CN105734502A - Relevant target materials for full-solid film lithium ion battery and manufacturing method of relevant target materials - Google Patents
Relevant target materials for full-solid film lithium ion battery and manufacturing method of relevant target materials Download PDFInfo
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- CN105734502A CN105734502A CN201610003698.1A CN201610003698A CN105734502A CN 105734502 A CN105734502 A CN 105734502A CN 201610003698 A CN201610003698 A CN 201610003698A CN 105734502 A CN105734502 A CN 105734502A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
Abstract
The invention relates to relevant target materials for a full-solid film lithium ion battery and a manufacturing method of the relevant target materials. The manufacturing method mainly comprises the steps of material selection, treatment before sintering, hot-pressed sintering, postreatment of the target materials and the like. The target materials which can be manufactured through the manufacturing method include LiCoO2, LiFePO4, Li3PO4 and the like. According to the manufacturing method, a graphite mold is adopted, molybdenum foil serves as isolating materials between the mold and the target materials, and both the upper surface and the lower surface of each target material are protected through the molybdenum foil; pre-pressing is conducted by 1-5 MPa, vacuumizing is conducted till the pressure reaches 10<-3> Pa, heating is conducted at the speed of 10-15 DEG C/min till the temperature reaches 100-400 DEG C, heat preservation is conducted for 0.5-1 h, and argon is introduced into the mold; then heating is conducted at the speed of 10-15 DEG C/min till the temperature reaches 400-1000 DEG C, the temperature is increased gradually, pressurization is conducted, the final sintering pressure is 20-60 MPa, and heat preservation is conducted for 1-5 h; and pressure maintaining and cooling with a furnace are conducted, the target materials are taken out, and the surface layers are ground off. By the adoption of the method, the high-purity and high-compactness target materials for the full-solid film lithium ion battery can be obtained, the technological process is designed to be simple and easy to implement, and the cost is low.
Description
Technical field
That prepared by the present invention is material LiCoO2, LiFePO4, Li3PO4 etc. of solid-State Thin Film Li-Ion Batteries use, and the method can prepare LiCoO2, LiFePO4, Li3PO4 sputtering target material of high-purity, high-compactness.Under proper condition, sputter the thin film of these target energy excellents, thus improve energy storage capacity and the cycle-index of solid-State Thin Film Li-Ion Batteries.
Background technology
The fast development of the electronic device miniaturizations such as sensor, MEMS, CMOS chip, it is desirable to have the miniature compact power supply that volume is little, lightweight, specific capacity is high matched.Solid-State Thin Film Li-Ion Batteries owing to having high power density, low self-discharge rate, excellent charge-discharge performance, shape and size can be arbitrarily devised, and without solution leakage, do not explode, use safety etc. advantage, the most at home and abroad obtaining extensive concern, Countries has realized industrialized production.This kind of battery can be used as independence or the stand-by power supply of various portable microelectronic component, and the power supply of MEMS, civilian or the most all shown wide application prospect.Solid-State Thin Film Li-Ion Batteries has its ample scope for abilities in different field, and as in space industry, this micro cell miniaturization, lightweight have considerable captivation to aerospace craft；Militarily, film lithium ion battery is all used for the micro cell chip technology of weapon Intellectualized monitoring and management system by U.S. Sandia National Laboratory, Oak Ridge National Laboratory (ORNL), jet jet laboratory (JPL) of NASA (NASA) and the Air Force Research Laboratory at active development；Its purposes also includes: micro surgical tool in miniature robot surveillance plane electrical source of power (including camera head power supply), multiple microsensor, CMOS integrated circuit, smart card (SmartCard), biochip and human body and mini-medical device etc..
The core component positive electrode (such as LiCoO2, LiFePO4 etc.) of solid-State Thin Film Li-Ion Batteries and electrolyte (such as LiPON etc.) are always focus of concern, and corresponding film performance directly determines capacity and the service life of battery.Therefore, superior in quality target also will become more important.The nitrogenous lithium phosphate of LiPON() prepared by sputtering Li3PO4 target in nitrogen environment.Generally speaking the production method of LiCoO2, LiFePO4, Li3PO4 target has sintering process, hot isostatic pressing method, pressure sintering etc. three kinds.Being compared as follows of these three method:
1, sintering process: general use to cold pressing add the method for sintering and prepare.In cold pressure procedure, in order to strengthen the mouldability of biscuit, can add the binding agent of 0.5%～2% wherein, pressing pressure can not be too big, discharges by binding agent since it is desired that reserve enough passages, but binding agent still has residual, adds the impurity content of target.Owing to the relative density of biscuit is 60%～70%, after target has sintered, the relative density of target can only achieve 70%～90%.
