CN106784988A - A kind of flexible all solid-state thin-film lithium battery and its production method - Google Patents

A kind of flexible all solid-state thin-film lithium battery and its production method Download PDF

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CN106784988A
CN106784988A CN201510824069.0A CN201510824069A CN106784988A CN 106784988 A CN106784988 A CN 106784988A CN 201510824069 A CN201510824069 A CN 201510824069A CN 106784988 A CN106784988 A CN 106784988A
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film layer
film
lithium battery
solid
collector
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陈牧
颜悦
刘伟明
周辰
张晓锋
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BEIJING INSTITUTE OF AERONAUTICAL MATERIALS CHINA AVIATION INDUSTRY GROUP Corp
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BEIJING INSTITUTE OF AERONAUTICAL MATERIALS CHINA AVIATION INDUSTRY GROUP Corp
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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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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 belongs to the all-solid lithium-ion battery technical field of high security energy storage, it is related to a kind of with flexible all solid-state thin-film lithium battery and its production method.Compared to conventional films lithium battery, flexible all solid-state thin-film lithium battery can cycle charge-discharge in bending, kinking, drawing process or under stationary state.The polymer film (100) that cell substrate is used in the present invention is ultra-thin, Ultralight flexible membrane, and the film layer (101) that positive pole is used is amorphous state lithium-containing compound, such a construction increases the energy density of battery.High annealing flow is reduced in production method, barrier layer flow is prepared, the complexity of battery production is simplified.

Description

A kind of flexible all solid-state thin-film lithium battery and its production method
Technical field
The invention belongs to the all-solid lithium-ion battery technical field of high security energy storage, and in particular to the full solid thin film lithium electricity with class two-dimensional structure Pond and its production method.
Background technology
Conventional lithium ion battery is generally basede on liquid organic electrolyte and barrier film, there is potential safety hazard in service life.Substituted using solid electrolyte Electrolyte, development all-solid lithium-ion battery is one of important aspect of solution cell safety hidden danger, it is ensured that battery is being subjected to high-strength impact and strike Under, personnel, equipment are not caused damage.Meanwhile, compared to conventional lithium ion battery, all-solid lithium-ion battery is improving energy density, is increasing Cycle life, widen the interval aspect of operating temperature and also have great development space：Liquid need not be encapsulated, can be using the manufacture or stacked of volume to volume large area Manufacture, improve production efficiency；Leakage and etching problem are avoided, heat endurance is high, simplify battery case, improve energy density；Solid electrolyte electricity Chemical window is wider, can be matched with high-voltage anode material, further hoisting power density and energy density.
Further, with the development of wearable electronic (wrist protector for sports, heart rate band, intelligent watch etc.), the secondary cell of supporting power supply is whole Body is needed during extraneous perturbation (bending, kinking, stretching etc.) or discharge and recharge under stationary state, and not harsh to requirements of installation space, is expected to Really realize man-machine motion compatibility.This requires that battery has the ultrathin flexible architectural feature of class two-dimensional, the full solid thin film lithium with membrane structure Battery is one of alternative.
Phase at the beginning of the nineties in last century, Oak Ridge National Laboratory Bates JB et al. are developed with the lithium phosphate of nitrogen doped as electrolytic thin-membrane All solid-state thin-film lithium battery (33-45 of Bates JB et al., Solid State Ionics 135 (2000)), its R＆D process is almost synchronous with lithium ion battery. Be to improve battery integrated performance index, such as energy density, high rate performance, cycle performance, cell substrate, anode thin film layer, electrolyte thin film layer, Negative film layer have passed through number generation change, also expedite the emergence of and improve various thin film preparation processes, improve preparation efficiency.It is existing all solid state thin at present Film lithium battery be based primarily upon thicker (thickness >=1mm) ceramic substrate (such as silicon, mica, sapphire) and metal substrate (such as stainless steel, titanium, Aluminium, iron, nickel, copper foil) manufacture, reason is the film layer LiCoO that conventional cathode is used2、LiMn2O4、LiFePO4、LiNixCo1-xO2Deng It is required for preparing under heated condition in the original location, or by follow-up 300 DEG C -900 DEG C of high annealing flow, and typically only has these substrates can be in height The lower stable existence of temperature.However, there is problems with this manufacture method：(1) thick and heavy substrate reduces the overall energy density of battery, also limits Use of the battery under Flexible Environment；(2) high annealing flow increased technological process complexity and production cost；(3) moved back to suppress high temperature Elements diffusion, substrate oxidation between substrate that fiery flow causes and anode thin film layer, conventional films lithium battery are needed in substrate and anode thin film layer Between increase metal or insulated barriers layer ((305) part in Fig. 3), increased technological process complexity and production cost.
