CN116253570A - LiPON target material and preparation method and application of film - Google Patents

LiPON target material and preparation method and application of film Download PDF

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CN116253570A
CN116253570A CN202310270356.6A CN202310270356A CN116253570A CN 116253570 A CN116253570 A CN 116253570A CN 202310270356 A CN202310270356 A CN 202310270356A CN 116253570 A CN116253570 A CN 116253570A
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lipon
powder
groups
film
biscuit
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周钧
刘孝伟
马贵龙
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Chaowei Power Group Co Ltd
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Chaowei Power Group Co Ltd
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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Abstract

The invention relates to a preparation method and application of a LiPON target material and a film, wherein the preparation method of the LiPON target material comprises the following steps: s1: nitriding the nano-grade lithium phosphate powder in nitrogen at the temperature of 400-600 ℃ to obtain nitrided LiPON powder; s2: granulating the nitrided LiPON powder to obtain LiPON granulated powder; s3: carrying out molding treatment on the LiPON granulation powder to obtain LiPON biscuit; s4: sintering the LiPON biscuit in an atmosphere containing nitrogen gas to obtain the LiPON ceramic. Compared with the existing electrolyte film, the LiPON film of the embodiment of the invention has higher ion conductivity.

Description

LiPON target material and preparation method and application of film
Technical Field
The invention relates to a LiPON film, in particular to a preparation method of a LiPON film for an all-solid-state battery.
Background
In another direction of the development of the lithium battery, the all-solid-state thin-film lithium ion battery has the advantages of high power density, low self-discharge rate, excellent charge-discharge cycle performance, arbitrary design of shape and size, no solution leakage, no explosion, safe use and the like, and is widely paid attention to at home and abroad in recent years. The battery can be used as an independent or standby power supply of various portable microelectronic devices and a power supply of MEMS, and has wide application prospect in civil use and military use. All-solid-state thin-film lithium ion batteries have great utility in different fields, such as aerospace, where miniaturization and weight saving of the micro-battery are of considerable interest to aerospace vehicles.
The main current method for preparing LiPON film mainly comprises the steps of using Li in a vacuum cavity 3 PO 4 The target material is a sputtering target, argon is used as an ion source, nitrogen is used as a reaction gas, and the LiPON film is deposited on the substrate through a magnetron sputtering process. Or depositing the LiPON film by chemical vapor deposition. The main stream preparation process is to introduce N in magnetron sputtering or chemical deposition 2 So that it is bonded with Li during sputtering 3 PO 4 Reacting to form LiPON; however, the magnetron sputtering coating process is a very rapid bombardment process, and N in the sputtering cavity is subjected to the bombardment process 2 The influence of the non-uniformity of the atmosphere does not make all Li 3 PO 4 Molecules are all with N 2 The reaction forms LiPON, causing a difference in ionic conductivity of the electrolyte membrane.
Disclosure of Invention
In order to overcome at least one of the above drawbacks of the prior art, in one aspect, an embodiment of the present invention provides a method for preparing a LiPON target, including the following steps:
s1: nitriding the nano-grade lithium phosphate powder in nitrogen at the temperature of 400-600 ℃ to obtain nitrided LiPON powder;
s2: granulating the nitrided LiPON powder to obtain LiPON granulated powder;
s3: carrying out molding treatment on the LiPON granulation powder to obtain LiPON biscuit; and
s4: sintering the LiPON biscuit in an atmosphere containing nitrogen gas to obtain the LiPON ceramic.
According to an embodiment of the present invention, in the step S1, the nitriding treatment is performed for 4 to 8 hours; and/or the number of the groups of groups,
the preparation process of the nano-scale lithium phosphate powder comprises the following steps:
li is mixed with 3 PO 4 The powder is subjected to liquid phase dispersion in a sand mill, so that the grain size of the slurry is less than 0.8um; and
spray drying the slurry to obtain the nano-grade lithium phosphate powder; and/or the number of the groups of groups,
the average grain diameter of the nano-grade lithium phosphate powder is 100-800 nm.
According to an embodiment of the present invention, the step S2 includes: performing liquid phase dispersion on the nitrided LiPON powder in a sand mill, adding an adhesive, and performing spray granulation through a spray granulator to obtain LiPON granulation powder; and/or the number of the groups of groups,
the step S3 includes: and pressing the LiPON granulation powder into a block, vacuum packaging the block, and performing strengthening treatment in a cold isostatic press under 180-300 MPa.
