder and the zirconia balls to a volume of the ball milling tank is one half.
Optionally, in the ball milling step, the ball milling pot is made of a hard ceramic material.
Optionally, in the ball milling step, the weight of the dispersant is three thousandths of the total weight of the premix powder.
Optionally, in the ball milling step, the first rotation speed is 30-60 rpm, the first time period is 3h, the second rotation speed is 200rpm, and the second time period is more than 12 h.
Optionally, in the ball milling step, the weight of the binder is one thousandth of the total weight of the pre-mixed powder; and the third rotation speed is 45rpm, and the third time period is 5h.
Optionally, in the sieving step, a 500 mesh sieve is passed.
Alternatively, 1500t is pressurized during the shock pressurization of the pressing step.
Optionally, in the pressurizing process of the pressing step by adopting the cold isostatic pressing mode, the pressure is 300Mpa, and the pressure is maintained for 50min.
Optionally, in the sintering step, in order of precedence:
the first group of temperature control temperature and temperature control time length of the temperature raising program are respectively 200 ℃ and 4 hours, and the corresponding sintering atmosphere is N 2 Ar (ratio 6:4) or vacuum degree of 10 -3 Pa；
The second group of temperature control temperature and temperature control time length of the temperature raising program are respectively 550 ℃ and 10 hours, and the corresponding sintering atmosphere is N 2 Ar (ratio 6:4) or vacuum degree of 10 -3 Pa；
The third group of temperature control temperature and temperature control time length of the temperature raising program are respectively 750 ℃ and 12 hours, and the corresponding sintering atmosphere is N 2 Ar (ratio 6:4) or vacuum degree of 10 -3 Pa；
The fourth group of temperature control temperature and temperature control time length of the temperature raising program are 950 ℃ and 15 hours respectively, and the corresponding sintering atmosphere is N 2 Ar (ratio 6:4) or vacuum degree of 10 -3 Pa；
The fifth group of temperature control temperature and temperature control time length of the temperature raising program are 1050 ℃ and 10 hours respectively, and the corresponding sintering atmosphere is N 2 Ar (ratio 6:4) or vacuum degree of 10 -3 Pa；
The sixth group of temperature control temperature and temperature control time length of the temperature raising program are 500 ℃ and 3 hours respectively, and the corresponding sintering atmosphere is N 2 Ar (ratio 6:4) or vacuum degree of 10 -3 Pa。
According to another aspect of the present application, there is also provided a lithium cobaltate positive electrode target prepared by the preparation method of any one of the above.
The lithium cobalt oxide positive electrode target for preparing the thin film lithium battery and the preparation method thereof can be specially applied to a scheme for preparing the all-solid-state thin film lithium battery by adopting a magnetron sputtering coating mode, and solve the problem of 'no available proper target' in the process of preparing the all-solid-state thin film lithium battery by adopting the magnetron sputtering coating mode. The contact surface resistance of the prepared all-solid-state thin-film lithium battery is obviously reduced and the performance of the battery is obviously improved based on the lithium cobalt oxide positive electrode target material and the magnetron sputtering coating technology.
Furthermore, based on the lithium cobaltate positive electrode target material, the preparation method thereof and the magnetron sputtering coating technology, the all-solid-state thin film lithium battery can very easily realize direct series connection of a plurality of single batteries, direct parallel connection of a plurality of single batteries and serial and parallel connection combination of a plurality of single batteries, thereby remarkably improving the output voltage of the battery, increasing the single capacity of the battery pack or realizing perfect combination of supercharging and expanding capacity, and having good application prospect.
The above, as well as additional objectives, advantages, and features of the present application will become apparent to those skilled in the art from the following detailed description of a specific embodiment of the present application when read in conjunction with the accompanying drawings.
Drawings
Some specific embodiments of the application will be described in detail hereinafter by way of example and not by way of limitation with reference to the accompanying drawings. The same reference numbers will be used throughout the drawings to refer to the same or like parts or portions. It will be appreciated by those skilled in the art that the drawings are not necessarily drawn to scale. In the accompanying drawings:
fig. 1 is a schematic diagram of a method of preparing a lithium cobaltate positive electrode target according to an embodiment of the present application.
