CN106048542A - Preparation method of lithium cobaltate target - Google Patents

Preparation method of lithium cobaltate target Download PDF

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Publication number
CN106048542A
CN106048542A CN201610004611.2A CN201610004611A CN106048542A CN 106048542 A CN106048542 A CN 106048542A CN 201610004611 A CN201610004611 A CN 201610004611A CN 106048542 A CN106048542 A CN 106048542A
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acid lithium
cobalt acid
target
lithium target
preparation
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Inventor
谢海保
劳景兴
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Huizhou Baiterui Technology Co Ltd
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Huizhou Baiterui Technology Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a lithium cobaltate target and a preparation method of the lithium cobaltate target. The purity of the target is equal to or larger than 99.9%, the relative density of the target is equal to or larger than 98%, and the average grain size of the target is smaller than or equal to 50 micrometers. The preparation method of the target comprises the following steps that (1) lithium cobaltate powder is provided, and a blank is hydraulically formed from the lithium cobaltate; (2) isostatic cool pressing is conducted on the blank; and (3) the blank processed in the step (2) is placed in a furnace to be sintered, and a multi-stage temperature-rise pressurization way is adopted in the sintering process. The lithium cobaltate target prepared through the method is small in grain size and high in compactness. Under the proper condition, a film which is excellent in performance can be obtained by sputtering the target, and accordingly the energy storage capacity and cycle index of a full-solid film lithium ion battery are improved.

