A kind of LiMn2O4/ doping NASICON/Li4Ti5O12All-solid film batteries and preparation method
Technical field
The present invention relates to a kind of high-performance All-solid film batteries manufacture method technical field.
Background technology
Lithium ion battery have volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, have extended cycle life, the high absolute advantage of power density, have in portable power source market, the whole world and exceed 30,000,000,000 dollar/year shares and exceed well over the market share of other batteries, it is the electrochmical power source [Wu Yuping most with market development prospect, Wan Chunrong, Jiang Changyin, lithium rechargeable battery, Beijing: Chemical Industry Press, 2002.]. Lithium rechargeable battery major part employing both at home and abroad is liquid electrolyte at present, liquid lithium ionic cell has some unfavorable factors, as: liquid organic electrolyte is likely to reveal, blast at too high a temperature thus causing security incident, it is impossible to be applied in some occasions that security requirement is high; Liquid electrolyte lithium ion battery ubiquity Capacity fading problem, uses after a period of time due to electrode active material dissolving in the electrolyte, reaction and degradation failure [Z.R.Zhang, Z.L.Gong, andY.Yang, J.Phys.Chem.B, 108,2004,17546.]. And all-solid-state battery safety is high, be substantially free of Capacity fading, solid electrolyte also acts the effect of barrier film, simplifies the structure of battery; Additionally, due to without completely cutting off air, also simplify the requirement to equipment in production process, the configuration design of battery is also more convenient and flexible, and [Wen Zhaoyin, Zhu Xiujian, permitted hero dawn etc., the research of solid state secondary battery, the 12nd Chinese solid-state ionics academic meeting paper collection, 2004.].
In all-solid lithium-ion battery, carrier migration rate in solid electrolyte is often far smaller than the ion diffusion rates in the electric charge transfer of electrode surface and positive electrode and becomes the rate determining step in whole electrode reaction kinetics, develops that to have the inorganic solid electrolyte of higher li ionic conductivity be build the key place of high performance lithium ion battery. But bad luck be up to the present can in atmosphere more stable, there is wider electrochemical window, ionic conductivity that the inorganic solid electrolyte of relatively reasonable preparation cost can reach is generally 10-5-10-7S.cm-1Left and right, the solid electrolyte sheet of general thickness is difficult to meet the Essential Performance Requirements of solid lithium battery. And commercial or study more anode material for lithium-ion batteries such as LiFePO4, LiMn2O4 etc. there is very low electronic conductivity and ionic conductivity, the battery that simple solid electrode sheet is constituted makes the overall performance of battery be subject to very big restriction.
And solid-State Thin Film Li-Ion Batteries is microminiaturized all-solid lithium-ion battery, its positive electrode-solid electrolyte-negative material is all the thin film of several microns to tens microns, it is possible to overcome electronic conductivity and ionic conductivity that positive electrode is low and the adverse effect that battery performance is brought by the low lithium ion conductivity of solid electrolyte. Solid-State Thin Film Li-Ion Batteries has a wide range of applications: including: miniature robot surveillance plane electrical source of power (includes camera head power supply), multiple microsensor, CMOS integrated circuit, smart card (SmartCard), portable set etc., thus becoming the focus of research and development side.
The preparation of current all solid-state thin-film lithium battery substantially adopts the method [Y.Iriyama such as r. f. magnetron sputtering, pulsed laser deposition, PECVD, M.Yokoyama, C.Yada, etal.Electrochem.SolidStateLett., 2004,7 (10): A340.]. These method equipment investments are huge, complex process, with high costs. Spray pyrolysis is also a kind of effective means depositing thin film. Spray pyrolysis have do not need vacuum environment, technical process is simple, equipment investment is few, has the ability preparing large area film.
