CN103268954B - LiSiPON (lithium silicon phosphorus) lithium-ion battery solid electrolyte film, and preparation method and application thereof - Google Patents

LiSiPON (lithium silicon phosphorus) lithium-ion battery solid electrolyte film, and preparation method and application thereof Download PDF

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CN103268954B
CN103268954B CN201310187125.5A CN201310187125A CN103268954B CN 103268954 B CN103268954 B CN 103268954B CN 201310187125 A CN201310187125 A CN 201310187125A CN 103268954 B CN103268954 B CN 103268954B
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film
lisipon
lithium
sputtering
ion battery
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CN103268954A (en
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李德军
李国珍
董磊
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Tianjin Normal University
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Abstract

The invention discloses a preparation method of a LiSiPON (lithium silicon phosphorus) lithium-ion battery solid electrolyte film. The LiSiPON lithium-ion battery solid electrolyte film is an LiSiPON film with the thickness of 80nm to 150nm which is obtained by utilizing ion beams with the volume ratio of N2 to Ar (nitrogen:argon) of 1: (5-1) to bombard Li3PO4 (lithium phosphate) and Si3N4 (silicon nitride). The invention also discloses an application of the LiSiPON lithium-ion battery solid electrolyte film in preparing a micro-type full-solid lithium battery material. The experiment shows that when the nitrogen content in the film is effectively improved by increasing the ratio of N2 and when the flow ratio of the nitrogen and argon is 1:1, the ion conductivity can reach 6.8*10<-6>S/cm. The LiSiPON lithium-ion battery solid electrolyte film can be combined with a film electrode to form a full-solid film lithium-ion battery. Not only is the method low in cost and simple in process, but also the prepared film is compact and uniform, the controllability of the preparation condition is strong, and convenience in commercialized mass production can be realized.