According to an embodiment of the present invention, the step S4 includes: sintering the LiPON biscuit at 600-800 ℃; and/or the number of the groups of groups,
sintering the LiPON biscuit in a nitrogen atmosphere; and/or the number of the groups of groups,
the method includes welding the LiPON ceramic to a copper plate.
In a second aspect, an embodiment of the present invention provides a LiPON target, which is prepared by the above method.
In a third aspect, an embodiment of the present invention provides a method for preparing a LiPON film, including: and performing magnetron sputtering treatment by using the LiPON target material to obtain the LiPON film.
According to an embodiment of the invention, the method comprises: introducing argon with the flow of 250-770 sccm into the coating chamber, and adjusting the pressure of the coating chamber to be below 0.52Pa for magnetron sputtering treatment; and/or the number of the groups of groups,
in the magnetron sputtering treatment, the coating chamber does not contain nitrogen or is filled with 13-26 sccm of nitrogen.
In a fourth aspect, an embodiment of the present invention provides a LiPON film, which is prepared by the above method.
In a fifth aspect, an embodiment of the present invention provides an application of the LiPON film as an electrolyte layer of a lithium ion battery.
In a sixth aspect, an embodiment of the present invention provides a lithium ion battery, including an electrolyte layer, where the electrolyte layer is the LiPON film described above.
Compared with the existing electrolyte film, the LiPON film prepared by the embodiment of the invention has higher ion conductivity.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and other advantages of the invention may be realized and attained by means of the instrumentalities and particularly pointed out in the specification.
Detailed Description
The following detailed description of the preferred embodiments of the invention is provided primarily for purposes of illustrating the principles of the invention and is not intended to limit the scope of the invention.
An embodiment of the present invention provides a method for preparing a LiPON target, including the following steps:
s1: nitriding the nano-grade lithium phosphate powder in nitrogen at the temperature of 400-600 ℃ to obtain nitrided LiPON powder;
s2: granulating the nitrided LiPON powder to obtain LiPON granulated powder;
s3: carrying out molding treatment on the LiPON granulation powder to obtain LiPON biscuit; and
s4: sintering the LiPON biscuit in an atmosphere containing nitrogen gas to obtain the LiPON ceramic.
In one embodiment, the average particle size of the nanoscale lithium phosphate powder is 100 to 800nm, for example 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm.
In one embodiment, the preparation process of the nanoscale lithium phosphate powder comprises the following steps:
(1) Li is mixed with 3 PO 4 The powder is subjected to liquid phase dispersion in a sand mill, so that the grain size of the slurry is less than 0.8um; and
(2) And (3) carrying out spray drying on the slurry to obtain the nano-grade lithium phosphate powder.
In one embodiment, li of step (1) 3 PO 4 The particle size of the powder is 10 to 50um, for example 15um, 20um, 25um, 30um, 35um, 40um, 45um.
In one embodiment, step (2) includes: introducing the slurry obtained in the step (1) into a spray dryer for spray drying to obtain nano-grade lithium phosphate powder; wherein the air inlet temperature of the spray dryer can be 220-300 ℃, such as 230 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃ and 290 ℃; the air outlet temperature can be 100-150 ℃, such as 110 ℃, 120 ℃, 130 ℃ and 140 ℃; the atomization rotational speed may be 5000 to 10000RPM, for example 5500RPM, 6000RPM, 6500RPM, 7000RPM, 7500RPM, 8000RPM, 8500RPM, 9000RPM, 9500RPM.
In one embodiment, in step S1, the nitriding treatment temperature of the nano-sized lithium phosphate powder is 400 to 600 ℃, for example, 420 ℃, 450 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃, 580 ℃.
In one embodiment, in step S1, nitriding treatment of the nano-sized lithium phosphate powder is performed in a positive pressure state; the nitriding treatment time may be 4 to 8 hours, for example, 5 hours, 6 hours, or 7 hours.
In one embodiment, step S1 includes: placing nano lithium phosphate powder in a vacuum furnace, vacuumizing, and removing air in the powder; and then introducing high-purity nitrogen, maintaining positive pressure, heating to 400-600 ℃ and maintaining the temperature for 4-8 hours, and cooling to obtain the LiPON powder with uniform nitridation.