Description

The preparation method of complete a kind of cobalt acid lithium target
Technical field
The present invention relates to the preparation method of complete a kind of cobalt acid lithium target.
Background technology
The fast development of the electronic device such as sensor, MEMS, CMOS chip miniaturization, it is desirable to have that volume is little, lightweight, ratio The miniature compact power supply that capacity is high is matched.Solid-State Thin Film Li-Ion Batteries is 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 various The independence of portable microelectronic component or stand-by power supply, and the power supply of MEMS, civilian or the most all represent Go out wide application prospect.Solid-State Thin Film Li-Ion Batteries has its ample scope for abilities in different field, as led in space flight In territory, this micro cell miniaturization, lightweight have considerable captivation to aerospace craft；Militarily, the U.S. Sandia National Laboratory, Oak Ridge National Laboratory (ORNL), the jet jet laboratory of NASA (NASA) And film lithium ion battery is all used for weapon Intellectualized monitoring and pipe at active development by the Air Force Research Laboratory (JPL) The micro cell chip technology of reason system；Its purposes also includes: miniature robot surveillance plane electrical source of power (includes shooting dress Put power supply), multiple microsensor, CMOS integrated circuit, smart card (SmartCard), miniature in biochip and human body Surgical device and mini-medical device etc..
The core component positive electrode of solid-State Thin Film Li-Ion Batteries is always focus of concern, corresponding Film performance directly determines capacity and the service life of battery.Therefore, superior in quality target also will become more important.One For as, the production method of cobalt acid lithium target has ordinary sinter method, hot isostatic pressing method, pressure sintering and pressure sintering four kinds.These four Being compared as follows of method:
1, ordinary sinter method: general use to cold pressing add the method for sintering and prepare.In cold pressure procedure, in order to strengthen the molding of biscuit Property, the binding agent of 0.5%～2% can be added wherein, pressing pressure can not be too big, since it is desired that reserve enough passages to allow bonding Agent is discharged, but binding agent still has residual, adds the impurity content of target.Due to the relative density of biscuit be 60%～ 70%, after target has sintered, the relative density of target can only achieve 70%～90%.
Hot isostatic pressing method: the method can be at more than pressure 100MPa, and sintering temperature is 600 DEG C～1500 DEG C sintering targets Material, 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 relatively Little, the processing capacity of following process is relatively big, then utilization rate of raw materials is relatively low.
Pressure sintering: the method can use refractory metal mould, ceramic die or graphite jig, protects in vacuum or other atmosphere Protecting down and be sintered, general sintering pressure is 20～80MPa, can obtain the target that relative density is 98%～100%.The method Production cost is relatively low, and technical process is relatively simple, specifically includes that charging, sintering, the demoulding, following process etc., and each step Control relatively simple, the stay in grade of product, it is possible to obtain the semi-finished product close to product requirement size.
Pressure sintering method: the method is generally used for producing ceramic target, is sintered under conditions of atmosphere protection, sintering Mode is that interim boosting heats up.This production method cost is relatively low, and technical process is controlled, and key step includes: hydraulic pressure compacting, cold Isostatic pressed compacting, interim sintering, cooling control, following process etc., each step simple to operate, core technology is agglomerant Skill.
But, cobalt acid its crystallite dimension of lithium target prepared according to the normal pressure atmosphere sintering process of prior art is bigger, Consistency is the highest.Under proper condition, employ and sputter the full solid thin film lithium-ion electric of the thin film obtained by these targets The energy storage capacity in pond and cycle-index also ratio is relatively low.
Summary of the invention
The technical problem to be solved is to overcome the deficiencies in the prior art, it is provided that a kind of cobalt acid lithium target and system thereof Preparation Method.
For solving above technical problem, the present invention adopts the technical scheme that: a kind of cobalt acid lithium target, its purity is more than In 99.9%, relative density more than equal to 98%, average grain size is less than or equal to 50 microns.
Preferably, the purity of described cobalt acid lithium target is more than or equal to 99.99%.
It is further preferred that the purity of described cobalt acid lithium target is more than or equal to 99.999%.
Preferably, the relative density of described cobalt acid lithium target is more than equal to 99%.
Preferably, the average crystal grain of described cobalt acid lithium target is less than or equal to 10 microns.
A kind of preparation method of cobalt acid lithium target, the method comprises the following steps:
(1) provide cobalt acid lithium powder, and be blank by its shaped by fluid pressure；
(2) described blank is carried out isostatic cool pressing processing；
(3) being placed in stove by the blank through step (2) and be sintered, during sintering, in stove, vacuum is 10-4~10-3Pa, first With the heating rate of 50 ~ 300 DEG C/h, temperature is risen to 800 DEG C ~ 900 DEG C, after being incubated 4 ~ 24 hours, be filled with noble gas, then With the heating rate of 100 ~ 400 DEG C/h, temperature is risen to 900 DEG C ~ 1200 DEG C, be down to room temperature after being incubated 4 ~ 24 hours and i.e. obtain described Cobalt acid lithium target, rate of temperature fall is 20 ~ 100 DEG C/h.
Preferably, in step (1), the purity of described cobalt acid lithium powder is 99.90% ~ 99.99%, mean diameter be 50 ~ 100nm。
Preferably, in step (1), the operating pressure of described shaped by fluid pressure is 5 ~ 50MPa.
Preferably, in step (2), the operating pressure carrying out isostatic cool pressing processing is 200 ~ 300MPa.
Preferably, described in step (3), noble gas is argon.
Due to the utilization of technique scheme, the present invention compared with prior art has following advantages and effect: according to this The cobalt acid lithium target that the preparation method of invention is prepared, its crystallite dimension is tiny and consistency is high.Under proper condition, this is sputtered The thin film of a little target energy excellents, thus improve energy storage capacity and the cycle-index of solid-State Thin Film Li-Ion Batteries.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the cobalt acid lithium target prepared according to the method for the present invention.
Detailed description of the invention
The present invention is further detailed explanation below, but the invention is not restricted to following example.
According to the present embodiment, it is made by the steps cobalt acid lithium target:
(1), with mean diameter as 100nm, purity be the cobalt acid lithium powder of 99.95% be raw material, by grind, screening method After removing the caking in powder；Using hydraulic press is blank by cobalt acid lithium powder shaped by fluid pressure, and the pressure that molding uses is 20MPa；
(2), blank being carried out isostatic cool pressing processing, pressing pressure is 250MPa, and isostatic cool pressing processing can improve the densification of blank Property, repressed after biscuit relative density be about 58%；
(3), for ensureing that in high-temperature sintering process, the flowing of material is carried out with bonding orderly stage, sintering process uses multistage The mode of Duan Shengwen pressurization completes sintering.Being placed in stove by blank after compacting and be sintered, during sintering, in stove, vacuum is 6.0×10-4Pa, rises to 800 DEG C with 100 DEG C/h speed by temperature, is filled with 1atm Ar gas after being incubated 8 hours, the most again with The ramp of 100 DEG C/h, to 1100 DEG C, is incubated 12 hours, finally cools the temperature to room temperature with the speed of 50 DEG C/h.
The target prepared is taken out, can be made into required size by mill processing method.
The cobalt acid lithium target of above-mentioned preparation is scanned electronic microscope photos, and Fig. 1 is gained scanning electron microscope (SEM) photograph, therefrom can see Going out, the crystallite dimension of cobalt acid lithium target is relatively fine and consistency is high, and relative density is about 99%.
Above-described embodiment, only for technology design and the feature of the explanation present invention, its object is to allow person skilled in the art Scholar will appreciate that present disclosure and implements according to this, can not limit the scope of the invention with this.All according to the present invention The equivalence that spirit is made changes or modifies, and all should contain within protection scope of the present invention.