Detailed Description
Fig. 1 is a schematic diagram of a method of preparing a lithium cobaltate positive electrode target according to an embodiment of the present application. The lithium cobaltate anode target is used for preparing a thin film lithium battery. By adopting a magnetron sputtering method, the lithium cobalt oxide positive electrode target material of the embodiment can be used for depositing a lithium cobalt oxide positive electrode film.
The preparation method of the lithium cobaltate cathode target material generally comprises the following steps:
step A: and a premixing step of mixing lithium salt powder and cobaltosic oxide powder according to a preset proportion to obtain premixed powder, wherein the lithium salt powder is selected from a substance group formed by lithium oxide, lithium carbonate and lithium nitrate.
And (B) step (B): and a ball milling step, namely mixing the premixed powder with zirconia balls with the preset particle size in a ball milling tank, adding a dispersing agent, performing ball milling according to a preset first rotating speed and a preset first time, performing ball milling according to a preset second rotating speed and a preset second time, adding a preset weight of binder, and performing ball milling according to a preset third rotating speed and a preset third time to obtain synthetic powder.
Step C: and a sieving step of sieving the synthetic powder.
Step D: and pressing, namely vibrating and pressurizing the screened synthetic powder, and then pressurizing the powder by adopting a cold isostatic pressing mode to obtain a blank.
Step E: and sintering the blank according to a preset heating program to obtain a sintering material, wherein the heating program comprises a plurality of groups of temperature control temperatures and temperature control durations which are in one-to-one correspondence, and each group of temperature control temperatures and temperature control durations is provided with a suitable sintering atmosphere respectively.
Step F: and a cooling step, wherein the sintered material is cooled to obtain the lithium cobalt oxide positive electrode target.
The lithium cobalt oxide positive electrode target for preparing the thin film lithium battery and the preparation method thereof can be specially applied to a scheme for preparing the all-solid-state thin film lithium battery by adopting a magnetron sputtering coating mode, and solve the problem of 'no available proper target' in the process of preparing the all-solid-state thin film lithium battery by adopting the magnetron sputtering coating mode. The contact surface resistance of the prepared all-solid-state thin-film lithium battery is obviously reduced and the performance of the battery is obviously improved based on the lithium cobalt oxide positive electrode target material and the magnetron sputtering coating technology.
In the premixing step, "the lithium salt powder is selected from the group consisting of lithium oxide, lithium carbonate and lithium nitrate" means that the lithium salt powder is one or more of lithium oxide, lithium carbonate and lithium nitrate. In this embodiment, the lithium salt powder is any one of lithium oxide, lithium carbonate, and lithium nitrate.
In some alternative embodiments, the ratio of the lithium salt powder to the cobaltosic oxide powder may be set according to actual needs, so long as the ratio of each element of the product can be ensured.
In the ball milling step, the particle size of the zirconia balls is 0.5-6 mm, the ratio of the total volume of the zirconia balls to the volume of the ball milling tank is not more than one third, and the ratio of the total volume of the premixed powder and the zirconia balls to the volume of the ball milling tank is one half.
In the ball milling step, the ball milling pot is made of a hard ceramic material. The ball milling tank can be placed in a ball mill. The rotational speed and duration of the ball milling step may be controlled by the ball mill.
In the ball milling step, the weight of the dispersant is three thousandths of the total weight of the premix powder. This ensures that the mixed powder is uniformly mixed and that the particles obtained in the ball milling process are fine.
In the ball milling step, the first rotating speed is 30 rpm-60 rpm, the first time period is 3h, the second rotating speed is 200rpm, and the second time period is more than 12 h.
In the ball milling step, the weight of the binder is one thousandth of the total weight of the premix powder. And the third rotation speed is 45rpm, and the third time period is 5h.