2, hot isostatic pressing method: the method can be at more than pressure 100MPa, and sintering temperature is 600 DEG C～1000 DEG C sintering targets, obtains the target that relative density is 98%～100%.But the method technical process is more complicated, specifically include that powder pre-treatment, make jacket, shove charge sintering, remove jacket, following process etc., and each step complete require higher, if target is less, the processing capacity of following process is relatively big, then utilization rate of raw materials is relatively low.Owing to the price of LiCoO2, LiFePO4, Li3PO4 raw material is higher, increase after heat and other static pressuring processes cost, target relatively costly.
3, pressure sintering: the method can use refractory metal mould, ceramic die or graphite jig, is sintered under vacuum or other atmosphere, and general sintering pressure is 20～80MPa, can obtain the target that relative density is 98%～100%.The method produces
Cost is relatively low, and technical process is relatively simple, specifically includes that charging, sintering, the demoulding, following process etc., and each step controls relatively simple, the stay in grade of product, it is possible to obtain the semi-finished product close to product requirement size.
LiCoO2 is the positive electrode of unique large-scale commercial, and the commercial lithium-ion batteries of current more than 90% uses LiCoO2 as positive electrode.The research comparative maturity of LiCoO2, high comprehensive performance, but expensive, capacity is relatively low, there is certain safety issue.
The LiFePO4 positive electrode of orthogonal olivine structural has been increasingly becoming the newest study hotspot.Preliminary study shows, this novel anode material has concentrated LiCoO2
And the respective advantage of derivant positive electrode: without noble element, cheaper starting materials, resource extreme enrichment；Running voltage moderate (3.4V)；Platform identity is good, and voltage pole is steadily (can match in excellence or beauty with regulated power supply)；Theoretical capacity is big (170mAh/g)；Stability Analysis of Structures, security performance splendid (O Yu P, with strong covalent bond strong bonded, makes material be difficult to analysis oxygen and decompose)；High-temperature behavior and heat stability are substantially better than other positive electrode known；Good cycle；Volume-diminished during charging, bulk effect when coordinating with carbon negative pole material is good；Good with most of electrolyte system compatibility, storge quality is good；Nontoxic, for real green material.Compared with LiCoO2 and derivant positive electrode thereof, LiFePO4 positive electrode has prominent advantage in terms of cost, high-temperature behavior, safety, it is expected to become middle Large Copacity, the positive electrode of middle high power lithium ion cell first-selection.
Nitrogenous lithium phosphate LiPON is the most attractive current solid electrolyte thin-film material, and it prepares by sputtering Li3PO4 target in nitrogen environment.The solid-State Thin Film Li-Ion Batteries of commercialization at present all uses LiPON as electrolyte.
The hot pressing that the present invention relates to tri-kinds of targets of LiCoO2, LiFePO4, Li3PO4 is standby.Detailed processing step and parameter are illustrated below.
Summary of the invention
The invention provides a kind of solid-State Thin Film Li-Ion Batteries to be correlated with the manufacture method of target, the method is obtained in that LiCoO2, LiFePO4, Li3PO4 target of densification high-purity, high.Protection due to high-purity argon gas, it is to avoid introduce impurity in air ambient sintering process；Lasting high pressure, allows target high densification.
Pressure sintering of the present invention production high-quality LiCoO2, the step of LiFePO4, Li3PO4 target specifically include that powder pre-treatment, degasification process, interim pressure sintering, target post processing.
I, powder pre-treatment
Be 100nm by mean diameter, purity be LiCoO2, LiFePO4, Li3PO4 of 99.95% be raw material, by grinding, the method for screening remove the caking in powder.
II, degasification process
Use graphite jig, make the isolated material of mould and target of molybdenum foil, upper and lower surface all with molybdenum foil as protection, it is also contemplated that use metal molybdenum liner and upper push-down head.Precompressed 1～5MPa, is evacuated to 10-3Pa, is heated to 100～400 DEG C with the speed of 10～15 DEG C/min, is incubated 0.5h～1h, is filled with argon.
III, interim pressure sintering
For ensureing that in high-temperature sintering process, the flowing of material is carried out with bonding orderly stage, hot pressing uses the mode of multistage intensification pressurization to complete sintering.It is forced into 10MPa, is then heated to 100 DEG C～400 DEG C with the firing rate of 10～15 DEG C/min, be incubated 1 hour, it is ensured that cavity body of mould uniformity of temperature profile.Finally being heated to 400 DEG C～1000 DEG C with the firing rate of 10～15 DEG C/min, be incubated 1 hour, during temperature rises, every 50 DEG C increase by 1～5MPa pressure, and final pressure is 20MPa.After insulation, closing heating system, pressurize is cold with stove.
IV, target post processing
Target is taken out, removes molybdenum foil protective layer, then by the method for attrition process, target is worked into specified size.