In one embodiment, step S2 includes: the nitrided LiPON powder was subjected to liquid phase dispersion in a sand mill, and an adhesive was added, and then subjected to spray granulation by a spray granulator to obtain LiPON granulated powder.
In one embodiment, the adhesive in step S2 may be polyvinyl alcohol.
In one embodiment, the air inlet temperature of the spray granulator of step S2 may be 220-300 ℃, such as 230 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃; the air outlet temperature can be 100-150 ℃, such as 110 ℃, 120 ℃, 130 ℃ and 140 ℃; the atomization rotational speed may be 5000 to 10000RPM, for example 5500RPM, 6000RPM, 6500RPM, 7000RPM, 7500RPM, 8000RPM, 8500RPM, 9000RPM, 9500RPM.
In one embodiment, step S3 includes: the LiPON granulation powder is pressed into blocks with specific shapes, and the blocks are subjected to vacuum packaging and then are subjected to strengthening treatment in a cold isostatic press under the pressure of 180-300 MPa and further under the pressure of 240-300 MPa.
In an embodiment, the block of the specific shape in step S3 may be a square block or a round block.
In an embodiment, the pressure of the cold isostatic press of step S3 may be 200MPa, 220MPa, 240MPa, 250MPa, 260MPa, 280MPa.
In one embodiment, step S4 includes: sintering the LiPON biscuit at 600-800 ℃ and 700-800 ℃; the temperature of the sintering treatment may be 620 ℃, 650 ℃, 680 ℃, 700 ℃, 720 ℃, 750 ℃, 780 ℃, for example.
In one embodiment, the sintering time in step S4 may be 4 to 8 hours, for example, 5 hours, 6 hours, 7 hours.
In one embodiment, the sintering process of step S4 is performed in an atmosphere containing nitrogen, and further, the volume content of nitrogen in the atmosphere of the sintering process is 90% or more, further 95% or more, further 98% or more, and further 99% or more.
In one embodiment, the sintering process of step S4 is performed in a nitrogen atmosphere.
In one embodiment, the density of the LiPON ceramic is 1.7-2.4 g/cm 3 For example 1.8g/cm 3 、2.0g/cm 3 、2.1g/cm 3 、2.2g/cm 3 、2.3g/cm 3 . The higher the density of the ceramic is, the better the compactness is, and the better the uniformity of the LiPON film prepared later is.
In one embodiment, the LiPON ceramic is processed by a machining device such as a grinder and then soldered to the copper plate by means of, for example, indium soldering.
According to the method provided by the embodiment of the invention, the LiPON target material with uniform nitridation can be prepared.
An embodiment of the invention provides a LiPON target material, which is prepared by the method.
An embodiment of the present invention provides a method for preparing a LiPON film, including: and performing magnetron sputtering treatment by using the LiPON target material to obtain the LiPON film.
In one embodiment, the method for preparing the LiPON film includes: and (3) introducing argon with the pressure of 250-770 sccm into the coating chamber, and adjusting the pressure of the coating chamber to be below 0.52Pa for magnetron sputtering treatment.
In one embodiment, the argon gas introduced into the coating chamber may be 300sccm, 350sccm, 400sccm, 450sccm, 500sccm, 550sccm, 600sccm, 650sccm, 700sccm, or 750sccm.
In one embodiment, the pressure of the coating chamber may be 0.52Pa or less, further 0.45Pa or less, and still further 0.35Pa or less.
In one embodiment, the pressure of the coating chamber may be 0.35 to 0.52Pa, for example 0.4Pa, 0.5Pa.
In one embodiment, 13-26 sccm of nitrogen gas is introduced into the coating chamber during the magnetron sputtering process, for example, the amount of nitrogen gas introduced may be 15sccm, 16sccm, 18sccm, 20sccm, 22sccm, 24sccm, 25sccm.
In one embodiment, no nitrogen is present in the coating chamber during magnetron sputtering.
An embodiment of the present invention provides a LiPON film, which is prepared by the above method.
In one embodiment, the LiPON film may have a thickness of 0.5-3 um, such as 1um, 1.5um, 2um, 2.5um.
An embodiment of the invention provides application of the LiPON film as an electrolyte layer of a lithium ion battery.
An embodiment of the present invention provides a lithium ion battery, including an electrolyte layer, where the electrolyte layer is the LiPON film described above.
In one embodiment, the lithium ion battery is an all-solid-state thin-film lithium ion battery.