That is, in the ball milling process, preliminary ball milling is performed at a low rotational speed, then "fine" ball milling is performed at a high rotational speed, then a binder is added, and then ball milling is performed at a low rotational speed. After the dispersant is added, the ball milling tank is firstly used for ball milling for 3 hours at an initial set rotating speed (namely, a first rotating speed), and then the ball milling tank is used for ball milling for more than 12 hours at a constant rotating speed (namely, a second rotating speed). Then, the binder was added to the ball mill tank in an amount of one thousandth of the weight of the pre-mixed powder, and then ball-milled for 5 hours at another constant rotational speed (i.e., a third rotational speed).
By using the method, the synthetic powder with uniform particle size can be obtained, and the particle size of the synthetic powder can be controlled within a preset reasonable range.
In the sieving step, a 500 mesh sieve was passed. Through the sieving step, the particle size of the sieved synthetic powder can be further controlled within a preset reasonable range, and the uniformity of the particle size of the synthetic powder is ensured. The grain diameter of the qualified synthetic powder after sieving is less than or equal to 500 meshes.
The pressing step is performed in two steps.
First, vibration pressurization is performed. When the sieved synthetic powder is subjected to vibration pressurization, the sieved and weighed synthetic powder is poured into a vibration die, and the pressure is increased by 1500t in the vibration pressurization process to form a molded blank.
And then pressurized by cold isostatic pressing. In the pressurizing process by adopting the cold isostatic pressing mode, the qualified blank obtained in the steps is placed into a cold isostatic pressing machine to be pressurized at 300Mpa and maintained for 50min.
By using the pressing method, the prepared blank is compact and fine and has good performance.
In the sintering step, the pressed green material is placed in an atmosphere sintering furnace (or in a vacuum sintering furnace), then a temperature-raising program of the atmosphere sintering furnace is set, and sintering is started. The temperature-increasing program can comprise six groups of temperature control temperatures and temperature control durations according to the sequence. It should be noted that the "temperature increase program" is a generic term for the temperature control process, and does not mean that each stage of the temperature control process is a temperature increase process.
The first group of temperature control temperature and temperature control time length of the temperature raising program are respectively 200 ℃ and 4 hours, and the corresponding sintering atmosphere is N 2 Ar (ratio 7:3) or vacuum degree of 10 -3 Pa. That is, in the process of sintering according to the first group of temperature control temperature and temperature control time period, N is always introduced 2 The mixed gas with Ar (ratio 7:3) or the vacuum degree is kept to be 10 in a vacuum sintering furnace all the time -3 Pa. Before the first group of temperature control and temperature control time are executed, the temperature is raised from room temperature to 200 ℃, and N is always introduced in the temperature raising process 2 The mixed gas with Ar (ratio 6:4) or the vacuum degree is kept to be 10 in a vacuum sintering furnace all the time -3 Pa。
The second group of temperature control temperature and temperature control time length of the temperature raising program are respectively 550 ℃ and 10 hours, and the corresponding sintering atmosphere is N 2 Ar (ratio 6:4) or vacuum degree of 10 -3 Pa. That is, in the process of sintering according to the second group of temperature control temperature and temperature control time period, N is always introduced 2 The mixed gas with Ar (ratio 6:4) or the vacuum degree is kept to be 10 in a vacuum sintering furnace all the time -3 Pa. Before the second group of temperature control and temperature control time are executed, the temperature is raised from 200 ℃ to 550 ℃ and the temperature raising process is always conductedIn N 2 The mixed gas with Ar (ratio 6:4) or the vacuum degree is kept to be 10 in a vacuum sintering furnace all the time -3 Pa。