But adopt the method to prepare all solid-state thin-film lithium battery and remain in the problem much waiting to solve:
1, film lithium cell at least needs 3 layer films, i.e. positive electrode-solid electrolyte-negative material, and the key factor affecting its overall performance is the tight of interface between layers and matching degree. The common underlayer temperature of spray pyrolysis is not high and kinetic energy limited (can not show a candle to magnetron sputtering or pulse laser) that carrier gas brings to microgranule cause layer and bed boundary closely and matching degree not high, therefore the grain boundary resistance at interface is higher, it will have a strong impact on the overall performance of battery.
2, the solid electrolyte material that prepared by applicable spray pyrolysis is less, and the solid electrolyte LiPON (N doping lithium phosphate) having better performance at present is prepared only by magnetron sputtering.
3, the hull cell formed after spraying is the presoma of material, positive electrode, negative material and dielectric substrate form the thing of oneself and also need to follow-up heat treatment mutually, but the synthesis temperature of these materials is often inconsistent, therefore easily cause reacting to each other and the underburnt of the burning of some component or some component between presoma composition.
Spray pyrolysis is prepared All-solid film batteries and has been carried out some explorations by current R&D Professional, if application number is the Chinese invention patent of 200910044488.7, such as document [P.FRAGNAND, RNAGARAJAN., D.VUJIC, J.PowerSources, 1995,54:362.], the negative or positive electrode sheet of the monolithic film membrane battery substantially still prepared with traditional spray pyrolysis method or electrolyte sheet, and it is difficult to overcome electrode slice and electrolyte sheet interface conductance difficulty each other, have impact on battery overall performance.
Summary of the invention
The present invention proposes a kind of comprehensive employing electrostatic spray pyrolysis according to technical background and HVAF builds film all-solid-state lithium ion battery LiMn layer by layer2O4/ doping NASICON/Li4Ti5O12Method. adopt spray pyrolysis to add between spray gun and substrate the means of electrostatic high-pressure carry out jet deposition both positive and negative polarity active material simultaneously, due to positive electrode material layer | solid electrolyte layer, solid electrolyte layer | the interface impedance between negative electrode material layer is the main resistance place hindering all-solid-state battery performance, the common underlayer temperature of spray pyrolysis is not high and kinetic energy that carrier gas brings to microgranule is limited, therefore HVAF deposition solid electrolyte is adopted, solid electrolyte is at high temperature made to be in semi-molten state high-speed impact on positive electrode material layer, interface is in close contact, greatly reduce the interface impedance between solid electrolyte and positive and negative pole material layer, additionally when depositing both positive and negative polarity active material presoma, adopt the electrolytical mode of HVAF deposition solid simultaneously, common contact interface is become whole contact layer, thus 2 contact interfaces of | solid electrolyte and negative material | solid electrolyte become not having obvious contact interface by positive electrode, greatly reduce positive and negative pole material | the interface impedance of solid electrolyte, and the ionic conductivity of positive and negative pole material can be improved significantly, thus improving the comprehensive electrochemical of all-solid-state battery.