Description

LiSiPON lithium ion battery solid electrolyte film and preparation method thereof and application
Technical field
The invention belongs to solid-State Thin Film Li-Ion Batteries technical field.Particularly relate to ion beam assisted depositing (IBAD) technology and prepare LiSiPON, utilize Low energy nitrogen ions to bombard by Li 3pO 4and Si 3n 4composition composite target and obtain the high electrolytic thin-membrane of nitrogen content.
Background technology
Along with electronic device is constantly to microminiaturized, lightweight future development, the minute sized chemical power source of an urgent demand matches with it.The particularly needs of microelectromechanical systems (Micro-Electronic Mechanical Systems, MEMS) technical development, micro cell has caused the attention of people.The micro cell series conducted a research at present has: micro zinc-nickel battery, miniature solid lithium battery, miniature solar battery, minitype thermoelectric cell, micro fuel cell etc.Wherein miniature solid lithium battery is considered to one of most suitable power supply, because lithium is the lightest metallic element, electronegativity is maximum simultaneously, can provide high-energy-density.This battery is expected to for aspects such as grapefruit satellite, portable electric appts space technology, national defense industry.Total solids film lithium cell because its specific energy is high, the advantage of good cycle and the aspect such as fail safe is high, adapted to that the energy is microminiaturized, light-weighted requirement, become study hotspot gradually.
As the critical material of solid-State Thin Film Li-Ion Batteries, solid electrolyte film is between both positive and negative polarity, it is the medium transmitting ion, therefore high ionic conductivity must be possessed, low electronic conductivity, wide electrochemical window and have good stability with both positive and negative polarity, reported many electrode film materials for all solid-state thin-film lithium battery both at home and abroad, but the research of electrolytic thin-membrane lags significantly behind electrode film.This has become restriction all solid-state thin-film lithium battery and has improved further and improve and move towards the heavy yoke in market from laboratory.Therefore, the electrolytic thin-membrane of development high-performance, low cost has very important significance to exploitation All-solid film batteries.
A kind of more stable indefiniteness inorganic thin film electrolysis material LiPON of reported first (LiPON such as the Bates of U.S.'s Oak Ridge National Laboratory in 1992, Lithium phosphorous oxynitride), this material plays very important effect to the performance improving film lithium cell.LiPON has good electrochemical stability, and room temperature electrochemical window (VS. Li) can reach more than 5.5V, and electrochemical window wide so is extremely convenient to the discharge and recharge in actual application; There is very high thermal stability, can not undergoing phase transition within the scope of 247 ~ 413K; Electronic conductivity is lower than 10 -14s/cm, LiPON are electrolytical hull cell when storage 12 months, and self discharge is insignificant.LiPON is except having very high electrochemical stability, and mechanical stability is also high especially, can not occur dendrite or cracking, powdered phenomenon in cyclic process as cathode material.General LiPON is at N 2magnetron sputtering Li under atmosphere 3pO 4target obtains, and the LiPON chemical composition obtained under varying experimental conditions is different, and show that the conductivity of film is with reaction atmosphere N 2pressure increase or LiPON in N content increase and increase.Korea S S.J.Lee etc. are with (1-x) Li 3pO 4xLi 2siO 3for target adopts radio-frequency magnetron sputter method to prepare Li-Si-P-O-N oxy-nitride film electrolyte in a nitrogen atmosphere.Research finds, along with Si content increases, membrane ion conductivity raises, and is up to 1.24 × 10 -5s/cm.Because ion beam assisted depositing can accurately control beam intensity and beam energy, obtain the film that nitrogen content is higher, thus improve ionic conductivity further.Therefore, article adopts Kaufman ion source low-energy ion beams bombardment Li 3pO 4and Si 3n 4composite target prepares LiSiPON.
Summary of the invention
The present invention improves nitrogen content by design composite target, is the Li of 50.8 mm by diameter 3pO 4circle target is fixed on the Si that the length of side is 69.5mm 3n 4above side's target.Adopt Si 3n 4can effectively introduce Si element, other influences be there is no to thin film composition simultaneously, and can sputter from target and obtain N, the nitrogen content in film can be improved.Due to adding of Si, change the cross-linked structure of LiPON, improve stability and the ionic conductivity of film further.LiSiPON film has excellent stability, chemical property, and cost is low, environmentally safe.The performance of these excellences becomes the hull cell electrolyte having very much application potential, has very large social benefit and potential economic benefit in new energy materials field.
The invention discloses a kind of LiSiPON lithium ion battery solid electrolyte film for achieving the above object.Also disclose the preparation method of LiSiPON film simultaneously.Technology contents of the present invention is as follows:
A kind of LiSiPON lithium ion battery solid electrolyte film, is characterized in that it is by N 2: Ar volume flow ratio is the ion beam bombardment Li of 1:5-1 3pO 4and Si 3n 4, the thick LiSiPON film for 80nm ~ 150nm obtained.
LiSiPON lithium ion battery solid electrolyte film of the present invention, the volume ratio of preferred nitrogen argon flow is 1:1.
The present invention further discloses the preparation method of LiSiPON lithium ion battery solid electrolyte film, it is characterized in that being undertaken by following step:
(1) before deposit film, by circular Li 3pO 4target is fixed on square Si 3n 4above target, use Ar +sputtering synthesis target, uses N simultaneously +carry out auxiliary bombardment;
(2) deposit film in (100) monocrystalline silicon piece substrate of single-sided polishing, adopt mechanical pump and molecular pump, during Control release, base vacuum is 2.8 × 10 -4pa ~ 3.0 × 10 -4pa, atmospheric pressure value is measured by ionization gauge, and in deposition process, sputter gas selects pure N 2, Ar 2, controlling its flow with mass flow controller is 3 standard milliliters/minute (sccm) ~ 6 standard milliliters/minute (sccm); Operating air pressure total in deposition process is 1.0 × 10 -2pa ~ 1.2 × 10 -2pa;
(3) experiment control N 2with the flow-rate ratio of Ar at 1:5 ~ 1:1.
