CN102299383B - Mist pyrolysis preparation method of all-solid-state film lithium battery - Google Patents
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Abstract
The invention discloses a mist pyrolysis preparation method of an all-solid-state film lithium battery. According to the invention, double spray guns are adopted to spray precursor solution of two layers at boundaries of electrode film layers simultaneously. A flow rate of the precursor solution at a lower layer is gradually reduced, and the flow rate of the precursor solution at an upper layer is gradually increased, and a buffering layer is formed between two settled layers. The contents of the components of the two layers in the buffering layer are morphing. The content of the components of the lower layer is gradually reduced, and the content of the components of the upper layer is gradually increased. The method is advantaged in that: with the method, the upper layer and the lower layer are compactly combined, the coupling between the two layers is increased, stress force and grain boundary are reduced, conductivities of the interfaces are increased, the influence of interface conductivities on the integral performance of the battery is reduced as far as possible, and the performance of the battery is improved.
Description
Technical field
The present invention relates to a kind of preparation method of lithium battery, especially relate to a kind of spray pyrolysis preparation method of all solid-state thin-film lithium battery.
Background technology
The all solid state lithium ion battery of forming with inorganic solid electrolyte has following advantage: have than traditional NI-G, specific energy that Ni-MH battery is higher; The configuration design of battery is also more convenient and flexible, almost can be prepared into Any shape and size, can directly be integrated in the circuit; Has superior charge-discharge performance; Self-discharge rate is little, can overcome that the liquid electrolyte lithium ion battery used after a period of time because dissolving and problem [Z. R. Zhang, Z. L. Gong, the and Y. Yang of degradation failure of electrode active material in electrolyte; J. Phys. Chem. B; 108,2004,17546.]; Safe, do not have gas during work and produce the leakage problem of the matter that can not produce electrolysis; Stable performance, operating temperature range big (50～180 ℃) can be used for many extreme occasions.
In all solid state lithium ion battery; The electric charge that the migration rate of charge carrier in solid electrolyte often is far smaller than electrode surface shift and positive electrode in ions diffusion speed and become the rate determining step in the entire electrode kinetics, the inorganic solid electrolyte that development has the higher li ionic conductivity is the core key point that makes up high performance lithium ion battery.The ionic conductivity that the inorganic solid electrolyte of the electrochemical window that yet bad is up to the present can be more stable in air, have broad, relatively reasonable preparation cost can reach is generally 10
-5-10
-7Scm
-1About, the solid electrolyte sheet of general thickness is difficult to satisfy the Essential Performance Requirements of solid lithium battery.And commercial or study more anode material for lithium-ion batteries such as LiFePO4, LiMn2O4 etc. have very low electronic conductivity and ionic conductivity, the battery that simple solid electric pole piece constitutes makes the overall performance of battery receive very big restriction.
And solid-State Thin Film Li-Ion Batteries is microminiaturized all solid state lithium ion battery; Its positive electrode-solid electrolyte-negative material all is several microns to tens microns a film, can overcome the adverse effect that the low lithium ion conductivity of low electronic conductivity of positive electrode and ionic conductivity and solid electrolyte brings battery performance.Solid-State Thin Film Li-Ion Batteries has a wide range of applications: comprising: miniature robot surveillance plane electrical source of power (comprising the camera head power supply), multiple microsensor, CMOS integrated circuit, smart card (Smart Card), portable set etc., thus become the focus of research and development side.
Method [Y. Iriyama such as rf magnetron sputtering deposition, pulsed laser deposition, PECVD are adopted in the preparation of present all solid-state thin-film lithium battery basically; M. Yokoyama, C. Yada, et al. Electrochem. Solid State Lett.; 2004,7 (10): A340.].Huge, the complex process, with high costs of these method equipment investments.Spray pyrolysis also is a kind of effective means of deposit film.Through high pressure carrier gas the precursor solution mist is changed into several microns little droplet and the substrate surface that heats with the fast speeds bombardment with these droplets; In this process; Droplet has experienced water evaporates, drying, pyrolysis, has formed the product thin layer attached to substrate surface; Along with constantly carrying out of atomizing pyrolysis, form fine and close film gradually.Spray pyrolysis has does not need vacuum environment, technical process is simple, equipment investment is few, has the ability of preparation large area film.
