CN106058305A - Method for in-situ preparation of minisized all-solid-state thin-film lithium-ion battery by using PLD - Google Patents

Method for in-situ preparation of minisized all-solid-state thin-film lithium-ion battery by using PLD Download PDF

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CN106058305A
CN106058305A CN201610664363.4A CN201610664363A CN106058305A CN 106058305 A CN106058305 A CN 106058305A CN 201610664363 A CN201610664363 A CN 201610664363A CN 106058305 A CN106058305 A CN 106058305A
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pld
situ
thin film
film
target
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CN106058305B (en
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钱婧
王亚平
包吴奇
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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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
    • H01M10/058—Construction or manufacture
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • 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
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a method for in-situ preparation of a minisized all-solid-state thin-film lithium-ion battery by using PLD, belonging to the technical field of lithium-ion batteries. The method comprises the following steps: 1) pretreatment of a substrate: cleaning a silica substrate and drying the substrate for subsequent usage; and 2) preparation of the battery: successively depositing metal platinum used as a current collector, lithium cobalt oxide used as a positive electrode, lithium phosphorus oxynitride used as an electrolyte, graphene used as an electron penetration and transition layer and graphite as a negative electrode film on the cleaned silica substrate in the step 1) by using PLD. The structure of the minisized all-solid-state thin-film lithium-ion battery employs PLD in-situ deposition and introduces graphene as the electron penetration and transition layer between the negative electrode graphite and the solid electrolyte, so the performance and cycle index of the battery can be effectively improved, heat stability of the battery is guaranteed, and heatproof requirements of welding are met.

Description

A kind of method that PLD prepares miniature solid-State Thin Film Li-Ion Batteries in situ
Technical field
The present invention relates to the preparation method of a kind of lithium ion battery, be specifically related to one PLD and prepare miniature complete solid in situ The method of state film lithium ion battery, belongs to technical field of lithium ion.
Background technology
Along with the development of the technical fields such as microelectronics, communication, medical treatment implantation, military affairs and radio frequency identification, its The miniaturization of electronic products of correspondence, miniaturization, the integrated trend place having become as global technology development.This comes for battery Say it is once to innovate and challenge, it is meant that the demand of minicell will day by day be increased.At present, research is actively developed both at home and abroad Minicell kind has lithium ion battery, zinc-nickel cell, solaode, fuel cell etc..Wherein, miniature lithium ion battery because of The advantages such as high-energy-density, high voltage, long circulation life, high safety performance, by the extensive concern of researcher.But lithium at present Ion battery uses liquid electrolyte mostly, the problem that it exists easily leakage, perishable, security reliability is relatively low.By contrast, Miniature solid-State Thin Film Li-Ion Batteries uses solid electrolyte because of it, the heat stability that had, there is not leakage and electricity Solve liquid loss problem, there is higher safety coefficient, therefore show one's talent in numerous Study on Li-ion batteries.In addition, Electrode and the electrolyte of miniature solid-State Thin Film Li-Ion Batteries are solid-state, eliminate barrier film, electrolyte, electrolytic salt and The use of the materials such as binding agent, simplifies the preparation process of lithium ion battery.Therefore, miniature solid-State Thin Film Li-Ion Batteries, It is expected to before the aspects such as future portable electronic equipment, defence equipment and microelectromechanical systems (MEMS) have a wide range of applications Scape
