CN106058305B - A method of miniature solid-State Thin Film Li-Ion Batteries being prepared in situ with PLD - Google Patents

A method of miniature solid-State Thin Film Li-Ion Batteries being prepared in situ with PLD Download PDF

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CN106058305B
CN106058305B CN201610664363.4A CN201610664363A CN106058305B CN 106058305 B CN106058305 B CN 106058305B CN 201610664363 A CN201610664363 A CN 201610664363A CN 106058305 B CN106058305 B CN 106058305B
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pld
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deposition
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CN106058305A (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 present invention discloses a kind of method that miniature solid-State Thin Film Li-Ion Batteries are prepared in situ with PLD, belongs to technical field of lithium ion, comprising the following steps: 1) pretreatment of substrate: silicon dioxide substrates is cleaned up, and dried for standby；2) preparation of battery: be sequentially depositing in the silicon dioxide substrates for using PLD to clean up in step 1) metal platinum as collector, cobalt acid lithium as anode, LiPON as electrolyte, graphene as penetration of electrons transition zone and graphite as negative film.Miniature full solid thin film lithium electricity structure of the invention is all made of PLD in-situ deposition, graphene is introduced between cathode graphite and solid electrolyte as electron-transport transition zone simultaneously, battery performance and cycle-index can be effectively improved, while guaranteeing thermal stability and the welding heatproof requirement of miniature lithium electricity.

Description

A method of miniature solid-State Thin Film Li-Ion Batteries being prepared in situ with PLD
Technical field
The present invention relates to a kind of preparation methods of lithium ion battery, and in particular to it is a kind of be prepared in situ with PLD it is miniature complete solid The method of state film lithium ion battery, belongs to technical field of lithium ion.
Background technique
With the continuous development of the technical fields such as microelectronics, communication, medical treatment implantation, military and radio frequency identification, Where corresponding miniaturization of electronic products, micromation, the integrated trend for having become global technology development.This carrys out battery Say it is primary innovation and challenge, it is meant that the demand to minicell will increasingly increase.Currently, actively developing research both at home and abroad Minicell type has lithium ion battery, zinc-nickel cell, solar battery, fuel cell etc..Wherein, miniature lithium ion battery because The advantages such as high-energy density, high voltage, long circulation life, high safety performance, the extensive concern by researcher.But current lithium Ion battery mostly uses greatly liquid electrolyte, there is a problem of that easily leakage, perishable, security reliability is lower.In contrast, Miniature solid-State Thin Film Li-Ion Batteries are because it uses solid electrolyte, and the thermal stability that has had, there is no leakage and electricity It solves liquid and problem is lost, there is higher safety coefficient, therefore show one's talent in numerous Study on Li-ion batteries.In addition to this, The electrode and electrolyte of miniature solid-State Thin Film Li-Ion Batteries are solid-state, be omitted diaphragm, electrolyte, electrolytic salt and The use of the materials such as binder simplifies the preparation process of lithium ion battery.Therefore, miniature solid-State Thin Film Li-Ion Batteries, It is expected in future portable electronic equipment, defence equipment and microelectromechanical systems (before having a wide range of applications in terms of MEMS Scape
Pulsed laser deposition technique (Pulsed Laser Deposition, PLD) is used as a kind of vacuum coating technology, quilt It is widely used in film preparation.Its working principle is exactly laser irradiation on target, and the particle in target becomes after ablation Plasma is from target to substrate transport, and cohesion nucleation forms a film on substrate.PLD has behaviour compared with other coating techniques Make the advantages such as simple, parameter easy-regulating；In addition, by selecting different targets, the sputtering parameter for regulating and controlling instrument can be prepared in situ The multilayer films of different pattern and different-thickness；At the same time, target and film composition can guarantee identical chemistry Metering ratio.Currently, PLD technology is successfully used to prepare LiCoO2/Li3.4V0.6Si0.4O4/ SnO solid film lithium battery Structure or anode film material LixMn2O4Or rich lithium phase Li2MnO3Film (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 smooth and cause by the electrolytic thin-membrane of PLD preparation Close, researcher also analyzes that show that film composition is able to maintain almost consistent with target component.After charge and discharge cycles, electrolyte Film still keeps homogeneity, and still smooth defect free cell interface structure (electrolyte/anode, electrolyte/cathode) occurs.This Outside, the hull cell prepared by PLD film deposition techniques can be obviously improved the interface impedance (lithium ion in solid electrolyte Conductivity is compared in liquid phase electrolyte or slightly lower, so that ohmic resistance be caused to increase).But pass through the PLD technology The film lithium ion battery (Electrochemistry Communications, 6 (2004) 417-421) of preparation is by the After charge and discharge cycles, capacity is gradually decayed, and discharge capacity only has first time circulation volume after 100 circulations 45%, the mainly Li due to SnO and insertion+Reaction generates Sn-Li alloy and Li2Caused by O.In addition, there is researcher by PLD Be combined from different sputtering technologies and realize continuous coating: i.e. PLD deposits anode LiCoO2, radio frequency and direct magnetic control deposit LiPON, heat Evaporated metal cathode of lithium (Solid State Ionics, 285 (2016) 118-121).Although this combination deposition technique can be with Realize whole vacuum preparation, interfacial contact is good, and cell manufacturing process not ingress of air, but this method is excessively cumbersome, no Conducive to industrialized large-scale production.Furthermore current researcher mostly uses metal when preparing solid-State Thin Film Li-Ion Batteries Lithium is as cathode, but lithium fusing point is lower (180 DEG C), the heatproof (250 with solder reflow technology in micro cell and integrated circuit DEG C) require incompatible, it is easy to form dead lithium in cycle charge-discharge.Furthermore lithium metal needs harshness to oxygen and water vapor sensitive Encapsulation technology keep stablize, seriously constrain the large-scale promotion application of full solid thin film lithium electricity.Therefore, develop a kind of prepare It is technically simple, realize that multiple circulation volume is kept, while meet the miniature full solid thin film lithium of thermal stability high temperature resistant requirement from Sub- battery, is of great significance.