The third group of temperature control temperature and temperature control time length of the temperature raising program are respectively 750 ℃ and 12 hours, and the corresponding sintering atmosphere is N 2 Ar (ratio 6:4) or vacuum degree of 10 -3 Pa. That is, in the process of sintering according to the third group of temperature control temperature and temperature control time period, N is always introduced 2 The mixed gas with Ar (ratio 6:4) or the vacuum degree is kept to be 10 in a vacuum sintering furnace all the time -3 Pa. Before the third group of temperature control and temperature control time are executed, the temperature is raised from 550 ℃ to 750 ℃, and N is always introduced in the heating process 2 The mixed gas with Ar (ratio 6:4) or the vacuum degree is kept to be 10 in a vacuum sintering furnace all the time -3 Pa。
The fourth group of temperature control temperature and temperature control time length of the temperature raising program are 950 ℃ and 15 hours respectively, and the corresponding sintering atmosphere is N 2 Ar (ratio 6:4) or vacuum degree of 10 -3 Pa. That is, in the sintering process according to the fourth group of temperature control temperature and temperature control time period, N is always introduced 2 The mixed gas with Ar (ratio 6:4) or the vacuum degree is kept to be 10 in a vacuum sintering furnace all the time -3 Pa. Before the fourth group of temperature control and temperature control time are executed, the temperature is firstly increased from 750 ℃ to 950 ℃, and N is always introduced in the heating process 2 The mixed gas with Ar (ratio 6:4) or the vacuum degree is kept to be 10 in a vacuum sintering furnace all the time -3 Pa。
The fifth group of temperature control temperature and temperature control time length of the temperature raising program are 1050 ℃ and 10 hours respectively, and the corresponding sintering atmosphere is N 2 Ar (ratio 6:4) or vacuum degree of 10 -3 Pa. That is, in the sintering process according to the fifth group of temperature control temperature and temperature control time period, N is always introduced 2 The mixed gas with Ar (ratio 6:4) or the vacuum degree is kept to be 10 in a vacuum sintering furnace all the time - 3 Pa. Before the fifth group of temperature control and temperature control time are executed, the temperature is raised from 950 ℃ to 1050 ℃, and N is always introduced in the process of temperature raising 2 The mixed gas with Ar (ratio 6:4) or the vacuum degree is kept to be 10 in a vacuum sintering furnace all the time -3 Pa。
The sixth group of temperature control temperature and temperature control time length of the temperature raising program are 500 ℃ and 3 hours respectively, and the corresponding sintering atmosphere is N 2 Ar (ratio 6:4) or vacuum degree of 10 -3 Pa. That is, in the sintering process according to the sixth group of temperature control temperature and temperature control time period, N is always introduced 2 The mixed gas with Ar (ratio 6:4) or the vacuum degree is kept to be 10 in a vacuum sintering furnace all the time -3 Pa. Before the fifth group of temperature control and temperature control duration are executed, the temperature is slowly reduced to 500 ℃ from 1050 ℃ along with the furnace, and N is always introduced in the process of temperature reduction 2 The mixed gas with Ar (ratio 6:4) or the vacuum degree is kept to be 10 in a vacuum sintering furnace all the time -3 Pa。
The sintering step is executed by utilizing the above six groups of temperature control temperatures and temperature control time durations of the temperature increasing program, so that the lithium cobalt oxide positive electrode target material with fine grains and uniform components and tissues can be obtained.
In the cooling step, the lithium cobalt oxide cathode target can be taken out after being naturally cooled to room temperature along with a furnace, and is machined to a proper size or shape, such as a round cake shape with a set thickness and a set diameter. Those skilled in the art should easily know and adjust the size and shape of the lithium cobaltate positive electrode target material on the basis of understanding the present application, and detailed description thereof will be omitted herein.
The lithium cobalt oxide anode target material prepared by the method can provide a proper target material for magnetron sputtering coating and provide favorable conditions for preparing an all-solid-state thin film lithium battery by adopting a magnetron sputtering coating mode.
Based on the lithium cobaltate positive electrode target material, the preparation method thereof and the magnetron sputtering coating technology, the all-solid-state thin film lithium battery can very easily realize direct series connection of a plurality of single batteries, direct parallel connection of the plurality of single batteries and serial and parallel connection combination of the plurality of single batteries, thereby remarkably improving the output voltage of the battery, increasing the single capacity of a battery pack or realizing perfect combination of supercharging and expanding capacity and having good application prospect.