Claims (10)

1. a cobalt acid lithium target, it is characterised in that: the purity of described cobalt acid lithium target more than or equal to 99.9%, relatively denser In equal to 98%, average grain size is less than or equal to 50 microns.
Cobalt acid lithium target the most according to claim 1, it is characterised in that: the purity of described cobalt acid lithium target is for being more than or equal to 99.99%。
Cobalt acid lithium target the most according to claim 2, it is characterised in that: the purity of described cobalt acid lithium target is for being more than or equal to 99.999%。
Cobalt acid lithium target the most according to claim 1, it is characterised in that: the relative density of described cobalt acid lithium target is more than In 99%.
Cobalt acid lithium target the most according to claim 1, it is characterised in that: the average crystal grain of described cobalt acid lithium target is less than In 10 microns.
6. the preparation method of a cobalt acid lithium target, it is characterised in that said method comprising the steps of:
(1) provide cobalt acid lithium powder, and be blank by its shaped by fluid pressure；
(2) described blank is carried out isostatic cool pressing processing；
(3) being placed in stove by the blank through step (2) and be sintered, during sintering, in stove, vacuum is 10-4~10-3Pa, first With the heating rate of 50 ~ 300 DEG C/h, temperature is risen to 800 DEG C ~ 900 DEG C, after being incubated 4 ~ 24 hours, be filled with noble gas, then With the heating rate of 100 ~ 400 DEG C/h, temperature is risen to 900 DEG C ~ 1200 DEG C, be down to room temperature after being incubated 4 ~ 24 hours and i.e. obtain described Cobalt acid lithium target, rate of temperature fall is 20 ~ 100 DEG C/h.
The preparation method of cobalt acid lithium target the most according to claim 6, it is characterised in that: in step (1), described cobalt acid lithium The purity of powder is 99.90% ~ 99.99%, mean diameter is 50 ~ 100nm.
The preparation method of cobalt acid lithium target the most according to claim 6, it is characterised in that: in step (1), described hydraulic pressure becomes The operating pressure of type is 5 ~ 50MPa.
The preparation method of cobalt acid lithium target the most according to claim 6, it is characterised in that: in step (2), carry out cold etc. quiet The operating pressure of pressure processing is 200 ~ 300MPa.
The preparation method of cobalt acid lithium target the most according to claim 6, it is characterised in that: indifferent gas described in step (3) Body is argon.
CN201610004611.2A 2016-01-07 2016-01-07 Preparation method of lithium cobaltate target Pending CN106048542A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111733393A (en) * 2020-08-18 2020-10-02 宁波江丰钨钼材料有限公司 Surface treatment method of molybdenum target blank after cold isostatic pressing
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
CN114085096A (en) * 2021-11-17 2022-02-25 鄂尔多斯市紫荆创新研究院 Annealing method of lithium cobaltate positive electrode target material and lithium cobaltate positive electrode target material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102181840A (en) * 2011-06-22 2011-09-14 苏州晶纯新材料有限公司 Lithium cobalt oxide target material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102181840A (en) * 2011-06-22 2011-09-14 苏州晶纯新材料有限公司 Lithium cobalt oxide target material and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111733393A (en) * 2020-08-18 2020-10-02 宁波江丰钨钼材料有限公司 Surface treatment method of molybdenum target blank after cold isostatic pressing
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
CN114085096A (en) * 2021-11-17 2022-02-25 鄂尔多斯市紫荆创新研究院 Annealing method of lithium cobaltate positive electrode target material and lithium cobaltate positive electrode target material
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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