Pulsed laser deposition technique (Pulsed Laser Deposition, PLD) is as a kind of vacuum coating technology, quilt It is widely used in film preparation.Its operation principle is exactly that laser is radiated on target, and the particle in target becomes after ablation Plasma to substrate transport, condenses nucleation film forming from target on substrate.PLD, compared with other coating technique, has behaviour Make the advantages such as simple, parameter easy-regulating；Additionally, by selecting different target, the sputtering parameter of regulation and control instrument can be prepared in situ Different patterns and the multilayer films of different-thickness；Meanwhile, target and film composition ensure that identical chemistry Metering ratio.At present, PLD technology is the most successfully used to prepare LiCoO2/Li3.4V0.6Si0.4O4/ SnO solid film lithium battery Structure or anode film material LixMn2O4Or richness lithium phase Li2MnO3Thin film (Electrochemistry Communications, 6(2004)417-421；Applied Surface Science,197-198(2002)516-521；Journal of Materials Chemistry A,2014,2(7):2283-2289).The electrolytic thin-membrane prepared by PLD is smoothed and causes Close, researcher is also analyzed and is shown that film composition can keep being close to consistent with target component.After charge and discharge cycles, electrolyte Thin film still keeps homogeneity, and cell interface structure (electrolyte/positive pole, electrolyte/negative pole) still smooth defect free occurs.This Outward, the hull cell prepared by PLD film deposition techniques can be obviously improved the interface impedance (lithium ion in solid electrolyte Electrical conductivity is the most lower slightly compared with liquid phase electrolyte, thus causes ohmic resistance to increase).But, by this PLD technology The film lithium ion battery (Electrochemistry Communications, 6 (2004) 417-421) of preparation is through the After charge and discharge cycles, capacity is gradually decayed, discharge capacity circulation volume the most for the first time after 100 circulations 45%, mainly due to the Li of SnO Yu embedding+Reaction generates Sn-Li alloy and Li2O is caused.Additionally, have researcher by PLD Continuous coating is realized: i.e. PLD deposits positive pole LiCoO from the combination of different sputtering technologies2, radio frequency and direct magnetic control deposition LiPON, heat Evaporated metal cathode of lithium (Solid State Ionics, 285 (2016) 118-121).Although this combination deposition technique is permissible Realizing omnidistance vacuum to prepare, interracial contact is good, and cell manufacturing process not ingress of air, but this method is the most loaded down with trivial details, no It is beneficial to industrialized large-scale production.In addition researcher mostly uses metal when preparing solid-State Thin Film Li-Ion Batteries at present Lithium is as negative pole, but lithium fusing point relatively low (180 DEG C), with micro cell and the heatproof (250 of solder reflow technology in integrated circuit DEG C) require incompatible, in cycle charge-discharge, easily form dead lithium.In addition lithium metal is to oxygen and water vapor sensitive, needs harshness Encapsulation technology keep stable, seriously constrain the large-scale promotion application of full solid thin film lithium electricity.Therefore, prepared by development one Technology is simple, realize repeatedly circulation volume keeps, meet simultaneously the miniature full solid thin film lithium of the high temperature resistant requirement of heat stability from Sub-battery, significant.
Summary of the invention
The problem existed for above-mentioned prior art, the present invention provides one PLD to prepare miniature full solid thin film in situ The method of lithium ion battery, can improve battery performance and cycle-index, ensures heat stability and the welding of miniature lithium electricity simultaneously Heatproof requirement.
To achieve these goals, one PLD that the present invention uses prepares miniature full solid thin film lithium-ion electric in situ The method in pond, comprises the following steps:
1) pretreatment of substrate: silicon dioxide substrates is cleaned up, and dried for standby；
2) preparation of battery: with PLD in step 1) in be sequentially depositing metal platinum in the silicon dioxide substrates that cleans up and make Make as penetration of electrons transition zone and graphite as electrolyte, Graphene as positive pole, LiPON for collector, cobalt acid lithium For negative film.
As improvement, described step 1) in, concrete cleaning step is:
I () is by silicon dioxide substrates ultrasonic cleaning 20min in acetone；
(ii) ultrasonic cleaning 20min the most in ethanol；
(iii) clean several times with deionized water.
As improvement, described step 2) preparation of battery, specifically include preparation and b) the produced in situ micro electric of a) target The each layer film in pond；
The preparation of described a) target:
When using PLD to prepare electrolyte lithium phosphorous oxynitride, the target of use is by Li3PO4Powder body tabletting sintering forms；
When deposit cobalt acid lithium is as positive pole, the target of use passes through LiCoO2Tabletting sintering is made；
When deposited graphite alkene is as penetration of electrons transition zone, the target of use is made by Graphene tabletting sintering；
When deposited graphite is as negative film, the target of use is made by graphite composite powder tabletting sintering.