Yet adopting this method to prepare all solid-state thin-film lithium battery remains in the problem that much waits to solve:
1, film lithium cell needs 3 layer films at least, i.e. positive electrode-solid electrolyte-negative material, the key factor that influences its overall performance be layer with layer between the interface closely reach matching degree.The not high and carrier gas of the common underlayer temperature of spray pyrolysis to the kinetic energy that particulate brings limited (can not show a candle to magnetron sputtering or pulse laser) caused layer and bed boundary closely and matching degree not high; Therefore the grain boundary resistance at interface is higher, will have a strong impact on the overall performance of battery.
2, the solid electrolyte material of suitable spray pyrolysis preparation is less, and the solid electrolyte LiPON (nitrogen doping phosphoric acid lithium) that has better performance at present can only be through the magnetron sputtering preparation.
3, the technological parameter that can regulate is more, and like distance of flow rate of carrier gas, mass flow, underlayer temperature, nozzle and substrate or the like, the optimization of process conditions is difficulty comparatively.
At present the research and development personnel prepare the full solid thin film battery to spray pyrolysis and have carried out some and explore, and are 200910044488.7 Chinese invention patent like application number, like document [P. FRAGNAND; R NAGARAJAN.; D. VUJIC, J. Power Sources, 1995; 54:362.]; Basically still with the negative or positive electrode sheet or the electrolyte sheet of the monolithic film membrane battery of traditional spray pyrolysis method preparation, and be difficult to overcome electrode slice and electrolyte sheet boundary's sheet conductance each other difficult, influenced cell integrated performance.
Summary of the invention
Technical problem to be solved by this invention provides a kind of spray pyrolysis preparation method who as far as possible reduces all solid-state thin-film lithium battery that boundary's sheet conductance exerts an influence to cell integrated performance.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of spray pyrolysis preparation method of all solid-state thin-film lithium battery; It is characterized in that concrete steps are following: 1) substrate is positioned over constant temperature 200-500 ℃ of heating work plate surface; Spray gun A is used to spray precursor aqueous solution I, and spray gun B is used to spray precursor aqueous solution II; Apart from 8-20cm, spray gun A and heating work plate surface form 50-85 to spray gun A apart from heating work plate Surface Vertical
oThe angle of cut;
2) be that the carrier gas of 60-300Kpa acts on spray gun A with pressure, spray gun A atomized spray precursor aqueous solution I to substrate, sustained firing 10-100 minute; Injection flow is 1-10mL/min, then reduces the injection of precursor aqueous solution I with the speed of 1-2mL/min
FlowAnd continue to spray precursor aqueous solution I, till stopping injection;
3) apart from 8-20cm, spray gun B and heating work plate surface form 50-85 to while spray gun B apart from heating work plate Surface Vertical
oThe angle of cut; The carrier gas of pressure 60-300Kpa is acted on spray gun B, and spray gun B atomized spray precursor aqueous solution II is to substrate, and the flow of precursor aqueous solution II is started from scratch to be increased with identical speed; Until injection flow is 1-10mL/min, and then injecting time continues 20-200 minute; Speed with 1-2mL/min reduces the flow of precursor aqueous solution II and continues to spray precursor aqueous solution II then; Till stopping injection;
4) spray precursor aqueous solution III with spray gun A, apart from 8-20cm, spray gun A and heating work plate surface form 50-85 to spray gun A apart from heating work plate Surface Vertical
oThe angle of cut; The carrier gas of pressure 60-300Kpa is acted on spray gun A, and spray gun A atomized spray precursor aqueous solution III is to substrate, and the flow of precursor aqueous solution III is started from scratch to be increased with identical speed; Until with injection flow be 1-10mL/min, then injecting time continues 10-100 minute;
5) AEI After End of Injection, after the working plate surface cool to be heated, with processing after
SubstratePut into Muffle furnace at 500-700 ℃ of following constant temperature 2-10 hour, promptly make all solid-state thin-film lithium battery.