To sum up, " flexibility " solid lithium battery that a class has layer structure turns into potential product.Such battery need to lift energy using ultrathin flexible substrate Metric density, from novel anode film layer, reduces annealing temperature during the high temperature anneal, and barrier layer is cancelled as far as possible.
The content of the invention
The deficiency that the present invention exists for above-mentioned prior art, it is proposed that flexible all solid-state thin-film lithium battery and its production method：What cell substrate was used Polymer film 100 is used to deposit multi-layer thin film layer, improves battery energy density；The film layer that positive pole is used is amorphous state lithium-containing compound, is reduced High annealing flow, eliminate unnecessary barrier films.The flexible all solid-state thin-film lithium battery that the present invention is provided can be in bending, kinking, drawing During stretching or discharge and recharge under stationary state.The present invention is achieved through the following technical solutions：
A kind of lithium battery, including cell substrate, positive pole, electrolyte, negative pole, collector and seal protection layer, cover collector on cell substrate, Positive pole is covered on collector, electrolyte is covered on positive pole, negative pole (such as Fig. 2) is covered on electrolyte.Described battery is flexible full solid thin film lithium electricity Pond, cell substrate uses polymer film 100, positive pole to use film layer 101, and electrolyte uses film layer 102, and negative pole uses film layer 103, collection Fluid uses film layer 104.
The thickness of the polymer film 100 that cell substrate is used is less than 500 μm, and polymer film 100 includes but is not limited to polyimides PI, poly- second Alkene PE, polyvinylchloride, PEN PEN, polystyrene PS, PVAC polyvinylalcohol, polypropylene PP, polyene hydroxyl POE, Polyamide PA.
The thickness of the film layer 101 that its positive pole is used is less than 10 μm, and film layer 101 uses amorphous state lithium-containing compound, including but not limited to contains There is WO4 2-Tungstates, PO4 3-Phosphate.
The film layer 102 that electrolyte is used, the film layer 103 that negative pole is used, the thickness of the film layer 104 that collector is used is less than 10 μm.
A kind of method of production flexibility all solid-state thin-film lithium battery, comprises the following steps：
The first step, surface preparation is carried out to the polymer film 100 that cell substrate is used；
Second step, both sides cover the film layer 104 that discrete collector is used on polymer film 100；
3rd step, the first side forms the film layer 101 that positive pole is used in the film layer 104 that collector is used；
4th step, is completely covered the film layer 102 of electrolyte use in the film layer 101 that positive pole is used, while the film layer 102 that electrolyte is used The side contacts of film layer 104 second used with collector；
5th step, is completely covered the film layer 103 of negative pole use in the film layer 102 that electrolyte is used, while the film layer 103 that negative pole is used The side contacts of film layer 104 second used with collector；
The process for surface preparation of polymer film 100 is described in the first step：Polymer film 100 is cleaned by under air with vacuum in situ, realizes that surface is put down Integralization, the surface roughness R of polymer film 100 after treatmentaIn below 100nm.
In the film layer 104 that collector described in 3rd step is used the first side formed the process conditions of film layer 101 that positive pole uses for：In vacuum ring After the film layer 104 that collector is used is formed under border, vacuum is not exposed, under 0 DEG C of -100 DEG C of environment temperature, formed just using vacuum deposition method The film layer 101 that pole uses, without subsequent high temperature annealing process.Further, coating process is adjusted using vacuum in situ stressometer, reduces positive pole and adopt The internal stress of film layer 101, it is to avoid flexible all solid-state thin-film lithium battery occurs film separation, failure phenomenon when producing and using.