This invention address that the method that above-mentioned technical problem adopts, it is characterised in that specifically comprise the following steps that
1) substrate is positioned over 200-500 DEG C of heating work plate surface of constant temperature, by substrate surface ground connection, liquid spray gun A connects precursor aqueous solution I, spray gun A distance heating work plate surface vertical dimension 8-20cm, forms the 50-85 �� of angle of cut with heating work plate surface and connects negative 40-80kV voltage simultaneously;
2) carrier gas that pressure is 10-30Kpa is acted on spray gun A, spray gun A atomized spray precursor aqueous solution I to substrate, sustained firing 1-30 minute, injection flow is 1-10mL/min;
3) while spray gun A starts injection, solid electrolyte is loaded on the hopper of supersonic spray gun B, light spray gun B burning combustible gas, regulate the ratio of fuel gas and oxygen, flame gun B is made to send bright blue light, the flame end distance heating work plate surface vertical dimension 15-30cm that flame gun B produces, flame gun B and heating work plate surface form the 70-90 �� of angle of cut and spray solid electrolyte to substrate, injection flow is 10-30mg/min, duration be spray gun A terminate injection after fill-before-fire 2-10 minute;
4) spray gun B injection is kept, precursor aqueous solution II is connected with spray gun A, spray gun A distance heating work plate surface vertical dimension 8-20cm, spray gun A forms the 50-85 �� of angle of cut with heating work plate surface, again negative 40-80kV voltage is applied between spray gun A and substrate, the carrier gas of pressure 10-30Kpa is acted on spray gun A, spray gun A atomized spray precursor aqueous solution II is to substrate, the flow of precursor aqueous solution II is 1-10mL/min, injecting time continues 5-30 minute, and spray gun A terminates the injection of spray gun B while terminating injection;
5) AEI After End of Injection, after the cooling of working plate surface to be heated, puts into Muffle furnace constant temperature 5-10 hour at 600-900 DEG C by the substrate after processing, namely prepares all solid-state thin-film lithium battery.
Precursor aqueous solution I is: concentration is the manganese oxalate of 0.2-2mol/L, concentration is 0.1-1mol/L Quilonorm (SKB) and mass percent concentration is the adjuvant water solution of 0.1-5wt%;This auxiliary agent is the one in the PVAC polyvinylalcohol of ethylene glycol monomethyl ether, n-amyl alcohol, mean molecule quantity < 5000.
Solid electrolyte is doping NASICON solid electrolyte, and concrete preparation method will be for will meet formula Li1+2x+2yAlxMgyTi2-x-ySixP3-xO12, x=0.1-0.5; Y=0.1-0.5; Tetraethyl orthosilicate TEOS, Al2O3��MgO��TiO2��NH4H2PO4��Li2CO3Homogeneous phase mixing, add 95% ethanol of 2%-6%, with rotating speed ball milling 10-30 hour of 200-400 rev/min in ball mill, ball milling dries 10-20 hour after terminating in 60 DEG C of-80 DEG C of vacuum drying ovens (vacuum is at 10Pa-100Pa), grinding in alms bowl at Achates after taking-up and re-grind 10-30 minute, the powder body after grinding is incubated with the ramp to 600-800 DEG C of 5-10 DEG C/min and within 5-10 hour, makes solid electrolyte powder body.
Precursor aqueous solution II consists of: acetic acid and the mass percent concentration of concentration is 0.1-1.6mol/L Quilonorm (SKB), concentration to be the tetrabutyl titanate of 0.125-2mol/L, concentration be 0.1-1mol/L are the adjuvant water solution of 0.1-5wt%; This auxiliary agent is the one in the PVAC polyvinylalcohol of ethylene glycol monomethyl ether, n-amyl alcohol, mean molecule quantity < 5000.
Substrate is the one in copper sheet, silicon chip, nickel sheet.
This fuel gas is the one in hydrogen, acetylene and butane.
Compared with prior art, it is an advantage of the current invention that to adopt liquid spray gun electrostatic spray pyrolysis both positive and negative polarity active material presoma, HVAF electrolyte material layer builds film all-solid-state lithium ion battery LiMn layer by layer2O4/ doping NASICON/Li4Ti5O12. voltage between substrate and spray gun, up to 40-80kV, drastically increases the close contact between positive electrode and collector and negative material and electrolyte, HVAF particle velocity is fast, and particle is in semi-molten state can form close contact with substrate, adopt electrostatic spray pyrolysis and HVAF to deposit the mode of both positive and negative polarity active material presoma and solid electrolyte simultaneously simultaneously, common contact interface is become whole contact layer, thus 2 contact interfaces of | solid electrolyte and negative material | solid electrolyte become not having obvious contact interface by positive electrode, greatly reduce positive and negative pole material | the interface impedance of solid electrolyte, and avoid electrolyte inconsistent with the synthesis temperature of positive and negative pole material and cause underburnt or burning, and the ionic conductivity of positive and negative pole material can be improved significantly, thus increasing substantially the comprehensive electrochemical of all-solid-state battery.