According to the preparation method, the LiPON target material with uniform nitridation is prepared, and then the film is coated in a nitrogen-free atmosphere through magnetron sputtering, so that the LiPON film with uniform nitridation can be prepared.
Compared with the existing electrolyte film, the LiPON film prepared by the embodiment of the invention has better uniformity and higher ion conductivity.
The ion conductivity of the LiPON film according to an embodiment of the invention may be 1.5X10 -4 ～9.0×10 -4 S/cm, e.g. 2.0X10 -4 S/cm、3.0×10 -4 S/cm、4.0×10 -4 S/cm、5.0×10 -4 S/cm、5.5×10 -4 S/cm、6.0×10 -4 S/cm、7.0×10 -4 S/cm、8.0×10 -4 S/cm。
The preparation and application of the LiPON film according to an embodiment of the present invention will be further described below with reference to specific examples. All materials used herein are commercially available unless otherwise specified.
Example 1
(1) Sanding of lithium phosphate powder
Commercially available Li 3 PO 4 The powder is put into a sand mill for liquid phase dispersion, so that the grain size of the slurry is less than 0.8um.
(2) Drying of lithium phosphate slurry
And (3) performing spray drying on the slurry obtained in the step (1) by a spray dryer at the air inlet temperature of 280 ℃ and the air outlet temperature of 120 ℃ and the atomization rotating speed of 7500rpm to obtain the nano-scale lithium phosphate powder.
(3) Powder nitriding
Extracting the nano lithium phosphate powder obtained in the step (2) in a vacuum furnace, removing air in the powder, introducing high-purity nitrogen, maintaining positive pressure, heating to 600 ℃ and maintaining the temperature for 8 hours; and cooling to obtain LiPON powder with uniform nitridation.
(4) Powder granulating
And (3) performing liquid phase dispersion on the nitrided LiPON powder in the step (3) in a sand mill, adding an adhesive, and performing spray granulation at an air inlet temperature of 280 ℃, an air outlet temperature of 120 ℃ and an atomization rotating speed of 7500rpm by using a spray granulator to obtain LiPON granulation powder.
(5) Shaping
And (3) pressing the LiPON granulation powder into square or round blocks with the specification shape by a four-column oil press, and carrying out vacuum packaging on the blocks, and then, strengthening the blocks under 300MPa by a cold isostatic press to obtain LiPON biscuit.
(6) Sintering of ceramic in nitrogen atmosphere
Introducing nitrogen into the atmosphere furnace, and sintering the LiPON biscuit at a high temperature of 800 ℃ for 8 hours to obtain the LiPON ceramic.
(7) LiPON ceramic processing
After being processed by machining equipment such as a grinder, the LiPON ceramic is welded to the copper plate in an indium welding mode.
(8) Magnetron sputtering coating film
And (3) introducing 770sccm argon into the coating chamber, adjusting the pressure of the coating chamber to 0.52Pa, and performing magnetron sputtering coating to obtain the LiPON electrolyte film with uniform nitridation.
Example 2
(1) Lithium phosphate powder sand grinding
Commercially available Li 3 PO 4 The powder is put into a sand mill for liquid phase dispersion, so that the grain size of the slurry is less than 0.8um.
(2) Drying of lithium phosphate slurry
And (3) performing spray drying on the slurry obtained in the step (1) by a spray dryer at the air inlet temperature of 280 ℃ and the air outlet temperature of 120 ℃ and the atomization rotating speed of 7500rpm to obtain the nano-scale lithium phosphate powder.
(3) Powder nitriding
Extracting the nano lithium phosphate powder obtained in the step (2) in a vacuum furnace, removing air in the powder, introducing high-purity nitrogen, maintaining positive pressure, heating to 500 ℃ and maintaining the temperature for 6 hours; and cooling to obtain LiPON powder with uniform nitridation.
(4) Powder granulating
And (3) performing liquid phase dispersion on the nitrided LiPON powder in the step (3) in a sand mill, adding an adhesive, and performing spray granulation at an air inlet temperature of 280 ℃, an air outlet temperature of 120 ℃ and an atomization rotating speed of 7500rpm by using a spray granulator to obtain LiPON granulation powder.
(5) Shaping
And (3) pressing the LiPON granulation powder into square or round blocks with the specification shape by a four-column oil press, and carrying out vacuum packaging on the blocks, and then, strengthening the blocks under 240MPa by a cold isostatic press to obtain LiPON biscuit.