Described vacuum deposition method includes but is not limited in the following manner：Electron-beam evaporation, thermal evaporation deposition, DC pulse magnetron sputtering deposition, R. f. magnetron sputtering, DC pulse/radio frequency mixing magnetron sputtering deposition, medium frequency magnetron sputtering deposition.
Beneficial effect illustrates novelty of the invention and novelty
Compared with traditional all solid-state thin-film lithium battery and its production method, innovative point of the present invention and advantage are：
(1) flexible all solid-state thin-film lithium battery can cycle charge-discharge in bending, kinking, drawing process or under stationary state；
(2) in flexible all solid-state thin-film lithium battery, the polymer film 100 that cell substrate is used is ultra-thin, Ultralight flexible membrane, Improve the overall energy density of battery；
(3) film layer 101 that positive pole is used is amorphous state lithium-containing compound, and flexible all solid-state thin-film lithium battery is in production process In need not move through high annealing flow, eliminate traditional barrier layer 305 for preventing element counterdiffusion.
Brief description of the drawings
Fig. 1：Flexible all solid-state thin-film lithium battery structural representation in the bent state.Wherein, 100：The polymer film that cell substrate is used.101： The film layer that positive pole is used.102：The film layer that electrolyte is used.103：The film layer that negative pole is used.104：The film layer that collector is used.
Fig. 2：Flexible all solid-state thin-film lithium battery structural representation just produced, under formation state.
Fig. 3：Using conventionally produced all solid-state thin-film lithium battery structural representation.Wherein, 300：Metal foil or potsherd；301：Just Very thin film layer；302：Electrolyte thin film layer；303：Negative film layer；304：Collector；305：Barrier layer.Compared to Fig. 2, obstruct is increased Layer 305.
Fig. 4：Film layer (101) LiFeWO that positive pole is used4X-ray diffraction spectrogram (on), LiFeWO4Target spectrogram (under) and surface Field emission microscope photo (upper left).
Fig. 5：With PI/Mo/LiFeWO4/ LiPON/Li is circulation of the flexible all solid-state thin-film lithium battery of battery structure under smooth and case of bending Charging and discharging curve.
Fig. 6：Film layer 101, electricity that the positive pole of the flexible all solid-state thin-film lithium battery with PET/Cu/FePON/LiPON/Li as battery structure is used The film layer 103 that the film layer 102, negative pole that solution matter is used is used is subject in the case of extraneous tensile stress, compression, the change of battery open circuit voltage.
Fig. 7：With PI/LiCoO2/ LiPON/Li is flexible all solid-state thin-film lithium battery cycle charge-discharge curve, wherein LiCoO2Film is without annealing Treatment.
Specific embodiment
Technical solution of the present invention is further described below with reference to drawings and Examples, it is to be understood that the present invention is not limited to this.
Basic thought of the invention is, in production flexibility all solid-state thin-film lithium battery, to utilize：(1) low mass density, good insulating, ultra-thin, electricity Polymer film 100 and its planarizing process method that pond substrate is used, the film layer 101 that (2) material is used for the positive pole of amorphous state lithium-containing compound And its planarizing preparation method and elimination internal stress method, (3) remove high annealing flow and the preparation flow of barrier layer 305 in process of production.Such as Fig. 1 and claim 2, substrate selection proposed by the present invention are the polymer film 100 of cell substrate use with insulation characterisitic, polymer film Thickness be no more than 500 μm, including polyimides (PI), polyethylene (PE), polyvinyl chloride (PVC), PEN (PEN), Polystyrene (PS), polyvinyl alcohol (PVA), polypropylene (PP), polyene hydroxyl (POE), polyamide (PA).By the various types of materials of following table Mass density is contrasted, it is seen that same volume, the cell substrate use mass of polymer film 100 is only that traditional all solid-state thin-film lithium battery selects metal foil Or the 1/10~1/2 of potsherd 300 (stainless steel, titanium, aluminium, iron, nickel, copper, silicon, mica, sapphire) quality, reduce inert matter Part mass, effectively improves the energy density (Wh/kg) of battery.