As improvement, described b) the produced in situ each layer film of minicell, specifically include following steps:
Utilize PLD plating layer of metal platinum as plus plate current-collecting body on (i) silicon chip after cleaning-drying；
(ii) on same PLD instrument, LiCoO is utilized2Target in-situ deposition positive pole LiCoO2Thin film；
(iii) on same PLD instrument, PLD deposition solid electrolyte LiPON is utilized；
(iv) on same PLD instrument, penetration of electrons transport layer graphene film is deposited；
V (), on same PLD instrument, deposited graphite is as negative film.
As improvement, described step (ii) concretely comprises the following steps:
LiCoO2Target is made at 900 DEG C of sintering 5h by dry-pressing powder body, and deposition process is passed through certain oxygen, and air pressure controls At 0.13Pa, underlayer temperature 400 DEG C；Laser frequency is 3Hz, and laser energy density is 1.0Jcm-2。
As improvement, described step (iii) concretely comprises the following steps:
When using PLD technology to prepare solid electrolyte LiPON thin film, Li3PO4Target is made at 600 DEG C of sintering 5h, deposition Time be passed through N2, air pressure is at 0.5Pa, and laser frequency is 6Hz, and laser energy density is 2.5Jcm-2, room temperature deposition.
As improvement, described step (iv) concretely comprises the following steps: be first filled with protective atmosphere Ar, and air pressure is at 0.5Pa, laser frequency Rate is 3Hz, and laser energy density is 1.0Jcm-2, room temperature deposition graphene film.
As improvement, described step (v) concretely comprises the following steps: when deposited graphite is as negative film, and the atmosphere of employing is Ar, Air pressure is at 0.1Pa, and laser frequency is 6Hz, and laser energy density is 2.0Jcm-2, room temperature deposition.
It addition, present invention also offers the miniature full solid thin film lithium-ion electric that a kind of described method of any of the above-described item prepares Pond.
Compared with prior art, there is advantages that
1) this miniature solid-State Thin Film Li-Ion Batteries uses graphite to substitute traditional lithium metal as negative film, it is to avoid Reaction between lithium metal and other metal, it also avoid the stroke of dead cathode of lithium simultaneously, substantially increases film all-solid-state The stability of lithium ion battery.
2) Graphene that employing has high conductivity, heat conductivity is good, insensitive to environment, introduces this thin-film electro by PLD In the material system of pond, it is placed between electrolyte and graphite cathode as penetration of electrons transport layer, the quick penetration of electronics can be realized, This Graphene/graphite cathode composite construction is possible not only to improve the chemical property of All-solid film batteries, but also ensures Hull cell thermally-stabilised.
3) this preparation method is quickly and easily, not only avoids and air and moisture, and optimizes solid-state thin-film battery Preparation flow and enhancing circulating battery cycle.
4) the miniature solid-State Thin Film Li-Ion Batteries prepared by PLD technology be expected to future portable electronic equipment, The aspects such as defence equipment and microelectromechanical systems (MEMS) have a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the principle schematic that the present invention uses pulsed laser deposition；
Fig. 2 is that the present invention prepares miniature All-solid film batteries structure section schematic diagram；
In figure: 1, laser instrument, 2, lens, 3, optical beam scanner, 4, power supply, 5, substrate heater, 6, substrate, 7, plumage brightness, 8, vacuum chamber, 9, target, 10, graphite, 11, LiPON, 12, metal platinum, 13, silicon dioxide substrates, 14, cobalt acid lithium, 15, stone Ink alkene.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention of greater clarity, below by drawings and Examples, to this Invention is further elaborated.However, it should be understood that specific embodiment described herein is only in order to explain the present invention, It is not limited to the scope of the present invention.