Accompanying drawing explanation
Fig. 1 is embodiment 2 50 cyclic discharge capacity decay patterns of speed discharge and recharge with 0.5 multiplying power on battery performance test instrument.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: by 0.1molTEOS, 0.05molAl2O3��0.1molMgO��1.8molTiO2��2.9molNH4H2PO4��0.7molLi2CO3Homogeneous phase mixing, add 95% ethanol of 2%, with the rotating speed ball milling 10 hours of 250 revs/min in ball mill, ball milling dries 10 hours after terminating in 60 DEG C of vacuum drying ovens (vacuum 20Pa), grinding in alms bowl at Achates after taking-up and re-grind 30 minutes, the powder body after grinding is incubated with the ramp to 700 DEG C of 5 DEG C/min and makes solid electrolyte powder body in 6 hours; Copper sheet is positioned over 250 DEG C of heating work plate surfaces of constant temperature, by copper sheet surface earthing, liquid spray gun A connects precursor aqueous solution I, solution composition is: concentration is the manganese oxalate of 0.6mol/L, concentration is the aqueous solution of 0.3mol/L Quilonorm (SKB) and ethylene glycol monomethyl ether that mass percent concentration is 0.2wt%, spray gun A distance heating work plate surface vertical dimension 8cm, forms 70 �� of angles of cut with heating work plate surface and connects negative 40kV voltage simultaneously;The carrier gas that pressure is 10Kpa is acted on spray gun A, spray gun A atomized spray precursor aqueous solution I to copper sheet, sustained firing 30 minutes, injection flow is 3mL/min; While spray gun A starts injection, solid electrolyte is loaded on the hopper of supersonic spray gun B, light spray gun B burning acetylene, regulate the ratio of acetylene and oxygen, flame gun B is made to send bright blue light, the flame end distance heating work plate surface vertical dimension 20cm that flame gun B produces, flame gun B and heating work plate surface form 80 �� of angles of cut and spray solid electrolyte to copper sheet, injection flow is 10mg/min, and duration is that spray gun A terminates fill-before-fire 2 minutes after injection; While keeping spray gun B injection, connecting precursor aqueous solution II with spray gun A, solution composition is: concentration is the Quilonorm (SKB) Li (CH of 0.4mol/L3COO), concentration is the tetrabutyl titanate Ti (OC of 0.5mol/L4H9)4, concentration be the acetic acid CH of 0.3mol/L3The aqueous solution of the PVAC polyvinylalcohol of COOH and mean molecule quantity < 5000 that mass percent concentration is 0.2wt%, spray gun A distance heating work plate surface vertical dimension 10cm, spray gun A forms 80 �� of angles of cut with heating work plate surface, again negative 40kV voltage is applied between spray gun A and copper sheet, the carrier gas of pressure 15Kpa is acted on spray gun A, spray gun A atomized spray precursor aqueous solution II is to copper sheet, the flow of precursor aqueous solution II is 2mL/min, injecting time continues 5 minutes, terminates the injection of spray gun B simultaneously; AEI After End of Injection, after the cooling of working plate surface to be heated, puts into Muffle furnace constant temperature 5 hours at 600 DEG C by the copper sheet after processing, namely prepares all solid-state thin-film lithium battery.