Mass density (the g/cm of main substrate3) contrast table
PI PE PVC PEN PS PVA PP POE PA
1.38 0.92 1.40 1.36 1.05 1.27 0.9 0.87 1.14
Stainless steel Titanium Aluminium Iron Nickel Copper Silicon Mica Sapphire
7.9 4.5 2.7 7.8 8.9 8.9 2.33 2.2 4
The selection of film layer 101 that positive pole proposed by the present invention is used includes containing (WO4)2-Tungstates (such as CuWO4、Ag2WO4、LiFeWO4) And (PO4)3-Phosphate (such as FePO4、FePO4-xNx), above-mentioned tungstates, phosphate raw material are synthesized using high temperature solid state reaction, full Sufficient claim 3.The film layer 102 that electrolyte is used, the film layer 103 that negative pole is used, the thickness of the film layer 104 that collector is used is no more than 10 μm, it is capable of achieving claim 4.
Using Fig. 2 production procedures from bottom to top, the specific production method of flexible all solid-state thin-film lithium battery proposed by the present invention is as follows：
To realize claim 5, the preprocess method of polymer film 100 that cell substrate is used for：Successively using absolute ethyl alcohol, deionized water to poly- Compound film is cleaned by ultrasonic, and removes surface organic impurities；Polymer film 100 is put into vacuum chamber, the high-energy band provided using ion gun Charged particle bombards polymer film 100, realizes that vacuum plasma is cleaned, and removes inorganic impurity.Further to increase uniform cleaning efficiency, it is desirable to right Polymer film 100 carries out rotation and surface heating.Characterized by AFM, the surface roughness R of polymer film 100aLess than 50nm.
The film layer 104 that collector is used is deposited directly on the polymer film 100 of cell substrate use, both sides is distributed in, with polymer film There is strong adhesive force, without the structure of barrier layer 305 using traditional all solid-state thin-film lithium battery between 100.The material of film layer 104 that collector is used Selected from one or two in Mo, Au, Ag, Cu, Ni, Co, W, Mn, Fe, the square resistance of film is not higher than 3 ohm-sqs to material.
According to claim 6, the preparation of the film layer 101 that positive pole is used is formed in vacuum chamber, under room temperature state, and deposition process will for right The electron-beam evaporation of 8 descriptions, thermal evaporation deposition, DC pulse magnetron sputtering deposition, r. f. magnetron sputtering, DC pulse/radio frequency is asked to mix Close magnetron sputtering deposition, medium frequency magnetron sputtering deposition.
The surfacing of film layer 101 that positive pole is used, thickness is between 200~4000nm.Characterized by X-ray diffractometer, what positive pole was used Film layer 101 is entirely amorphous structure.Characterized by AFM, the surface roughness R of film layer 101 that positive pole is usedaLess than 20nm Below.Using the laser stress ga(u)ge installed in situ, thin film preparation process is can adjust so that the stress value of film layer 101 that positive pole is used is controlled ± 10 Within MPa, film layer 101 internal stress that positive pole is used that reduces of claim 7 description is met, it is to avoid flexible all solid-state thin-film lithium battery is in life There is the phenomenons such as film separation, failure when producing and using.
In the case that the film layer 101 in the positive pole use described in not allowing proposed with reference to claim 6 is exposed to air ambient, used in positive pole (300 DEG C~900 DEG C) treatment of high annealing flow are needed not move through in film layer 101, the film layer 102, negative pole for sequentially forming electrolyte use is used Film layer 103, packaging protection layer, complete the production of flexible all solid-state thin-film lithium battery.
The film that the electrolyte of film layer 101/ that the positive pole of film layer 104/ that the collector of polymer film 100/ used with cell substrate is used is used is used The layer film layer 103 that uses of 102/ negative pole is structure, and (embodiment 1, battery structure is for the flexible all solid-state thin-film lithium battery of production PI/Mo/LiFeWO4/ LiPON/Li) it is capable of achieving claim 1.Battery first discharge specific capacity is 65.5 μ Ah/cm2.Under formation state, with 1C rate charge-discharges, specific discharge capacity (59.7 μ Ah/cm after 2000 circulations2) keep 91.2%；In the bent state, with 1C multiplying power charge and discharges Electricity, specific discharge capacity (52.5 μ Ah/cm after 1000 circulations2) keep 80.2%.