Unless otherwise defined, all of technical term used herein and scientific terminology are led with the technology belonging to the present invention The implication that the technical staff in territory is generally understood that is identical, and the term used the most in the description of the invention is intended merely to retouch State the purpose of specific embodiment, it is not intended that in limiting the present invention.
The pulsed laser deposition principle used in the inventive method, as it is shown in figure 1, by laser instrument 1 through lens 2, then By optical beam scanner 3 by laser bombardment on target 9, the electrodeposition substance fallen by laser bombardment on the substrate 6, and substrate 6 Using plumage brightness 7, power supply 4 and substrate heater 5 to heat, it is ensured that deposition effect, wherein bombardment, deposition process are all in vacuum Room 8 is carried out.
Embodiment one
A kind of method that PLD in situ prepares miniature solid-State Thin Film Li-Ion Batteries, specifically includes following steps:
1) pretreatment of substrate:
A) first, by silicon dioxide substrates 13 ultrasonic cleaning, the step of cleaning is: (i) ultrasonic cleaning in acetone 20min；(ii) ultrasonic cleaning 20min in ethanol, cleans several times with deionized water the most again；
2) preparation of target:
PLD is used to prepare electrolyte Li3PO4-xNx(LiPON), during thin film, the target of use is by Li3PO4Powder body tabletting burns Knot forms, for positive pole LiCoO2Thin film, electric transmission layer graphene and negative pole graphite linings, its target used all passes through LiCoO2, Graphene and graphite composite powder tabletting sintering make；
3) each layer film of growth in situ minicell:
Miniature All-solid film batteries structure section schematic diagram is as shown in Figure 2:
Utilize PLD plating layer of metal platinum 12 (deposit thickness is 100nm) as positive pole on (i) silicon chip after cleaning-drying Collector metallic film；
(ii) on same PLD instrument, LiCoO is utilized2Target in-situ deposition positive pole cobalt acid lithium 14 thin film (thickness 200nm)；
Wherein, LiCoO2Target is made by dry-pressing powder sintering (900 DEG C of sintering 5h), and deposition process is passed through certain oxygen Gas, air pressure controls at 0.13Pa, underlayer temperature 400 DEG C；Laser frequency is 3Hz, and laser energy density is 1.0Jcm-2；
(iii) on same PLD instrument, PLD deposition solid electrolyte Li is utilized3PO4-xNx(LiPON 11 thin film, This thin film deposition thickness is 1 μm)；
When using PLD technology to prepare solid electrolyte LiPON thin film, target is Li3PO4(600 DEG C of sintering 5h), deposition Time be passed through N2, air pressure is at 0.5Pa, and laser frequency is 6Hz, and laser energy density is 2.5Jcm-2, room temperature deposition；
(iv) on same PLD instrument, depositing penetration of electrons transport layer Graphene 15 thin film, thickness is 100nm；
First being filled with protective atmosphere Ar, air pressure is at 0.5Pa, and laser frequency is 3Hz, and laser energy density is 1.0Jcm-2, room Temperature deposition；
V (), on same PLD instrument, deposited graphite 10 is as negative pole (graphite linings thickness is 500nm), the atmosphere of employing For Ar, air pressure is at 0.1Pa, and laser frequency is 6Hz, and laser energy density is 2.0Jcm-2, room temperature deposition.
In whole preparation process, every kind of target being screwed in target and smashs, base substrate also screws in substrate and smashs, and closes chamber Door, to cavity mechanical pump and molecular pump evacuation.When intracavity vacuum is evacuated to 10-4Pa, is passed through the reacting gas of correspondence, and adjusts To certain air pressure；Opening target and substrate rotating switch, regulation target rotating speed rotates at 120rpm, and substrate rotating speed is at 60rpm. Panel inputs laser energy density and frequency values, opens laser instrument and start deposition process；After arriving sedimentation time, close Close laser instrument and rotating switch, after underlayer temperature is down to room temperature, takes out sample, place and be dried in sealer, in case carrying out structure Morphology characterization or electrochemical property test.If not wanting test event, the most not taking out sample, only need to close laser instrument, adjust Next target location whole and deposition parameter, start deposition process, until last negative film preparation terminates.