Summary of the invention
Miniature full solid thin film is prepared in situ with PLD in view of the above existing problems in the prior art, the present invention provides a kind of Battery performance and cycle-index can be improved in the method for lithium ion battery, while guaranteeing thermal stability and the welding of miniature lithium electricity Heatproof requirement.
To achieve the goals above, what the present invention used a kind of is prepared in situ miniature full solid thin film lithium-ion electric with PLD The method in pond, comprising the following steps:
1) pretreatment of substrate: silicon dioxide substrates are cleaned up, and dried for standby；
2) metal platinum work the preparation of battery: is sequentially depositing in the silicon dioxide substrates cleaned up in step 1) with PLD Make as electrolyte, graphene as penetration of electrons transition zone and graphite for collector, cobalt acid lithium as anode, LiPON For negative film.
As an improvement, in the step 1), specific cleaning step are as follows:
(i) silicon dioxide substrates are cleaned by ultrasonic 20min in acetone；
(ii) then it is cleaned by ultrasonic 20min in ethanol；
(iii) it is cleaned several times with deionized water.
As an improvement, the preparation of the step 2) battery, specifically includes a) preparation of target and b) produced in situ micro electric Each layer film in pond；
The preparation of a) target:
When preparing electrolyte lithium phosphorous oxynitride using PLD, the target used is by Li3PO4Powder tabletting is sintered；
When depositing cobalt acid lithium as anode, the target used passes through LiCoO2Tabletting sintering is made；
When depositing graphene as penetration of electrons transition zone, the target used is made up of graphene tabletting sintering；
When depositing graphite as negative film, the target used is made up of graphite composite powder tabletting sintering.
As an improvement, each layer film of b) the produced in situ minicell, specifically includes the following steps:
(i) one layer of metal platinum is plated as plus plate current-collecting body using PLD on the silicon wafer after cleaning-drying；
(ii) on same PLD instrument, LiCoO is utilized2Target in-situ deposition anode LiCoO2Film；
(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, graphite is deposited as negative film.
As an improvement, step (ii) specific steps are as follows:
LiCoO2Target is made up of dry-pressing powder in 900 DEG C of sintering 5h, and deposition process is passed through certain oxygen, pressure control In 0.13Pa, 400 DEG C of underlayer temperature；Laser frequency is 3Hz, laser energy density 1.0Jcm-2。
As an improvement, step (iii) specific steps are as follows:
When preparing solid electrolyte LiPON film using PLD technology, Li3PO4Target is made in 600 DEG C of sintering 5h, deposition When be passed through N2, air pressure is in 0.5Pa, laser frequency 6Hz, laser energy density 2.5Jcm-2, room temperature deposition.
As an improvement, step (iv) specific steps are as follows: be filled with protective atmosphere Ar first, air pressure is in 0.5Pa, laser frequency Rate is 3Hz, laser energy density 1.0Jcm-2, room temperature deposition graphene film.
As an improvement, step (v) specific steps are as follows: deposition graphite as negative film when, the atmosphere used for Ar, Air pressure is in 0.1Pa, laser frequency 6Hz, laser energy density 2.0Jcm-2, room temperature deposition.
In addition, the present invention also provides miniature full solid thin film lithium-ion electrics made from a kind of any of the above-described the method Pond.
Compared with prior art, the invention has the following beneficial effects:
1) the miniature solid-State Thin Film Li-Ion Batteries substitute traditional lithium metal as negative film using graphite, avoid Reacting between lithium metal and other metals, while also avoiding the stroke of dead cathode of lithium, substantially increase film all-solid-state The stability of lithium ion battery.