Embodiment 1
The polymer film 100 that cell substrate is used is the PI films of 6 μm of thickness, after installing protecting tool set-up, is sequentially placed into absolute ethyl alcohol, deionized water Middle to be cleaned by ultrasonic 15 minutes, high-purity argon gas purging is placed in dried process in thermal station.In vacuum chamber, using anode layer ion source ionize argon from Sub (0.09Pa, 800~1000V, 0.1~0.3A) uniform bombardment PI films 10~20 minutes, during bombardment PI films with 5 revs/min just to ion Source rotates.
Using the method for DC pulse magnetron sputtering deposition, 500nm thickness, the Mo film (nothings of the ohm-sq of sheet resistance 2 are directly deposited on PI films Barrier layer 305 need to be considered, as the film layer 104 that collector is used.Mo films can be examined by the adhesive force of 5B.
The film layer 101 that positive pole is used selects LiFeWO4Film, using the method for DC pulse/radio frequency mixing magnetron sputtering deposition, specially： By the lithium carbonate after grinding, iron oxide, tungsten oxide multiple high temp sintering, cold pressing and be made LiFeWO4Target；Using vacuum pump group, by chamber background Vacuum is evacuated to 1.0 × 10-4Below Pa, it is 1 to be passed through flow proportional：1~4：1 argon gas/oxygen mixed gas, it is heavy to be sputtered under 0.1~3Pa air pressure Product LiFeWO4Film, sputtering power is 2~5W/cm2, deposition velocity is 10~200nm/h, LiFeWO4Film thickness is 1000nm.Base Piece using revolution and rotation combination by the way of, with LiFeWO4Target distance is 4~12cm, and substrate temperature is room temperature, and surface is undeformed.In sputtering During, by the laser stress ga(u)ge installed in situ, monitor LiFeWO4Membrane stress value, feeds back to splash-proofing sputtering process parameter (air pressure, power Deng), proof stress value is within ± 10MPa.
X-ray diffraction spectrum as shown in Figure 4 is measured：LiFeWO4Target material composition is consistent with block materials, and LiFeWO4Film is entirely without fixed The amorphous structure of shape, the Flied emission electromicroscopic photograph display smooth densification of film surface, without particle, pin hole.
Under same vacuum environment, high-temperature heat treatment flow is needed not move through, directly in LiFeWO4Film surface, r. f. magnetron sputtering electricity The film layer 102LiPON that solution matter is used, film thickness is no less than 500nm.1000nm thickness, negative pole are prepared using the method for thermal evaporation deposition The film layer 103Li of use.
By forming flexible all solid-state thin-film lithium battery after encapsulation, material and structure are PI/Mo/LiFeWO4/LiPON/Li.Such as Fig. 5, battery is first Specific discharge capacity is 65.5 μ Ah/cm2, having at 3.0V and 1.6V respectively has an obvious discharge platform.Battery under formation state, with 1C Rate charge-discharge, specific discharge capacity keeps the 91.2% of initial specific capacities after 2000 circulations, is 59.7 μ Ah/cm2；In the bent state, with 1C Rate charge-discharge, specific discharge capacity keeps the 80.2% of initial specific capacities after 1000 circulations, is 52.5 μ Ah/cm2。
Embodiment 2
The polymer film 100 that cell substrate is used is the PET of 25 μm of thickness, after installing protecting tool set-up, is sequentially placed into absolute ethyl alcohol, deionized water Middle to be cleaned by ultrasonic 15 minutes, high-purity argon gas purging is placed in dried process in thermal station.In vacuum chamber, using anode layer ion source ionize argon from Sub (0.09Pa, 800~1000V, 0.1~0.3A) uniformly bombards PET film (having stiffened coat side) 10~20 minutes, PET film during bombardment Just ion gun is rotated with 5 revs/min.
Using the method for DC pulse magnetron sputtering deposition, 500nm thickness, the Cu/Au two of the ohm-sq of sheet resistance 1 are directly deposited on a pet film Layer film (without considering barrier layer 305), as the film layer 104 that positive collector is used.Cu films can be examined by the adhesive force of 5B.