As for the preparation method of the all-solid-state thin film lithium battery, further explanation will be made according to examples 1 to 3 below.
Example 1:
the lithium cobaltate positive electrode target prepared by the method adopts a magnetron sputtering coating technology to deposit a single graphene-based thin film lithium battery: and coating a graphene collector film with the thickness of 6 mu m on the surface of a copper foil with the thickness of 1 square meter, and sequentially depositing a negative electrode film, a solid electrolyte film, a positive electrode film and the graphene collector film on the graphene collector film. Wherein the thickness of the deposited negative electrode film is 4.5 mu m, the thickness of the deposited solid electrolyte film is 1.5 mu m, and the thickness of the deposited positive electrode film is 15 mu m. And coating a 6-mu m graphene collector film on the positive electrode film. The capacity of the obtained battery after the formation was 12240 (mA.h).
Example 2:
the lithium cobaltate positive electrode target prepared by the method adopts a magnetron sputtering coating technology to deposit two graphene-based thin film lithium batteries in series connection: and coating a graphene collector film with the thickness of 7 mu m on the surface of a copper foil with the thickness of 1 square meter, and sequentially depositing a negative electrode film, a solid electrolyte film, a positive electrode film, a graphene collector film, a negative electrode film, a solid electrolyte film, a positive electrode film and a graphene collector film on the graphene collector film. Wherein, the thickness of the deposited negative film of each battery is 5.5 μm, the thickness of the solid electrolyte film of each battery is 2.0 μm, the thickness of the positive film of each battery is 18.5 μm, and the thickness of the graphene collector film is 7 μm. The capacity of the obtained battery after the formation was 15096 (ma·h).
Example 3:
the lithium cobaltate positive electrode target prepared by the method adopts a magnetron sputtering coating technology to deposit two graphene-based thin film lithium batteries which are connected in parallel: and coating a graphene collector film with the thickness of 7 mu m on the surface of a copper foil with the thickness of 1 square meter, and sequentially depositing a negative electrode film, a solid electrolyte film, a positive electrode film, a graphene collector film, a positive electrode film, a solid electrolyte film, a negative electrode film and a graphene collector film on the graphene collector film. Wherein, the thickness of the deposited negative film of each cell is 6.5 μm, the thickness of the deposited solid electrolyte film of each cell is 2.5 μm, the thickness of the deposited positive film of each cell is 22 μm, and the thickness of the graphene collector film is 7 μm. The capacity of the obtained battery after formation was 35904 (mA.h).
In the above examples 1 to 3, the positive electrode thin film, the solid electrolyte thin film and the negative electrode thin film were all prepared by the magnetron sputtering method. For example, the negative electrode film may be a tin alloy film, the solid electrolyte film may be a lithium phosphate film, and the positive electrode film may be a lithium cobaltate film. The graphene collector film is prepared by a coating or growing method.
The lithium cobalt oxide positive electrode target for preparing the thin film lithium battery and the preparation method thereof can be specially applied to a scheme for preparing the all-solid-state thin film lithium battery by adopting a magnetron sputtering coating mode, and solve the problem of 'no available proper target' in the process of preparing the all-solid-state thin film lithium battery by adopting the magnetron sputtering coating mode. The contact surface resistance of the prepared all-solid-state thin-film lithium battery is obviously reduced and the performance of the battery is obviously improved based on the lithium cobalt oxide positive electrode target material and the magnetron sputtering coating technology.
By now it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the application have been shown and described herein in detail, many other variations or modifications of the application consistent with the principles of the application may be directly ascertained or inferred from the present disclosure without departing from the spirit and scope of the application. Accordingly, the scope of the present application should be understood and deemed to cover all such other variations or modifications.