Precursor aqueous solution I is: concentration is that the ammonium metavanadate of 0.1-2mol/L, ammoniacal liquor, the concentration that concentration is 0.05-0.3 mol/L are the 0.1-2mol/L lithium acetate, and mass percent concentration is the adjuvant water solution of 0.1-5wt%; This auxiliary agent can be EGME, n-amyl alcohol, mean molecule quantity < a kind of in 5000 the PVAC polyvinylalcohol.
Precursor aqueous solution II consists of: concentration is the lanthanum nitrate of 0.1-2mol/L; Concentration is the tetrabutyl titanate of 0.1-2mol/L; Concentration is the acetic acid of 0.1-1mol/L, and concentration is the lithium acetate of 0.1-2mol/L, and mass percent concentration is the adjuvant water solution of (0.1-5wt%); This auxiliary agent can be EGME, n-amyl alcohol, mean molecule quantity < a kind of in 5000 the PVAC polyvinylalcohol.
Precursor aqueous solution III consists of: concentration is the 0.1-2mol/L lithium acetate, and concentration is the tetrabutyl titanate of 0.1-2mol/L, and concentration is that acetic acid and the mass percent concentration of 0.1-1mol/L is the adjuvant water solution of 0.1-5wt%; This auxiliary agent can be EGME, n-amyl alcohol, mean molecule quantity < a kind of in 5000 the PVAC polyvinylalcohol.
Substrate can be a kind of in copper sheet, silicon chip, the nickel sheet.
Compared with prior art; The invention has the advantages that adopt two spray guns through in the electrode thin film layer boundary part spray the precursor aqueous solution of two layers simultaneously, the precursor aqueous solution flow of lower floor reduces gradually, upper strata precursor aqueous solution flow increases gradually; Between two sedimentary deposits, produce a resilient coating; The content of two composition of layer is gradual changes in this resilient coating, and the content of following composition of layer diminishes gradually, and the content of upper component becomes big gradually.Thereby form combining closely of levels, increase bilevel coupling, reduce stress and crystal boundary, improve the electricity at interface and lead, reduce boundary's sheet conductance as far as possible, improve the performance of battery cell integrated Effect on Performance.
Description of drawings
Fig. 1 discharges and recharges the cyclic discharge capacity decay pattern 100 times for embodiment 2 speed with 0.5 multiplying power on the battery performance test appearance.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1: the copper sheet substrate is positioned over 250 ℃ of heating work plate surfaces of constant temperature, and spray gun A is used to spray precursor aqueous solution I: concentration is the ammonium metavanadate NH of 0.3mol/L
4VO
3, concentration is the ammoniacal liquor NH of 0.08 mol/L
3H
2O, concentration is the lithium acetate Li (CH of 0.1mol/L
3COO), reaching mass percent concentration is the aqueous solution of the EGME of 0.2wt%.Spray gun B is used to spray precursor aqueous solution II: concentration is the lanthanum nitrate La (NO of 0.2mol/L
3)
3, concentration is the tetrabutyl titanate Ti (OC of 0.4mol/L
4H
9)
4, the acetic acid CH of concentration 0.2mol/L
3COOH, concentration is the lithium acetate Li (CH of 0.18mol/L
3COO), reaching mass percent concentration is the aqueous solution of the n-amyl alcohol of 0.1wt%.Spray gun A apart from heating work plate Surface Vertical apart from 10cm, spray gun A and the heating work plate surface angle of cut 55
o, be that the carrier gas of 60Kpa acts on spray gun A with pressure, spray gun A atomized spray precursor aqueous solution I is to the copper sheet substrate, and sustained firing 30 minutes, injection flow are 3mL/min; Then the speed with 1mL/min reduces the flow of precursor aqueous solution I and continues to spray precursor aqueous solution I, till stopping injection;
Apart from 10cm, spray gun B and heating work plate surface form 55 to spray gun B apart from heating work plate Surface Vertical simultaneously
oThe angle of cut; With pressure is that the carrier gas of 60Kpa acts on spray gun B, and spray gun B atomized spray precursor aqueous solution II is to the copper sheet substrate, and the speed that the flow of precursor aqueous solution II is started from scratch with 1mL/min increases; Until injection flow is 3mL/min, and then injecting time continues 50 minutes.Speed with 1mL/min reduces the flow of precursor aqueous solution II and continues to spray precursor aqueous solution II then; Till stopping injection;