The technological parameter that different targets are corresponding is as follows:
Table 1 each target Fabrication parameter
The invention provides a kind of high-quality LiCoO2, the production technology of LiFePO4, Li3PO4 target, under inert gas shielding, complete the hot pressed sintering of LiCoO2, LiFePO4, Li3PO4 target.The method has the advantage that
1, present invention process process is simple, and in vacuum suction temperature-rise period, the gas molecule in LiCoO2, LiFePO4, Li3PO4 powder is progressively discharged.
2, the present invention uses the mode of multistage increasing temperature and pressure, the character of bond material itself, and different phase uses different heating rate, reduces the production time, and different temperatures uses different pressure, allows LiCoO2, LiFePO4, Li3PO4 powder densification step by step.
3, temperature-fall period preferably avoids the Stress Release that temperature-fall period is likely to result in, and for a long time with the cold stress being conducive to being reduced or eliminated between target powder inside of stove, to prevent the cracking of target, improves target intensity and compactness.
Detailed description of the invention
Embodiment 1
Be 100nm by mean diameter, purity be the LiCoO2 of 99.95% be raw material, by grinding, the method for screening remove the caking in powder.Use graphite jig, make the isolated material of mould and target of molybdenum foil, upper and lower surface all with molybdenum foil as protection.Precompressed 3MPa, is evacuated to 10-3Pa, is heated to 400 DEG C with the speed of 10 DEG C/min, is incubated 1 hour, is filled with argon.It is forced into 10MPa, is then heated to 600 DEG C with the firing rate of 15 DEG C/min, be incubated 1 hour, it is ensured that cavity body of mould uniformity of temperature profile.Finally being heated to 900 DEG C with the firing rate of 10 DEG C/min, be incubated 1 hour, during temperature rises, every 50 DEG C increase 5MPa pressure, and final pressure is 20MPa.After insulation, closing heating system, pressurize is cold with stove.Target is taken out, removes molybdenum foil protective layer, then by the method for mill processing, target is worked into specified size.Target density is surveyed with Archimedes's drainage,；Each essential element content, addition calculation target purity is measured with ICP-MS；With metallurgical microscope or scanning electron microscopic observation target interior tissue pattern, measure crystal grain mean diameter.
The fundamental performance parameter of target is as shown in table 2:
Table 2 pressure sintering produces the performance parameter of LiCoO2 target
| Material | Purity | Relative density | Size | Mean diameter |
| LiCoO2 | 99.9% | >98% | 100mm×100mm×10mm | <10 Micron |
Embodiment 2
Be 100nm by mean diameter, purity be the Li3PO4 of 99.95% be raw material, by grinding, the method for screening remove the caking in powder.Use graphite jig, make the isolated material of mould and target of molybdenum foil, upper and lower surface all with molybdenum foil as protection.Precompressed 3MPa, is evacuated to 10-3Pa, is heated to 400 DEG C with the speed of 10 DEG C/min, is incubated 1 hour, is filled with argon.It is forced into 10MPa, is then heated to 600 DEG C with the firing rate of 15 DEG C/min, be incubated 1 hour, it is ensured that cavity body of mould uniformity of temperature profile.Finally being heated to 750 DEG C with the firing rate of 10 DEG C/min, be incubated 1 hour, during temperature rises, every 50 DEG C increase 5MPa pressure, and final pressure is 20MPa.After insulation, closing heating system, pressurize is cold with stove.Target is taken out, removes molybdenum foil protective layer, then by the method for attrition process, target is worked into specified size.Target density is surveyed with Archimedes's drainage；Each essential element content, addition calculation target purity is measured with ICP-MS；With metallurgical microscope or scanning electron microscopic observation target interior tissue pattern, measure crystal grain mean diameter.
The fundamental performance parameter of target is as shown in table 3:
Table 3 pressure sintering produces the performance parameter of Li3PO4 target
| Material | Purity | Relative density | Size | Mean diameter |
| Li3PO4 | >99.9% | >98% | 100mm×100mm×10mm | <10 Micron |
Embodiment 3
Be 100nm by mean diameter, purity be the LiFePO4 of 99.95% be raw material, by grinding, the method for screening remove the caking in powder.Use graphite jig, make the isolated material of mould and target of molybdenum foil, upper and lower surface all with molybdenum foil as protection.Precompressed 3MPa, is evacuated to 10-3Pa, is heated to 400 DEG C with the speed of 10 DEG C/min, is incubated 1 hour, is filled with argon.It is forced into 10MPa, is then heated to 600 DEG C with the firing rate of 15 DEG C/min, be incubated 1 hour, it is ensured that cavity body of mould uniformity of temperature profile.Finally being heated to 750 DEG C with the firing rate of 10 DEG C/min, be incubated 1 hour, during temperature rises, every 50 DEG C increase 5MPa pressure, and final pressure is 20MPa.After insulation, closing heating system, pressurize is cold with stove.Target is taken out, removes molybdenum foil protective layer, then by the method for attrition process, target is worked into specified size.Target density is surveyed with Archimedes's drainage；Each essential element content, addition calculation target purity is measured with ICP-MS；With metallurgical microscope or scanning electron microscopic observation target interior tissue pattern, measure crystal grain mean diameter.