2) using having high conductivity, the graphene that thermal conductivity is good, insensitive to environment, which is introduced by PLD In the material system of pond, it is placed between electrolyte and graphite cathode as penetration of electrons transport layer, it can be achieved that the quick penetration of electronics, The chemical property of All-solid film batteries not only can be improved in this graphene/graphite cathode composite construction, but also guarantees The thermostabilization of hull cell.
3) preparation method is quick and easy, not only avoid with air and moisture, but also optimize solid-state thin-film battery Preparation flow and enhancing circulating battery period.
4) by miniature solid-State Thin Film Li-Ion Batteries prepared by PLD technology be expected to future portable electronic equipment, Defence equipment and microelectromechanical systems (MEMS) etc. have a wide range of applications.
Detailed description of the invention
Fig. 1 is schematic illustration of the present invention using pulse laser deposition；
Fig. 2 is that miniature All-solid film batteries structure section schematic diagram is made in the present invention；
In figure: 1, laser, 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 Black alkene.
Specific embodiment
In order to make the objectives, technical solutions and advantages of the present invention clearer, below by accompanying drawings and embodiments, to this Invention is further elaborated.However, it should be understood that the specific embodiments described herein are merely illustrative of the present invention, The range being not intended to restrict the invention.
Unless otherwise defined, all technical terms and scientific terms used herein are led with technology of the invention is belonged to The normally understood meaning of the technical staff in domain is identical, and term as used herein in the specification of the present invention is intended merely to retouch State the purpose of specific embodiment, it is not intended that in the limitation present invention.
The pulse laser deposition principle used in the method for the present invention, as shown in Figure 1, lens 2 are passed through by laser 1, 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 It is heated using plumage brightness 7, power supply 4 and substrate heater 5, it is ensured that deposition effect, wherein bombardment, deposition process are all in vacuum Room 8 carries out.
Embodiment one
A method of miniature solid-State Thin Film Li-Ion Batteries being prepared in situ with PLD, specifically includes the following steps:
1) pretreatment of substrate:
A) firstly, silicon dioxide substrates 13 are cleaned by ultrasonic, the step of cleaning are as follows: (i) is cleaned by ultrasonic in acetone 20min；(ii) it is cleaned by ultrasonic 20min in ethanol, is then cleaned several times with deionized water again；
2) preparation of target:
Electrolyte Li is prepared using PLD3PO4-xNx(LiPON) when film, the target used is by Li3PO4Powder tabletting is burnt It ties, for positive LiCoO2Film, electron transfer layer graphene and cathode graphite linings, used in target pass through LiCoO2, graphene and graphite composite powder tabletting sintering be made；
3) each layer film of growth in situ minicell:
Miniature All-solid film batteries structure section schematic diagram is as shown in Figure 2:
(i) one layer of metal platinum 12 (deposition thickness 100nm) is plated as anode using PLD on the silicon wafer after cleaning-drying Collector metallic film；
(ii) on same PLD instrument, LiCoO is utilized214 film (thickness of target in-situ deposition anode cobalt acid lithium 200nm)；
Wherein, LiCoO2Target is made up of dry-pressing powder sintering (900 DEG C of sintering 5h), and deposition process is passed through certain oxygen Gas, pressure control is in 0.13Pa, and 400 DEG C of underlayer temperature；Laser frequency is 3Hz, laser energy density 1.0Jcm-2；
(iii) on same PLD instrument, PLD deposition solid electrolyte Li is utilized3PO4-xNx(11 film of LiPON, The film deposition thickness is 1 μm)；
When preparing solid electrolyte LiPON film using PLD technology, target Li3PO4(600 DEG C of sintering 5h), deposition When be passed through N2, air pressure is in 0.5Pa, laser frequency 6Hz, laser energy density 2.5Jcm-2, room temperature deposition；
(iv) on same PLD instrument, 15 film of penetration of electrons transport layer graphene is deposited, with a thickness of 100nm；
It is filled with protective atmosphere Ar first, air pressure is in 0.5Pa, laser frequency 3Hz, laser energy density 1.0Jcm-2, room Temperature deposition；
(v) on same PLD instrument, deposition graphite 10 is used as cathode (graphite linings are with a thickness of 500nm), the atmosphere of use For Ar, air pressure is in 0.1Pa, laser frequency 6Hz, laser energy density 2.0Jcm-2, room temperature deposition.