Spray gun A sprays precursor aqueous solution III: concentration is the lithium acetate Li (CH of 0.4mol/L
3COO), concentration is the tetrabutyl titanate Ti (OC of 0.5mol/L
4H
9)
4, concentration is the acetic acid CH of 0.3mol/L
3COOH and mass percent concentration are the PVAC polyvinylalcohol (mean molecule quantity of 0.2wt%<5000) the aqueous solution.Spray gun A apart from heating work plate Surface Vertical apart from 10m, spray gun A and the heating work plate surface angle of cut 55
o, be that the carrier gas of 60Kpa acts on spray gun A with pressure, spray gun A atomized spray precursor aqueous solution III is to the copper coin substrate, and the speed that the flow of precursor aqueous solution III is started from scratch with 1mL/min increases, and is 3mL/min until injection flow.Then injecting time continues 30 minutes.AEI After End of Injection after the working plate surface cool to be heated, is put into Muffle furnace 500 ℃ of following constant temperature 3 hours with the substrate after the processing, promptly makes all solid-state thin-film lithium battery.
Embodiment 2: silicon chip substrate is positioned over 350 ℃ of heating work plate surfaces of constant temperature, and spray gun A is used to spray precursor aqueous solution I: concentration is the ammonium metavanadate NH of 1.0mol/L
4VO
3, concentration is the ammoniacal liquor NH of 0.15mol/L
3H
2O, concentration is the lithium acetate Li (CH of 0.3mol/L
3COO), reaching mass percent concentration is the aqueous solution of the EGME of 2wt%.Spray gun B sprays precursor aqueous solution II: concentration is the lanthanum nitrate La (NO of 0.5mol/L
3)
3, concentration is 1.0mol/L tetrabutyl titanate Ti (OC
4H
9)
4, concentration is the acetic acid CH of 0.5mol/L
3COOH, concentration is the lithium acetate Li (CH of 0.52mol/L
3COO) and mass percent concentration be the PVAC polyvinylalcohol (mean molecule quantity of 2.2wt%<5000) the aqueous solution.Spray gun A apart from heating work plate Surface Vertical apart from 15cm, spray gun A and the heating work plate surface angle of cut 70
o, be that the carrier gas of 150Kpa acts on spray gun A with pressure, spray gun A atomized spray precursor aqueous solution I is to substrate, and sustained firing 50 minutes, injection flow are 6mL/min.Then the speed with 1.5mL/min reduces the flow of precursor aqueous solution I and continues injection precursor aqueous solution I, till injection stops;
Simultaneously spray gun B apart from heating work plate Surface Vertical apart from 15cm, the spray gun B and the surperficial angle of cut 70 of heating work plate
o, the carrier gas of pressure 150Kpa is acted on spray gun B, spray gun B atomized spray precursor aqueous solution II is to substrate, and the flow of precursor aqueous solution II is started from scratch with the speed increase of 1.5mL/min, is 6mL/min up to injection flow, and then injecting time continues 100 minutes.Speed with 1.5mL/min reduces the flow of precursor aqueous solution II and continues to spray precursor aqueous solution II then, till stopping injection;
Spray gun A sprays precursor aqueous solution III: concentration is the lithium acetate Li (CH of 1.0mol/L
3COO), concentration is the tetrabutyl titanate Ti (OC of 1.25mol/L
4H
9)
4, concentration is 0.45mol/L acetic acid CH
3COOH and mass percent concentration are the aqueous solution of 1.9wt% n-amyl alcohol.Spray gun A apart from heating work plate Surface Vertical apart from 15m, spray gun A and the heating work plate surface angle of cut 70
o, be that the carrier gas of 150Kpa acts on spray gun A with pressure, spray gun A atomized spray precursor aqueous solution III is to substrate, and the speed that the flow of precursor aqueous solution III is started from scratch with 1.5mL/min increases, and is 6mL/min up to injection flow.Then injecting time continues 55 minutes.AEI After End of Injection after the working plate surface cool to be heated, is put into Muffle furnace 700 ℃ of following constant temperature 10 hours with substrate, promptly makes all solid-state thin-film lithium battery.