(6) Sintering of ceramic in nitrogen atmosphere
Introducing nitrogen into the atmosphere furnace, and sintering the LiPON biscuit at a high temperature of 700 ℃ for 6 hours to obtain the LiPON ceramic.
(7) LiPON ceramic processing
After being processed by machining equipment such as a grinder, the LiPON ceramic is welded to the copper plate in an indium welding mode.
(8) Magnetron sputtering coating film
And (3) introducing argon with the depth of 500sccm into the coating chamber, adjusting the pressure of the coating chamber to be less than 0.45Pa, and performing magnetron sputtering coating to finish the coating to obtain the LiPON electrolyte film with uniform nitridation.
Example 3
(1) Sanding of lithium phosphate powder
Commercially available Li 3 PO 4 The powder is put into a sand mill for liquid phase dispersion, so that the grain size of the slurry is less than 0.8um.
(2) Drying of lithium phosphate slurry
And (3) performing spray drying on the slurry obtained in the step (1) by a spray dryer at the air inlet temperature of 280 ℃ and the air outlet temperature of 120 ℃ and the atomization rotating speed of 7500rpm to obtain the nano-scale lithium phosphate powder.
(3) Powder nitriding
Extracting the nano lithium phosphate powder obtained in the step (2) in a vacuum furnace, removing air in the powder, introducing high-purity nitrogen, maintaining positive pressure, heating to 400 ℃ and maintaining the temperature for 4 hours; and cooling to obtain LiPON powder with uniform nitridation.
(4) Powder granulating
And (3) performing liquid phase dispersion on the nitrided LiPON powder in the step (3) in a sand mill, adding an adhesive, and performing spray granulation at an air inlet temperature of 280 ℃, an air outlet temperature of 120 ℃ and an atomization rotating speed of 7500rpm by using a spray granulator to obtain LiPON granulation powder.
(5) Shaping
And (3) pressing the LiPON granulation powder into square or round blocks with the specification shape by a four-column oil press, and carrying out vacuum packaging on the blocks and then reinforcing the blocks under 180MPa by a cold isostatic press to obtain LiPON biscuit.
(6) Sintering of ceramic in nitrogen atmosphere
Introducing nitrogen into the atmosphere furnace, and sintering the LiPON biscuit at a high temperature of 600 ℃ for 4 hours to obtain the LiPON ceramic.
(7) LiPON ceramic processing
After being processed by machining equipment such as a grinder, the LiPON ceramic is welded to the copper plate in an indium welding mode.
(8) Magnetron sputtering coating film
And (3) introducing argon with the depth of 250sccm into the coating chamber, adjusting the pressure of the coating chamber to be less than 0.35Pa, and performing magnetron sputtering coating to finish the coating to obtain the LiPON electrolyte film with uniform nitridation.
Comparative example 1
(1) Sanding of lithium phosphate powder
Commercially available Li 3 PO 4 The powder is put into a sand mill for liquid phase dispersion, so that the grain size of the slurry is less than 0.8um.
(2) Granulation of lithium phosphate slurry
And (3) carrying out spray granulation on the slurry obtained in the step (1) by a spray dryer at the inlet air temperature of 280 ℃ and the outlet air temperature of 120 ℃ and the atomization rotating speed of 7500rpm to obtain the lithium phosphate granulation powder.
(3) Shaping
The granulated powder is pressed into square or round blocks with the specification shape by a four-column oil press, and the blocks are strengthened under 300MPa of a cold isostatic press after vacuum packaging to obtain Li 3 PO 4 And (5) biscuit.
(4) Sintering of ceramics
Li will be added at 800 ℃ in an atmospheric furnace 3 PO 4 Sintering the biscuit at high temperature for 8h to obtain Li 3 PO 4 And (3) ceramics.
(5)Li 3 PO 4 Ceramic processing
Li is mixed with 3 PO 4 After being processed by machining equipment such as a grinder, the ceramic is welded on the copper plate in an indium welding mode.
(6) Magnetron sputtering coating film
Introducing 770sccm argon into the coating chamber, adjusting the pressure of the coating chamber to 0.45Pa, and performing magnetron sputtering coating to obtain Li 3 PO 4 A film.
Comparative example 2
(1) Sanding of lithium phosphate powder
Commercially available Li 3 PO 4 The powder is put into a sand mill for liquid phase dispersion, so that the grain size of the slurry is less than 0.8um.