Embodiment two
Contrast test.(iv) step in embodiment one being omitted, (v) step makees following adjustment, and remaining step is consistent:
(v) on same PLD instrument, deposition negative pole graphite linings (600nm), employing atmosphere is Ar, air pressure at 0.1Pa, Laser frequency is 6Hz, and laser energy density is 2.0Jcm-2, room temperature deposition.
Embodiment three
Contrast test.(v) step in embodiment one being omitted, (iv) step makees following adjustment, and remaining step is consistent:
(iv) on same PLD instrument, deposition negative metal lithium layer thin film (600nm).Atmosphere is Ar, and air pressure exists 0.1Pa, laser frequency is 6Hz, and laser energy density is 2.0Jcm-2, room temperature deposition.
Embodiment four
The structure and morphology of the miniature solid-State Thin Film Li-Ion Batteries that employing the inventive method prepares and chemical property Characterize:
Use ac impedance spectroscopy and discharge and recharge cabinet test the impedance spectrogram of solid film lithium battery, Cyclic voltamogram curve And charging and discharging curve, by scanning electron microscope monitoring cell structure and surface topography, utilize X-ray diffractometer to analyze PLD and sink Long-pending thin film phase structure, composes test interface chemical valence state by X-ray energy dispersion thus analyzes the heat stability of battery structure.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention Any amendment, equivalent or the improvement etc. made within god and principle, should be included within the scope of the present invention.

Claims (9)

1. the method preparing miniature solid-State Thin Film Li-Ion Batteries in situ with PLD, it is characterised in that include following step Rapid:
1) pretreatment of substrate: silicon dioxide substrates (13) is cleaned up, and dried for standby；
2) preparation of battery: be sequentially depositing metal platinum in the silicon dioxide substrates (13) cleaned up in step 1) with PLD (12) wear as electronics as electrolyte, Graphene (15) as positive pole, LiPON (11) as collector, cobalt acid lithium (14) Transition zone and graphite (10) are as negative film thoroughly.
The method that a kind of PLD the most according to claim 1 prepares miniature solid-State Thin Film Li-Ion Batteries in situ, it is special Levying and be, in described step 1), concrete cleaning step is:
(i) by silicon dioxide substrates (13) ultrasonic cleaning 20min in acetone；
Ultrasonic cleaning 20min the most in ethanol；
(iii) clean several times with deionized water.
The method that a kind of PLD the most according to claim 1 prepares miniature solid-State Thin Film Li-Ion Batteries in situ, it is special Levy and be, described step 2) preparation of battery, specifically include preparation and b) each layer film of produced in situ minicell of a) target；
The preparation of described a) target:
When using PLD to prepare electrolyte lithium phosphorous oxynitride (11), the target of use is by Li3PO4Powder body tabletting sintering forms；
When deposit cobalt acid lithium (14) is as positive pole, the target of use passes through LiCoO2Tabletting sintering is made；
When deposited graphite alkene (15) is as penetration of electrons transition zone, the target of use is made by Graphene tabletting sintering；
When deposited graphite (10) is as negative film, the target of use is made by graphite composite powder tabletting sintering.
The method that a kind of PLD the most according to claim 3 prepares miniature solid-State Thin Film Li-Ion Batteries in situ, it is special Levy and be, described b) the produced in situ each layer film of minicell, specifically include following steps:
Utilize PLD plating layer of metal platinum (12) as plus plate current-collecting body on (i) silicon chip after cleaning-drying；
(ii) on same PLD instrument, LiCoO is utilized2Target in-situ deposition positive pole LiCoO2Thin film；
(iii) on same PLD instrument, PLD deposition solid electrolyte LiPON is utilized；
(iv) on same PLD instrument, penetration of electrons transport layer graphene film is deposited；
V (), on same PLD instrument, deposited graphite (10) is as negative film.