Like Fig. 1 is instance 2 100 cyclic discharge capacity decay patterns of high power charging-discharging with 0.5 multiplying power on the battery performance test appearance that the blue electric Electronics Co., Ltd. in Wuhan produces.As seen from the figure, 6 circulations at the beginning are low slightly owing to electrode active material need activate discharge capacity, yet just reach the stable capacity of 130mAhg very soon, and in 100 circulations, almost have no decay.
Embodiment 3: nickel sheet substrate is positioned over 500 ℃ of heating work plate surfaces of constant temperature, and spray gun A is used for injection and drives solution I: concentration is the ammonium metavanadate NH of 2.0mol/L
4VO
3, concentration is the ammoniacal liquor NH of 0.28mol/L
3H
2O, concentration is the lithium acetate Li (CH of 0.7mol/L
3COO), reaching mass percent concentration is the aqueous solution of the n-amyl alcohol of 4.5wt%.Spray gun B sprays precursor aqueous solution II: concentration is the lanthanum nitrate La (NO of 1.0mol/L
3)
3, concentration is the tetrabutyl titanate Ti (OC of 2.0mol/L
4H
9)
4, concentration is the acetic acid CH of 0.9mol/L
3COOH, concentration is the lithium acetate Li (CH of 0.95mol/L
3COO), reaching mass percent concentration is the aqueous solution of the EGME of 4.7wt%.Spray gun A apart from heating work plate Surface Vertical apart from 19cm, spray gun A and the heating work plate surface angle of cut 80
o, be that the carrier gas of 300Kpa acts on spray gun A with pressure, spray gun A atomized spray precursor aqueous solution I is to substrate; Sustained firing 90 minutes; Injection flow is 10mL/min, and then the speed with 2mL/min reduces the flow of precursor aqueous solution I and continues to spray precursor aqueous solution I, till stopping injection;
Simultaneously spray gun B apart from heating work plate Surface Vertical apart from 19cm, the spray gun B and the surperficial angle of cut 80 of heating work plate
o, be that the carrier gas of 300Kpa acts on the spray gun B with pressure, spray gun B atomized spray precursor aqueous solution II is to substrate, and the speed that the flow of precursor aqueous solution II is started from scratch with 2mL/min increases, and is 10mL/min up to injection flow, and then injecting time continues 180 minutes.Speed with 2mL/min reduces the flow of precursor aqueous solution II and continues to spray precursor aqueous solution II then, till stopping injection;
Spray gun A sprays precursor aqueous solution III: concentration is the lithium acetate Li (CH of 1.6mol/L
3COO), concentration is the tetrabutyl titanate Ti (OC of 2.0mol/L
4H
9)
4, concentration is the acetic acid CH of 0.92mol/L
3COOH and mass percent concentration are the aqueous solution of the EGME of 4.3wt%.Spray gun A apart from heating work plate Surface Vertical apart from 19m, the spray gun A and the heating work plate angle of cut 80
o, be that the carrier gas of 300Kpa acts on spray gun A with pressure, spray gun A atomized spray precursor aqueous solution III is to substrate, and the speed that the flow of precursor aqueous solution III is started from scratch with 2mL/min increases, and to 10mL/min, then injecting time continues 90 minutes up to injection flow.AEI After End of Injection after the working plate surface cool to be heated, is put into Muffle furnace 600 ℃ of following constant temperature 6 hours with substrate, promptly makes all solid-state thin-film lithium battery.