(2) Granulating lithium phosphate slurry
And (3) carrying out spray granulation on the slurry obtained in the step (1) by a spray dryer at the inlet air temperature of 280 ℃ and the outlet air temperature of 120 ℃ and the atomization rotating speed of 7500rpm to obtain the lithium phosphate granulation powder.
(3) Shaping
The lithium phosphate granulated powder is pressed into square or round blocks with the specification shape by a four-column oil press, and the blocks are subjected to vacuum packaging and then are reinforced under 300MPa by a cold isostatic press to obtain Li 3 PO 4 And (5) biscuit.
(4) Sintering of ceramics
Li will be added at 800 ℃ in an atmospheric furnace 3 PO 4 Sintering the biscuit at high temperature for 8h to obtain Li 3 PO 4 And (3) ceramics.
(5)Li 3 PO 4 Ceramic processing
Li is mixed with 3 PO 4 After being processed by machining equipment such as a grinder, the ceramic is welded on the copper plate in an indium welding mode.
(6) Magnetron sputtering coating film
And (3) introducing 770sccm of argon, 26-45 sccm of oxygen and 13-26 sccm of nitrogen into the film coating chamber to perform sputtering, and adjusting the pressure of the film coating chamber to be less than 0.52Pa to finish the LiPON film obtained through film coating.
Table 1 lists some of the process conditions and relevant product parameters for examples 1 to 3, comparative examples 1 to 2. Wherein the ceramic density is measured by a drainage method, and the obtained LiPON film (or Li 3 PO 4 Film) membrane is measured by an ac blocking electrode method.
TABLE 1
Figure BDA0004134407400000131
In comparative example 1, since the lithium phosphate powder was sintered in an air atmosphere and no LiPON powder was formed, and at the same time, nitrogen was not introduced during the film plating process, the lithium phosphate material was not nitrided to form LiPON, and thus the film was unable to pass ions, and therefore the ion conductivity value was not present.
In examples 1 to 3 of the present invention, lithium phosphate powder was sintered in a nitrogen atmosphere of high Wen Zhengya, and then reacted with nitrogen to produce LiPON powder, and LiPON ceramic prepared using the powder was prepared into LiPON electrolyte thin film without introducing nitrogen as a reaction gas during magnetron sputtering, and the ionic conductivity of the prepared electrolyte thin film was one order of magnitude higher than that of the reaction coating film of comparative example 2. In addition, the higher the powder nitriding temperature is, the longer the nitriding time is, and the better the film ion conductivity is after film coating.
Referring to the results of examples 1 to 3 and comparative examples 1 to 2 in table 1, it is known that the sintering density of lithium phosphate ceramic is related to the sintering temperature and the isostatic strengthening pressure, and the higher the sintering temperature and the isostatic strengthening pressure, the higher the density of the obtained ceramic, the better the compactness, and the better the uniformity of the subsequently prepared LiPON film; in the sintering treatment process of the LiPON biscuit, preferably, the isostatic pressing strengthening pressure is 240-300 MPa, and the sintering temperature is 700-800 ℃.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.

Claims (10)

1. The preparation method of the LiPON target comprises the following steps:
s1: nitriding the nano-grade lithium phosphate powder in nitrogen at the temperature of 400-600 ℃ to obtain nitrided LiPON powder;
s2: granulating the nitrided LiPON powder to obtain LiPON granulated powder;
s3: carrying out molding treatment on the LiPON granulation powder to obtain LiPON biscuit; and
s4: sintering the LiPON biscuit in an atmosphere containing nitrogen gas to obtain the LiPON ceramic.
2. The method according to claim 1, wherein in the step S1, the nitriding treatment is performed for 4 to 8 hours; and/or the number of the groups of groups,
the preparation process of the nano-scale lithium phosphate powder comprises the following steps:
li is mixed with 3 PO 4 The powder is subjected to liquid phase dispersion in a sand mill, so that the grain size of the slurry is less than 0.8um; and
spray drying the slurry to obtain the nano-grade lithium phosphate powder; and/or the number of the groups of groups,
the average grain diameter of the nano-grade lithium phosphate powder is 100-800 nm.
3. The method according to claim 1, wherein the step S2 comprises: performing liquid phase dispersion on the nitrided LiPON powder in a sand mill, adding an adhesive, and performing spray granulation through a spray granulator to obtain LiPON granulation powder; and/or the number of the groups of groups,
the step S3 includes: and pressing the LiPON granulation powder into a block, vacuum packaging the block, and performing strengthening treatment in a cold isostatic press under 180-300 MPa.