Embodiment 2: by 0.2molTEOS, 0.1molAl2O3��0.5molMgO��1.3molTiO2��2.8molNH4H2PO4��1.2molLi2CO3Homogeneous phase mixing, add 95% ethanol of 4%, with the rotating speed ball milling 30 hours of 200 revs/min in ball mill, ball milling dries 20 hours after terminating in 80 DEG C of vacuum drying ovens (vacuum 10Pa), grinding in alms bowl at Achates after taking-up and re-grind 20 minutes, the powder body after grinding is incubated with the ramp to 600 DEG C of 10 DEG C/min and makes solid electrolyte powder body in 8 hours; Nickel sheet is positioned over 200 DEG C of heating work plate surfaces of constant temperature, by nickel sheet surface earthing, liquid spray gun A connects precursor aqueous solution I, solution composition is: concentration is the manganese oxalate of 2mol/L, concentration is the aqueous solution of 1mol/L Quilonorm (SKB) and ethylene glycol monomethyl ether that mass percent concentration is 3wt%, spray gun A distance heating work plate surface vertical dimension 20cm, forms 50 �� of angles of cut with heating work plate surface and connects negative 60kV voltage simultaneously; The carrier gas that pressure is 20Kpa is acted on spray gun A, spray gun A atomized spray precursor aqueous solution I on nickel sheet, sustained firing 20 minutes, injection flow is 10mL/min; While spray gun A starts injection, solid electrolyte is loaded on the hopper of supersonic spray gun B, light spray gun B burning hydrogen, regulate the ratio of hydrogen and oxygen, flame gun B is made to send bright blue light, the flame end distance heating work plate surface vertical dimension 30cm that flame gun B produces, flame gun B and heating work plate surface form 70 �� of angles of cut and spray solid electrolyte to nickel sheet, injection flow is 30mg/min, and duration is that spray gun A terminates fill-before-fire 6 minutes after injection; While keeping spray gun B injection, connecting precursor aqueous solution II with spray gun A, solution composition is: concentration is the Quilonorm (SKB) Li (CH of 0.8mol/L3COO), concentration is the tetrabutyl titanate Ti (OC of 1mol/L4H9)4, concentration be the acetic acid CH of 0.5mol/L3The aqueous solution of the PVAC polyvinylalcohol of COOH and mean molecule quantity < 5000 that mass percent concentration is 4wt%, spray gun A distance heating work plate surface vertical dimension 8cm, spray gun A forms 85 �� of angles of cut with heating work plate surface, again negative 60kV voltage is applied between spray gun A and nickel sheet, the carrier gas of pressure 20Kpa is acted on spray gun A, spray gun A atomized spray precursor aqueous solution II is on nickel sheet, the flow of precursor aqueous solution II is 1mL/min, injecting time continues 10 minutes, terminates the injection of spray gun B simultaneously;AEI After End of Injection, after the cooling of working plate surface to be heated, puts into Muffle furnace constant temperature 10 hours at 700 DEG C by the nickel sheet after processing, namely prepares all solid-state thin-film lithium battery.
Embodiment 3: by 0.3molTEOS, 0.15molAl2O3��0.2molMgO��1.5molTiO2��2.7molNH4H2PO4��1molLi2CO3Homogeneous phase mixing, add 95% ethanol of 6%, with the rotating speed ball milling 20 hours of 300 revs/min in ball mill, ball milling dries 15 hours after terminating in 70 DEG C of vacuum drying ovens (vacuum 50Pa), grinding in alms bowl at Achates after taking-up and re-grind 10 minutes, the powder body after grinding is incubated with the ramp to 800 DEG C of 5 DEG C/min and makes solid electrolyte powder body in 10 hours; Silicon chip is positioned over 500 DEG C of heating work plate surfaces of constant temperature, by silicon chip surface ground connection, liquid spray gun A connects precursor aqueous solution I, solution composition is: concentration is the manganese oxalate of 1.6mol/L, concentration is 0.8mol/L Quilonorm (SKB) and n-amyl alcohol aqueous solution that mass percent concentration is 4wt%, spray gun A distance heating work plate surface vertical dimension 10cm, forms 85 �� of angles of cut with heating work plate surface and connects negative 80kV voltage simultaneously; The carrier gas that pressure is 30Kpa is acted on spray gun A, spray gun A atomized spray precursor aqueous solution I to silicon chip, sustained firing 10 minutes, injection flow is 5mL/min; While spray gun A starts injection, solid electrolyte is loaded on the hopper of supersonic spray gun B, light spray gun B burning butane, regulate the ratio of butane and oxygen, flame gun B is made