The film layer 101FePON films of positive pole use are prepared using the method for DC pulse magnetron sputtering deposition：Ferric phosphate after grinding is repeatedly high Temperature sintering, after increasing carbons conductive agent, high temperature insostatic pressing (HIP) is into ferric phosphate target；Using vacuum pump group, chamber base vacuum is evacuated to 4.0 × 10-4Pa with Under, the high pure nitrogen that flow is 10~30sccm is passed through, the sputtering sedimentation FePON films under 0.1~1Pa air pressure, sputtering power is 5W/cm2, Deposition velocity is 10~100nm/h.Substrate is 6~10cm with ferric phosphate target distance by the way of revolution and rotation are combined, and substrate temperature is room Temperature, surface is undeformed.In sputter procedure, by the laser stress ga(u)ge installed in situ, FePON membrane stress values are monitored, feed back to sputtering work Skill parameter (air pressure, power etc.), proof stress value is within ± 10MPa.The smooth densification of film surface, without particle, pin hole.
Under same vacuum environment, high annealing flow is needed not move through, directly in FePON film surfaces, r. f. magnetron sputtering electrolyte The film layer 102LiPON of use, film thickness is no less than 500nm.1000nm thickness, negative pole use are prepared using the method for thermal evaporation deposition Film layer 103Li.
By forming flexible all solid-state thin-film lithium battery after encapsulation, material and structure are PET/Cu-Au/FePON/LiPON/Li.Battery can be close 180 ° of bendings are lower for light emitting diode stable power-supplying.On homemade Apparatus for Bending at low-temp (Fig. 6), battery is by positive (towards pellicular front bending) and anti- (bent towards air surface) to bending, film is correspondingly subject to compression and tensile stress, when radius of curvature is 24.2mm/12.1mm, from the side Battery (battery 76mm long) is bent into semicircle/full circle shape, and in whole test process, radius of curvature is down to 10mm from 55mm, and being pressurized should Within 2mV (0.13%)/5mV (0.31), satisfaction is powered in the bent state for power/tensile stress cell voltage change.
Embodiment 3
The polymer film 100 that cell substrate is used is the PI films of 6 μm of thickness, after installing protecting tool set-up, is sequentially placed into absolute ethyl alcohol, deionized water Middle to be cleaned by ultrasonic 15 minutes, high-purity argon gas purging is placed in dried process in thermal station.In vacuum chamber, using anode layer ion source ionize argon from Sub (0.09Pa, 800~1000V, 0.1~0.3A) uniform bombardment PI films 10~20 minutes, during bombardment PI films with 5 revs/min just to ion Source rotates.
Using the method for DC pulse magnetron sputtering deposition, 500nm thickness, the Mo film (nothings of 2 ohm/square meter of sheet resistance are directly deposited on PI films Barrier layer 305 need to be considered), as the film layer 104 that positive collector is used.Mo films can be examined by the adhesive force of 5B.
The film layer 101LiCoO of positive pole use is prepared using the method for DC pulse magnetron sputtering deposition2Film：Using vacuum pump group, by chamber sheet Bottom vacuum is evacuated to 4.0 × 10-4Below Pa, it is 2 to be passed through flow proportional：1~3：1 argon gas/oxygen mixed gas, sputter under 0.1~3Pa air pressure Deposition LiCoO2Film, sputtering power is 1W/cm2~3W/cm2, deposition velocity is 10~200nm/h, LiCoO2Film thickness is 1000nm. Substrate using revolution and rotation combination by the way of, with LiCoO2Target distance is 4~12cm, and substrate temperature is room temperature, and surface is undeformed.In sputtering During, by the laser stress ga(u)ge installed in situ, monitor LiCoO2Membrane stress value, feeds back to splash-proofing sputtering process parameter, proof stress value ± Within 10MPa.The smooth densification of film surface, without particle, pin hole.
Under same vacuum environment, not by high annealing flow, directly in LiCoO2Film surface, r. f. magnetron sputtering electrolyte The film layer 102LiPON of use, film thickness is no less than 500nm.1000nm thickness, negative pole use are prepared using the method for thermal evaporation deposition Film layer 103Li.