Claims (10)
1. A preparation method of a lithium cobalt oxide positive electrode target material for preparing a thin film lithium battery comprises the following steps of
A premixing step of mixing lithium salt powder and cobaltosic oxide powder according to a preset proportion to obtain premixed powder, wherein the lithium salt powder is one or more of lithium oxide, lithium carbonate and lithium nitrate;
a ball milling step, namely mixing the premixed powder with zirconia balls with the preset particle size in a ball milling tank, adding a dispersing agent, performing ball milling according to a preset first rotating speed and a first time length, performing ball milling according to a preset second rotating speed and a second time length, adding a preset weight of binder, and performing ball milling according to a preset third rotating speed and a third time length to obtain synthetic powder;
a sieving step of sieving the synthetic powder;
pressing, namely vibrating and pressurizing the screened synthetic powder, and then pressurizing the synthetic powder in a cold isostatic pressing mode to obtain a blank;
sintering the blank according to a preset heating program to obtain a sintered material, wherein the heating program comprises a plurality of groups of temperature control temperatures and temperature control durations which are in one-to-one correspondence, and each group of temperature control temperatures and temperature control durations is provided with an applicable sintering atmosphere correspondingly;
a cooling step, namely cooling the sintering material to obtain a lithium cobalt oxide positive electrode target;
in the sintering step, the following sequence is adopted:
the first group of temperature control temperature and temperature control duration of the temperature raising program are 200 ℃ and 4 hours respectively, and the corresponding sintering atmosphere is N2/Ar with the volume ratio of 7:3 or the vacuum degree is 10 < -3 > Pa;
the second group of temperature control temperature and temperature control duration of the temperature raising program are 550 ℃ and 10 hours respectively, and the corresponding sintering atmosphere is N2/Ar with the volume ratio of 6:4 or the vacuum degree is 10 < -3 > Pa;
the third group of temperature control temperature and temperature control duration of the temperature raising program are respectively 750 ℃ and 12 hours, and the corresponding sintering atmosphere is N2/Ar with the volume ratio of 6:4 or the vacuum degree is 10 < -3 > Pa;
the fourth group of temperature control temperature and temperature control duration of the temperature raising program are 950 ℃ and 15 hours respectively, and the corresponding sintering atmosphere is N2/Ar with the volume ratio of 6:4 or the vacuum degree is 10 < -3 > Pa;
the fifth group of temperature control temperature and temperature control duration of the temperature rise program are 1050 ℃ and 10 hours respectively, and the corresponding sintering atmosphere is N2/Ar with the volume ratio of 6:4 or the vacuum degree is 10 < -3 > Pa;
the sixth group of temperature control temperature and temperature control duration of the temperature rise program are 500 ℃ and 3 hours respectively, and the corresponding sintering atmosphere is N2/Ar with the volume ratio of 6:4 or the vacuum degree is 10 < -3 > Pa.
2. The preparation method according to claim 1, wherein,
in the ball milling step, the particle size of the zirconia balls is 0.5-6 mm, the ratio of the total volume of the zirconia balls to the volume of the ball milling tank is not more than one third, and the ratio of the total volume of the premixed powder and the zirconia balls to the volume of the ball milling tank is one half.
3. The preparation method according to claim 1, wherein,
in the ball milling step, the ball milling pot is made of a hard ceramic material.
4. The preparation method according to claim 1, wherein,
in the ball milling step, the weight of the dispersing agent is three thousandths of the total weight of the premixed powder.
5. The preparation method according to claim 1, wherein,
in the ball milling step, the first rotating speed is 30-60 rpm, the first time period is 3h, the second rotating speed is 200rpm, and the second time period is more than 12 h.
6. The preparation method according to claim 1, wherein,
in the ball milling step, the weight of the binder is one thousandth of the total weight of the pre-mixed powder; and is also provided with
The third rotation speed is 45rpm, and the third time period is 5h.
7. The preparation method according to claim 1, wherein,
in the sieving step, a 500 mesh sieve was passed.
8. The production method according to claim 1, wherein
During the vibration pressurization of the pressing step, 1500t was pressurized.
9. The production method according to claim 1, wherein
In the pressurizing process of the pressing step by adopting the cold isostatic pressing mode, 300Mpa is pressurized and the pressure is maintained for 50min.
10. A lithium cobaltate positive electrode target prepared by the preparation method of any one of claims 1 to 9.
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