to send bright blue light, the flame end distance heating work plate surface vertical dimension 15cm that flame gun B produces, flame gun B and the heating work plate surface shape angle of cut in 90 �� spray solid electrolyte to silicon chip, injection flow is 10mg/min, and duration is that spray gun A terminates fill-before-fire 8 minutes after injection; While keeping spray gun B injection, connecting precursor aqueous solution II with spray gun A, solution composition is: concentration is the Quilonorm (SKB) Li (CH of 1.2mol/L3COO), concentration is the tetrabutyl titanate Ti (OC of 1.5mol/L4H9)4, concentration be the acetic acid CH of 1mol/L3The aqueous solution of COOH and ethylene glycol monomethyl ether that mass percent concentration is 5wt%, spray gun A distance heating work plate surface vertical dimension 20cm, spray gun A forms 75 �� of angles of cut with heating work plate surface, again negative 80kV voltage is applied between spray gun A and silicon chip, the carrier gas of pressure 30Kpa acts on spray gun A, and spray gun A atomized spray precursor aqueous solution II is to silicon chip, and the flow of precursor aqueous solution II is 10mL/min, injecting time continues 20 minutes, terminates the injection of spray gun B simultaneously; AEI After End of Injection, after the cooling of working plate surface to be heated, puts into Muffle furnace constant temperature 7 hours at 800 DEG C by the silicon chip after processing, namely prepares all solid-state thin-film lithium battery.
Embodiment 4: by 0.5molTEOS, 0.25molAl2O3��0.1molMgO��1.4molTiO2��2.5molNH4H2PO4��1.1molLi2CO3Homogeneous phase mixing, add 95% ethanol of 2%, with the rotating speed ball milling 15 hours of 400 revs/min in ball mill, ball milling dries 15 hours after terminating in 60 DEG C of vacuum drying ovens (vacuum 100Pa), grinding in alms bowl at Achates after taking-up and re-grind 20 minutes, the powder body after grinding is incubated with the ramp to 650 DEG C of 8 DEG C/min and makes solid electrolyte powder body in 5 hours; Copper sheet is positioned over 400 DEG C of heating work plate surfaces of constant temperature, by copper sheet surface earthing, liquid spray gun A connects precursor aqueous solution I, solution composition is: concentration is the manganese oxalate of 0.2mol/L, concentration is 0.1mol/L Quilonorm (SKB) and n-amyl alcohol aqueous solution that mass percent concentration is 5wt%, spray gun A distance heating work plate surface vertical dimension 15cm, forms 65 �� of angles of cut with heating work plate surface and connects negative 40kV voltage simultaneously;The carrier gas that pressure is 10Kpa is acted on spray gun A, spray gun A atomized spray precursor aqueous solution I to copper sheet, sustained firing 1 minute, injection flow is 8mL/min; While spray gun A starts injection, solid electrolyte is loaded on the hopper of supersonic spray gun B, light spray gun B burning hydrogen, regulate the ratio of hydrogen and oxygen, flame gun B is made to send bright blue light, the flame end distance heating work plate surface vertical dimension 20cm that flame gun B produces, flame gun B and heating work plate surface form 70 �� of angles of cut and spray solid electrolyte to copper sheet, injection flow is 20mg/min, and duration is that spray gun A terminates fill-before-fire 10 minutes after injection; While keeping spray gun B injection, connecting precursor aqueous solution II with spray gun A, solution composition is: concentration is the Quilonorm (SKB) Li (CH of 1.6mol/L3COO), concentration is the tetrabutyl titanate Ti (OC of 2mol/L4H9)4, concentration be the acetic acid CH of 0.1mol/L3The aqueous solution of the PVAC polyvinylalcohol of COOH and mean molecule quantity < 5000 that mass percent concentration is 2wt%, spray gun A distance heating work plate surface vertical dimension 15cm, spray gun A forms 50 �� of angles of cut with heating work plate surface, again negative 40kV voltage is applied between spray gun A and copper sheet, the carrier gas of pressure 10Kpa is acted on spray gun A, spray gun A atomized spray precursor aqueous solution II is to copper sheet, the flow of precursor aqueous solution II is 8mL/min, injecting time continues 30 minutes, terminates the injection of spray gun B simultaneously; AEI After End of Injection, after the cooling of working plate surface to be heated, puts into Muffle furnace constant temperature 8 hours at 900 DEG C by the copper sheet after processing, namely prepares all solid-state thin-film lithium battery.