Claims (2)
1. the spray pyrolysis preparation method of an all solid-state thin-film lithium battery is characterized in that concrete steps are following: 1) substrate is positioned over constant temperature 200-500 ℃ of heating work plate surface, spray gun A is used to spray precursor aqueous solution I, and spray gun B is used to spray precursor aqueous solution II; Apart from 8-20cm, spray gun A and heating work plate surface form 50-85 to spray gun A apart from heating work plate Surface Vertical
oThe angle of cut;
2) be that the carrier gas of 60-300Kpa acts on spray gun A with pressure, spray gun A atomized spray precursor aqueous solution I to substrate, sustained firing 10-100 minute; Injection flow is 1-10mL/min, and then the speed with 1-2mL/min reduces the injection flow of precursor aqueous solution I and continues to spray precursor aqueous solution I, till stopping injection;
3) apart from 8-20cm, spray gun B and heating work plate surface form 50-85 to while spray gun B apart from heating work plate Surface Vertical
oThe angle of cut; The carrier gas of pressure 60-300Kpa is acted on spray gun B, and spray gun B atomized spray precursor aqueous solution II is to substrate, and the flow of precursor aqueous solution II is started from scratch to be increased with identical speed; Until injection flow is 1-10mL/min, and then injecting time continues 20-200 minute; Speed with 1-2mL/min reduces the flow of precursor aqueous solution II and continues to spray precursor aqueous solution II then; Till stopping injection;
4) spray precursor aqueous solution III with spray gun A, apart from 8-20cm, spray gun A and heating work plate surface form 50-85 to spray gun A apart from heating work plate Surface Vertical
oThe angle of cut; The carrier gas of pressure 60-300Kpa is acted on spray gun A, and spray gun A atomized spray precursor aqueous solution III is to substrate, and the flow of precursor aqueous solution III is started from scratch to be increased with identical speed; Until injection flow is 1-10mL/min, and then injecting time continues 10-100 minute;
5) AEI After End of Injection after the working plate surface cool to be heated, is put into Muffle furnace at 500-700 ℃ of following constant temperature 2-10 hour with the substrate after the processing, promptly makes all solid-state thin-film lithium battery;
Precursor aqueous solution I is: concentration is that the ammonium metavanadate of 0.1-2mol/L, ammoniacal liquor, the concentration that concentration is 0.05-0.3 mol/L are the 0.1-2mol/L lithium acetate, and mass percent concentration is the adjuvant water solution of 0.1-5wt%; This auxiliary agent is EGME, n-amyl alcohol, mean molecule quantity < a kind of in 5000 the polyvinyl alcohol;
Precursor aqueous solution II consists of: concentration is the lanthanum nitrate of 0.1-2mol/L; Concentration is the tetrabutyl titanate of 0.1-2mol/L,, concentration is the acetic acid of 0.1-1mol/L; Concentration is the lithium acetate of 0.1-2mol/L, and mass percent concentration is the adjuvant water solution of (0.1-5wt%); This auxiliary agent is EGME, n-amyl alcohol, mean molecule quantity < a kind of in 5000 the polyvinyl alcohol;
Precursor aqueous solution III consists of: concentration is the 0.1-2mol/L lithium acetate, and concentration is the tetrabutyl titanate of 0.1-2mol/L, and concentration is that acetic acid and the mass percent concentration of 0.1-1mol/L is the adjuvant water solution of 0.1-5wt%; This auxiliary agent is EGME, n-amyl alcohol, mean molecule quantity < a kind of in 5000 the polyvinyl alcohol.
2. the spray pyrolysis preparation method of all solid-state thin-film lithium battery according to claim 1 is characterized in that substrate is a kind of in copper sheet, silicon chip, the nickel sheet.
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