The method that a kind of PLD the most according to claim 4 prepares miniature solid-State Thin Film Li-Ion Batteries in situ, it is special Levying and be, described step (ii) concretely comprises the following steps:
LiCoO2Target is made at 900 DEG C of sintering 5h by dry-pressing powder body, and deposition process is passed through certain oxygen, and air pressure controls 0.13 Pa, underlayer temperature 400oC；Laser frequency is 3 Hz, and laser energy density is 1.0 Jcm-2。
The method that a kind of PLD the most according to claim 4 prepares miniature solid-State Thin Film Li-Ion Batteries in situ, it is special Levying and be, described step (iii) concretely comprises the following steps:
When using PLD technology to prepare solid electrolyte LiPON thin film, Li3PO4Target is made at 600 DEG C of sintering 5h, logical during deposition Enter N2, air pressure is at 0.5 Pa, and laser frequency is 6 Hz, and laser energy density is 2.5 Jcm-2, room temperature deposition.
The method that a kind of PLD the most according to claim 4 prepares miniature solid-State Thin Film Li-Ion Batteries in situ, it is special Levying and be, described step (iv) concretely comprises the following steps: be first filled with protective atmosphere Ar, and air pressure is at 0.5Pa, and laser frequency is 3 Hz, Laser energy density is 1.0 Jcm-2, room temperature deposition graphene film.
The method that a kind of PLD the most according to claim 4 prepares miniature solid-State Thin Film Li-Ion Batteries in situ, it is special Levying and be, described step (v) concretely comprises the following steps: when deposited graphite (10) is as negative film, and the atmosphere of employing is Ar, and air pressure exists 0.1 Pa, laser frequency is 6 Hz, and laser energy density is 2.0 Jcm-2, room temperature deposition.
9. one kind uses the miniature solid-State Thin Film Li-Ion Batteries that method described in any one of claim 1-8 prepares.
CN201610664363.4A 2016-08-12 2016-08-12 A method of miniature solid-State Thin Film Li-Ion Batteries being prepared in situ with PLD Active CN106058305B (en)

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CN106848390A (en) * 2016-12-05 2017-06-13 东莞市绿骏电动自行车科技有限公司 A kind of film lithium cell of 3D structures
CN110335697A (en) * 2019-07-11 2019-10-15 四川大学 A kind of high abundance98The preparation method of Tc
CN114551116A (en) * 2022-02-22 2022-05-27 中北大学 Preparation method of lithium ion capacitor based on LiPON solid electrolyte

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CN104518208A (en) * 2013-09-30 2015-04-15 三星电子株式会社 Composite, carbon composite including the composite, electrode, lithium battery, electroluminescent device, biosensor, semiconductor device, and thermoelectric device including the composite and/or the carbon composite
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CN104518208A (en) * 2013-09-30 2015-04-15 三星电子株式会社 Composite, carbon composite including the composite, electrode, lithium battery, electroluminescent device, biosensor, semiconductor device, and thermoelectric device including the composite and/or the carbon composite
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Publication number Priority date Publication date Assignee Title
CN106848390A (en) * 2016-12-05 2017-06-13 东莞市绿骏电动自行车科技有限公司 A kind of film lithium cell of 3D structures
CN106848390B (en) * 2016-12-05 2019-02-01 东莞市绿骏电动自行车科技有限公司 A kind of film lithium cell of 3D structure
CN110335697A (en) * 2019-07-11 2019-10-15 四川大学 A kind of high abundance98The preparation method of Tc
CN114551116A (en) * 2022-02-22 2022-05-27 中北大学 Preparation method of lithium ion capacitor based on LiPON solid electrolyte
CN114551116B (en) * 2022-02-22 2023-08-29 中北大学 Preparation method of LiPON solid electrolyte-based lithium ion capacitor

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