Embodiment 5: by 0.2molTEOS, 0.1molAl2O3��0.3molMgO��1.5molTiO2��2.8molNH4H2PO4��1molLi2CO3Homogeneous phase mixing, add 95% ethanol of 4%, with the rotating speed ball milling 10 hours of 250 revs/min in ball mill, ball milling dries 10 hours after terminating in 80 DEG C of vacuum drying ovens (vacuum 80Pa), grinding in alms bowl at Achates after taking-up and re-grind 10 minutes, the powder body after grinding is incubated with the ramp to 750 DEG C of 7 DEG C/min and makes solid electrolyte powder body in 6 hours; Silicon chip is positioned over 300 DEG C of heating work plate surfaces of constant temperature, by silicon chip surface ground connection, liquid spray gun A connects precursor aqueous solution I, solution composition is: concentration is the manganese oxalate of 0.8mol/L, concentration is the PVAC polyvinylalcohol aqueous solution of 0.4mol/L Quilonorm (SKB) and mean molecule quantity < 5000 that mass percent concentration is 0.1wt%, spray gun A distance heating work plate surface vertical dimension 8cm, forms 70 �� of angles of cut with heating work plate surface and connects negative 60kV voltage simultaneously; The carrier gas that pressure is 20Kpa is acted on spray gun A, spray gun A atomized spray precursor aqueous solution I to silicon chip, sustained firing 10 minutes, injection flow is 1mL/min; While spray gun A starts injection, solid electrolyte is loaded on the hopper of supersonic spray gun B, light spray gun B burning acetylene, regulate the ratio of acetylene and oxygen, flame gun B is made to send bright blue light, the flame end distance heating work plate surface vertical dimension 30cm that flame gun B produces, flame gun B and heating work plate surface form 80 �� of angles of cut and spray solid electrolyte to silicon chip, injection flow is 30mg/min, and duration is that spray gun A terminates fill-before-fire 2 minutes after injection; While keeping spray gun B injection, connecting precursor aqueous solution II with spray gun A, solution composition is: concentration is the Quilonorm (SKB) Li (CH of 0.1mol/L3COO), concentration is the tetrabutyl titanate Ti (OC of 0.125mol/L4H9)4, concentration be the acetic acid CH of 0.5mol/L3The aqueous solution of COOH and n-amyl alcohol that mass percent concentration is 0.1wt%, spray gun A distance heating work plate surface vertical dimension 20cm, spray gun A forms 65 �� of angles of cut with heating work plate surface, again negative 60kV voltage is applied between spray gun A and silicon chip, the carrier gas of pressure 15Kpa acts on spray gun A, and spray gun A atomized spray precursor aqueous solution II is to silicon chip, and the flow of precursor aqueous solution II is 6mL/min, injecting time continues 20 minutes, terminates the injection of spray gun B simultaneously;AEI After End of Injection, after the cooling of working plate surface to be heated, puts into Muffle furnace constant temperature 10 hours at 600 DEG C by the silicon chip after processing, namely prepares all solid-state thin-film lithium battery.