In whole preparation process, every kind of target is screwed in target button, base substrate also screws in substrate button, closes chamber Door, cavity is vacuumized with mechanical pump and molecular pump.When intracavitary vacuum is evacuated to 10-4Pa is passed through corresponding reaction gas, and adjusts To certain air pressure；Target and substrate rotating switch are opened, target revolving speed is adjusted and is rotated in 120rpm, substrate revolving speed is in 60rpm. Laser energy density and frequency values are inputted on control panel, are opened laser and are started deposition process；After reaching sedimentation time, close Laser and rotating switch are closed, is cooled to room temperature taking-up sample to underlayer temperature, is placed in dry sealer, in case carrying out structure Morphology characterization or electrochemical property test.If not wanting test item, then sample is not taken out, only need to close laser, adjusted Whole next target location and deposition parameter start deposition process, until the preparation of last negative film terminates.
Embodiment two
Comparative test.(iv) step in embodiment one is omitted, (v) step makees following adjustment, remaining step is consistent:
(v) on same PLD instrument, deposit cathode graphite linings (600nm), use atmosphere for Ar, air pressure in 0.1Pa, Laser frequency is 6Hz, laser energy density 2.0Jcm-2, room temperature deposition.
Embodiment three
Comparative test.(v) step in embodiment one is omitted, (iv) step makees following adjustment, remaining step is consistent:
(iv) it on same PLD instrument, deposits negative metal lithium layer film (600nm).Atmosphere is Ar, and air pressure exists 0.1Pa, laser frequency 6Hz, laser energy density 2.0Jcm-2, room temperature deposition.
Example IV
Using the structure and morphology and chemical property of miniature solid-State Thin Film Li-Ion Batteries made from the method for the present invention Characterization:
Using the impedance spectra of ac impedance spectroscopy and charge and discharge electric cabinet test solid film lithium battery, Cyclic voltamogram curve And charging and discharging curve, it is heavy using X-ray diffractometer analysis PLD by scanning electron microscope monitoring cell structure and surface topography Long-pending film phase structure disperses spectrum test interface chemical valence state by X-ray energy to analyze the thermal stability of battery structure.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (3)

1. a kind of method that miniature solid-State Thin Film Li-Ion Batteries are prepared in situ with PLD, which is characterized in that including following step It is rapid:
1) pretreatment of substrate: silicon dioxide substrates (13) are cleaned up, and dried for standby；
2) preparation of battery: metal platinum is sequentially depositing in the silicon dioxide substrates (13) cleaned up in step 1) with PLD (12) it is worn as electrolyte, graphene (15) as electronics as collector, cobalt acid lithium (14) as anode, LiPON (11) Saturating transport layer and graphite (10) are used as negative film；
The preparation of the step 2) battery specifically includes a) preparation of target and b) each layer film of produced in situ minicell；
The preparation of a) target:
When preparing electrolyte lithium phosphorous oxynitride (11) using PLD, the target used is by Li3PO4Powder tabletting is sintered；
When depositing cobalt acid lithium (14) as anode, the target used passes through LiCoO2Tabletting sintering is made；
When depositing graphene (15) as penetration of electrons transport layer, the target used is made up of graphene tabletting sintering；
When depositing graphite (10) as negative film, the target used is made up of graphite composite powder tabletting sintering；
Each layer film of b) the produced in situ minicell, specifically includes the following steps:
(i) one layer of metal platinum (12) is plated as plus plate current-collecting body using PLD on the silicon wafer after cleaning-drying；
(ii) on same PLD instrument, LiCoO is utilized2Target in-situ deposition anode LiCoO2Film；
(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, deposition graphite (10) is used as negative film；
Step (ii) specific steps are as follows:
LiCoO2Target is made up of dry-pressing powder in 900 DEG C of sintering 5h, and deposition process is passed through certain oxygen, and pressure control exists 0.13Pa, 400 DEG C of underlayer temperature；Laser frequency is 3Hz, laser energy density 1.0Jcm-2；
Step (iii) specific steps are as follows:
When preparing solid electrolyte LiPON film using PLD technology, Li3PO4Target is made in 600 DEG C of sintering 5h, logical when deposition Enter N2, air pressure is in 0.5Pa, laser frequency 6Hz, laser energy density 2.5Jcm-2, room temperature deposition；
Step (iv) specific steps are as follows: be filled with protective atmosphere Ar first, air pressure is in 0.5Pa, laser frequency 3Hz, laser Energy density is 1.0Jcm-2, room temperature deposition graphene film；
Step (v) specific steps are as follows: when deposition graphite (10) is used as negative film, for Ar, air pressure exists the atmosphere used 0.1Pa, laser frequency 6Hz, laser energy density 2.0Jcm-2, room temperature deposition.
2. a kind of method that miniature solid-State Thin Film Li-Ion Batteries are prepared in situ with PLD according to claim 1, special Sign is, in the step 1), specific cleaning step are as follows:
(i) silicon dioxide substrates (13) are cleaned by ultrasonic 20min in acetone；
(ii) then it is cleaned by ultrasonic 20min in ethanol；
(iii) it is cleaned several times with deionized water.
3. a kind of using miniature solid-State Thin Film Li-Ion Batteries made from any one of claim 1-2 the method.
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