By forming flexible all solid-state thin-film lithium battery after encapsulation, material and structure are PI/Mo/LiCoO2/LiPON/Li.Such as Fig. 7, battery is first Specific discharge capacity is 63.1 μ Ah/cm2, and discharge off platform, reason is LiCoO2 films different from the amorphous state LiFeWO4 films that the present invention is used, Need to could occur discharge platform under crystalline state by high annealing flow.The battery after 10 times circulate, discharges under formation state Special capacity fade decays to less than 50% to 93.1% (1C discharge and recharges) of initial specific capacities after 100 circulations.The structure of comparison diagram 5 is The flexible all solid-state thin-film lithium battery of PI/Mo/LiFeWO4/LiPON/Li, specific discharge capacity keeps initial specific capacities after its 2000 times circulations 91.2%.Therefore, the selection of film layer 101 that positive pole is used contains the tungstates of (WO4) 2-, the phosphate of (PO4) 3- has advantage.

Claims (8)

1. a kind of lithium battery, including cell substrate, positive pole, electrolyte, negative pole, collector and seal protection layer, cover collector on cell substrate, positive pole is covered on collector, and electrolyte is covered on positive pole, and negative pole is covered on electrolyte, it is characterised in that：Described battery is flexible all solid-state thin-film lithium battery, cell substrate uses polymer film (100), positive pole uses film layer (101), electrolyte uses film layer (102), negative pole uses film layer (103), and collector uses film layer (104).
2. a kind of lithium battery according to claim 1, it is characterised in that：The thickness of the polymer film (100) that its cell substrate is used is less than 500 μm, and polymer film (100) includes but is not limited to polyimides (PI), polyethylene (PE), polyvinyl chloride (PVC), PEN (PEN), polystyrene (PS), polyvinyl alcohol (PVA), polypropylene (PP), polyene hydroxyl (POE), polyamide (PA).
3. a kind of lithium battery according to claim 1, it is characterised in that：Film layer (101) thickness that its positive pole is used is less than 10 μm, and film layer (101) uses amorphous state lithium-containing compound, including but not limited to contains (WO4)2-Tungstates, (PO4)3-Phosphate.
4. according to a kind of lithium battery of one of claim 1-3, it is characterised in that：The film layer (102) that electrolyte is used, the film layer (103) that negative pole is used, the thickness of the film layer (104) that collector is used is less than 10 μm.
5. a kind of method of production flexibility all solid-state thin-film lithium battery, comprises the following steps：
The first step, surface preparation is carried out to the polymer film (100) that cell substrate is used；
Second step, both sides cover the film layer (104) that discrete collector is used on polymer film (100)；
3rd step, the first side forms the film layer (101) that positive pole is used in the film layer (104) that collector is used；
4th step, the film layer (102) of electrolyte use is completely covered in the film layer (101) that positive pole is used, while the side contacts of film layer (104) second that the film layer (102) that electrolyte is used is used with collector；
5th step, the film layer (103) of negative pole use is completely covered in the film layer (102) that electrolyte is used, while the side contacts of film layer (104) second that the film layer (103) that negative pole is used is used with collector；Characterized in that, polymer film described in the first step (100) process for surface preparation is：Polymer film (100) is cleaned by under air with vacuum in situ, realizes surface flattening, polymer film (100) surface roughness R after treatmentaIn below 100nm.
6. a kind of method of production flexibility all solid-state thin-film lithium battery as claimed in claim 5, characterized in that, in the film layer (104) that uses of the collector described in the 3rd step the first side formed the process conditions of the film layer (101) that positive pole is used for：After forming the film layer (104) that collector is used under vacuum conditions, vacuum is not exposed, under 0 DEG C of -100 DEG C of environment temperature, the film layer (101) that positive pole is used is formed using vacuum deposition method, without subsequent high temperature annealing process.
7. a kind of method of production flexibility all solid-state thin-film lithium battery as claimed in claim 6, it is characterized in that, coating process is adjusted using vacuum in situ stressometer, reduce film layer (101) internal stress that positive pole is used, it is to avoid flexible all solid-state thin-film lithium battery occurs film separation, failure phenomenon when producing and using.
8. a kind of method of production flexibility all solid-state thin-film lithium battery as claimed in claim 6, it is characterised in that described thin film layer method includes but is not limited in the following manner：Electron-beam evaporation, thermal evaporation deposition, DC pulse magnetron sputtering deposition, r. f. magnetron sputtering, DC pulse/radio frequency mixing magnetron sputtering deposition, medium frequency magnetron sputtering deposition.
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