The fundamental performance parameter of target is as shown in table 3:
Table 4 pressure sintering produces the performance parameter of LiFePO4 target
| Material | Purity | Relative density | Size | Mean diameter |
| LiFePO4 | >99.9% | >98% | 100mm×100mm×10mm | <10 Micron |
Claims (10)
1. the invention provides production high-quality LiCoO2, a kind of hot-press method of LiFePO4, Li3PO4 target, its step specifically includes that powder pre-treatment, degasification process, interim pressure sintering, target post processing.
( 1 ),The method use graphite jig, make the isolated material of mould and target of molybdenum foil, upper and lower surface all with molybdenum foil as protection.
( 2 ),Precompressed 1～5MPa, is evacuated to 10-3Pa, is heated to 100～400 DEG C with the speed of 10～15 DEG C/min, is incubated 0.5h～1h, is filled with argon.
( 3 ),Then being heated to 400 DEG C～1000 DEG C with the speed of 10～15 DEG C/min, progressively heat up, pressurization, final sintering pressure is 20～60MPa, is incubated 1～5h.
( 4 ),Pressurize is cold with stove, takes out and is ground off on top layer.
2., by the method for right 1, the LiCoO2 sputtering target material of production, its purity is at least 99.9%, and density is not less than 98%, and average crystal grain is not more than 10 microns.
3., by the method for right 1, the LiCoO2 sputtering target material of production, its purity is at least 99.9%, and density is not less than 98%, and average crystal grain is not more than 5 microns.
4., by the method for right 1, the LiCoO2 sputtering target material of production, its purity is at least 99.9%, and density is not less than 99%, and average crystal grain is not more than 5 microns.
5., by the method for right 1, the LiFePO4 sputtering target material of production, its purity is at least 99.9%, and density is not less than 98%, and average crystal grain is not more than 10 microns.
6., by the method for right 1, the LiFePO4 sputtering target material of production, its purity is at least 99.9%, and density is not less than 98%, and average crystal grain is not more than 5 microns.
7., by the method for right 1, the LiFePO4 sputtering target material of production, its purity is at least 99.9%, and density is not less than 99%, and average crystal grain is not more than 5 microns.
8., by the method for right 1, the Li3PO4 sputtering target material of production, its purity is at least 99.9%, and density is not less than 98%, and average crystal grain is not more than 10 microns.
9., by the method for right 1, the Li3PO4 sputtering target material of production, its purity is at least 99.9%, and density is not less than 98%, and average crystal grain is not more than 5 microns.
10., by the method for right 1, the Li3PO4 sputtering target material of production, its purity is at least 99.9%, and density is not less than 99%, and average crystal grain is not more than 5 microns.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018115100A (en) * | 2017-01-20 | 2018-07-26 | 三井金属鉱業株式会社 | LiCoO2 SINTERED BODY AND PRODUCTION METHOD THEREOF |
| CN114057233A (en) * | 2021-11-17 | 2022-02-18 | 鄂尔多斯市紫荆创新研究院 | Lithium cobaltate anode target material for preparing thin-film lithium battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090045053A1 (en) * | 2007-08-17 | 2009-02-19 | Poong Kim | Method of producing a lithium phosphate sintered body and sputtering target |
| CN102206802A (en) * | 2010-03-29 | 2011-10-05 | 北京品一材料科技有限责任公司 | All-solid-state film lithium ion battery related target material and manufacturing method thereof |
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2016
- 2016-01-07 CN CN201610003698.1A patent/CN105734502A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090045053A1 (en) * | 2007-08-17 | 2009-02-19 | Poong Kim | Method of producing a lithium phosphate sintered body and sputtering target |
| CN102206802A (en) * | 2010-03-29 | 2011-10-05 | 北京品一材料科技有限责任公司 | All-solid-state film lithium ion battery related target material and manufacturing method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018115100A (en) * | 2017-01-20 | 2018-07-26 | 三井金属鉱業株式会社 | LiCoO2 SINTERED BODY AND PRODUCTION METHOD THEREOF |
| CN114057233A (en) * | 2021-11-17 | 2022-02-18 | 鄂尔多斯市紫荆创新研究院 | Lithium cobaltate anode target material for preparing thin-film lithium battery and preparation method thereof |
| CN114057233B (en) * | 2021-11-17 | 2023-09-26 | 鄂尔多斯市紫荆创新研究院 | Lithium cobalt oxide positive electrode target material for preparing thin film lithium battery and preparation method thereof |
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Application publication date: 20160706 |