4. The method according to claim 1, wherein the step S4 comprises: sintering the LiPON biscuit at 600-800 ℃; and/or the number of the groups of groups,
sintering the LiPON biscuit in a nitrogen atmosphere; and/or the number of the groups of groups,
the method includes welding the LiPON ceramic to a copper plate.
5. A LiPON target prepared by the method of any one of claims 1 to 4.
6. A preparation method of a LiPON film comprises the following steps: performing magnetron sputtering treatment by using the LiPON target material according to claim 5 to obtain the LiPON film.
7. The method of claim 6, comprising: introducing argon with the flow of 250-770 sccm into the coating chamber, and adjusting the pressure of the coating chamber to be below 0.52Pa for magnetron sputtering treatment; and/or the number of the groups of groups,
in the magnetron sputtering treatment, the coating chamber does not contain nitrogen or is filled with 13-26 sccm of nitrogen.
8. A LiPON film made by the method of claim 6 or 7.
9. Use of the LiPON film of claim 8 as an electrolyte layer for a lithium ion battery.
10. A lithium ion battery comprising an electrolyte layer that is the LiPON film of claim 8.
CN202310270356.6A 2023-03-20 2023-03-20 LiPON target material and preparation method and application of film Pending CN116253570A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020007881A (en) * 2000-07-19 2002-01-29 박호군 Fabrication Method of Lithium Phosphate Target for High Performance Electrolyte of Thin Film Micro-Battery
FR2914653A1 (en) * 2007-04-06 2008-10-10 H E F Soc Par Actions Simplifi TARGET OF CATHODIC OXYNITRIDE SPRAY
WO2010041598A1 (en) * 2008-10-07 2010-04-15 トヨタ自動車株式会社 Method for producing lithium phosphorus oxynitride compound
JP2011001221A (en) * 2009-06-18 2011-01-06 Toyota Motor Corp Method for producing sheet containing lithium phosphorus oxynitride compound
JP2013001925A (en) * 2011-06-14 2013-01-07 Ulvac Japan Ltd Method for depositing lithium phosphorus oxynitride film, device for depositing lithium phosphorus oxynitride film, and lithium phosphorus oxynitride film
CN105256275A (en) * 2015-11-03 2016-01-20 基迈克材料科技（苏州）有限公司 Electrolyte layer material lithium phosphate target material powder metallurgy preparation technology for thin film lithium batteries
CN109553409A (en) * 2018-12-28 2019-04-02 有研工程技术研究院有限公司 A kind of solid electrolyte film Li3PO4The preparation method and application of target
CN110527974A (en) * 2018-05-25 2019-12-03 中国电子科技集团公司第十八研究所 Preparation method of atomic layer deposition LiPON solid electrolyte film

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020007881A (en) * 2000-07-19 2002-01-29 박호군 Fabrication Method of Lithium Phosphate Target for High Performance Electrolyte of Thin Film Micro-Battery
FR2914653A1 (en) * 2007-04-06 2008-10-10 H E F Soc Par Actions Simplifi TARGET OF CATHODIC OXYNITRIDE SPRAY
WO2010041598A1 (en) * 2008-10-07 2010-04-15 トヨタ自動車株式会社 Method for producing lithium phosphorus oxynitride compound
JP2011001221A (en) * 2009-06-18 2011-01-06 Toyota Motor Corp Method for producing sheet containing lithium phosphorus oxynitride compound
JP2013001925A (en) * 2011-06-14 2013-01-07 Ulvac Japan Ltd Method for depositing lithium phosphorus oxynitride film, device for depositing lithium phosphorus oxynitride film, and lithium phosphorus oxynitride film
CN105256275A (en) * 2015-11-03 2016-01-20 基迈克材料科技（苏州）有限公司 Electrolyte layer material lithium phosphate target material powder metallurgy preparation technology for thin film lithium batteries
CN110527974A (en) * 2018-05-25 2019-12-03 中国电子科技集团公司第十八研究所 Preparation method of atomic layer deposition LiPON solid electrolyte film
CN109553409A (en) * 2018-12-28 2019-04-02 有研工程技术研究院有限公司 A kind of solid electrolyte film Li3PO4The preparation method and application of target

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