(100) monocrystalline silicon piece of single-sided polishing of the present invention, first cleans 15 minutes with acetone, EtOH Sonicate successively, sends into immediately in vacuum deposition chamber after drying up; Before deposit film, first use 500eV, the Ar of 5mA +cleaning 5 min ~ 10min is carried out to sample, during deposit film, regulates nitrogen argon than the sputtering time also accurately controlling each sample, plasma sputter source technological parameter: sputtering energy 0.9keV ~ 1.1keV, sputtering line 15mA ~ 20mA.
The preparation method of the present invention one preferred LiSiPON lithium ion battery solid electrolyte film is as follows:
FJL560CIZ type ultra high vacuum magnetic control is utilized to combine equipment for Ion Beam Assisted Deposition in sputtering system with ion beam, before deposit film, by circular Li 3pO 4be fixed on square Si 3n 4above target, be placed in the position of equipment sputtering target.During deposit film, can utilize computer program that the sputtering time accurately controlling target is set.Substrate is (100) monocrystalline silicon piece of single-sided polishing, uses acetone and absolute ethyl alcohol ultrasonic cleaning 15min before masking respectively, dries and is placed on rotating sample stage.During plated film, base vacuum reaches 2.8 × 10 -4pa, Ar +while sputtering target, use low energy N +carry out auxiliary bombardment, in whole deposition process, total operating air pressure remains on 1.2 × 10 -2pa.Plasma sputter source technological parameter: sputtering energy 1.1keV, sputtering line 20mA.Control passes into gas flow control N 2be 1:1 respectively with the flow-rate ratio of Ar, sputter gas selects pure N 2, Ar 2, with mass flow controller control N 2flow is 2sccm, Ar flow is 2sccm.Sputtering time is 2h, and the thickness of film is about 100nm.
The preparation method of another preferred LiSiPON lithium ion battery solid electrolyte film of the present invention is as follows:
FJL560CIZ type ultra high vacuum magnetic control is utilized to combine equipment for Ion Beam Assisted Deposition in sputtering system with ion beam, before deposit film, by circular Li 3pO 4be fixed on square Si 3n 4above target, be placed in the position of equipment sputtering target.During deposit film, can utilize computer program that the sputtering time accurately controlling target is set.Substrate is (100) monocrystalline silicon piece of single-sided polishing, uses acetone and absolute ethyl alcohol ultrasonic cleaning 15min before masking respectively, dries and is placed on rotating sample stage.During plated film, base vacuum is higher than 3 × 10 -4pa, Ar +while sputtering target, use low energy N +carry out auxiliary bombardment, in whole deposition process, total operating air pressure remains on 1.2 × 10 -2pa.Plasma sputter source technological parameter: sputtering energy 1.1keV, sputtering line 20mA.Control passes into gas flow control N 2be 1:2 respectively with the flow-rate ratio of Ar, sputter gas selects pure N 2, Ar 2, with mass flow controller control N 2flow is 1sccm, Ar flow is 2sccm.Sputtering time is 2h, and the thickness of film is about 100nm.
The method of LiSiPON films test prepared by the present invention is as follows:
The present invention makes full use of the bombardment effect of ion beam, accurately controls film composition, obtains level and smooth fine and close film.This experiment prepares film at three kinds of different nitrogen argons than in situation, carries out structured testing, stability test and electro-chemical test.Draw experimental result under each condition and carry out a series of performance evaluation, having drawn the reasonable nitrogen argon ratio of chemical property.The film of the present invention to synthesis has carried out X-ray diffraction (XRD) structural analysis, X-ray energy dispersion spectrum (EDS) is analyzed, x-ray photoelectron power spectrum (XPS) is analyzed, adopt the stability of vacuum tube furnace (OTF-1200X) testing film under different oxygen concentrations, utilize electrochemical workstation to carry out ac impedance measurement.
The present invention relates to and utilize ion beam assisted deposition (IBAD), design utilizes composite target, and prepare a kind of novel thin film lithium electricity electrolytic thin-membrane, lithium ion conductivity can reach 6.8 × 10 -6s/cm, utilizes ion beam assisted deposition, controls to pass into the GN 2 argon flow-rate ratio, its objective is the relation for finding nitrogen content in gas flow and film.Use Ar +bombardment Li 3pO 4and Si 3n 4the composite target of composition, the Si(100 at single-sided polishing) deposit film in substrate, adopt mechanical pump and molecular pump, base vacuum 2.8 × 10 -4pa ~ 3.0 × 10 -4pa, atmospheric pressure value is measured by ionization gauge, and in deposition process, sputter gas selects pure Ar and N 2.Controlling its flow with mass flow controller is 3sccm ~ 6 sccm; In deposition process, operating air pressure is about 1.2 × 10 -2pa, plasma sputter source technological parameter: sputtering energy 0.9keV ~ 1.1keV, sputtering line 15mA ~ 20mA.Its technological parameter: discharge voltage: 40V ~ 45V, discharging current: 0.4A ~ 0.8A, heater current: 6A ~ 8A, accelerating voltage: 190V ~ 200V, accelerates electric current: 1mA ~ 4mA.
The result of test of the present invention:
Fig. 1 is by Li 3pO 4and Si 3n 4the composite target schematic diagram of composition, Fig. 2 is Au/ LiSiPON/Au sandwich structure schematic diagram (vertical view and end view), for carrying out the mensuration of ionic conductivity; Fig. 3 is the XRD diffracting spectrum of LiSiPON film, and the Main Morphology of display film is amorphous state, has more space and be convenient to lithium ion transport and conduction in the skeleton of noncrystal membrane; Fig. 4 is contained elementary analysis in the energy dispersion collection of illustrative plates of LiSiPON film and three kinds of samples, and the figure illustrates Low energy nitrogen ions bombardment and effectively N and Si is injected film, wherein nitrogen argon is than during for 1:1, and in film, nitrogen content is the highest, secondly for nitrogen argon is than being 1:2; The XPS collection of illustrative plates of Fig. 5 electrolytic thin-membrane, can see that N has entered into Li 3pO 4in molecular framework, form P-N< structure of staggered interconnection to raising Li +mobility have contribution; Fig. 6 illustrates the ac impedance spectroscopy of 1#, and relatively high nitrogen content is conducive to improving its ionic conductivity.
The performance of LiSiPON film product prepared by the present invention is as follows:
Be improved N by experiment 2intake effectively improve nitrogen content in film, all containing a large amount of Si in the film under different condition.And at optimum proportioning: measure its ionic conductivity when nitrogen argon flow-rate ratio is 1:1, can 6.8 × 10 be reached -6s/cm.The LiSiPON film of preparation changes the distribution of orthophosphates anion and forms staggered interconnection structure due to the introducing of Si and N, there is in the skeleton of noncrystal membrane more space and be convenient to lithium ion motion and conduction, reduce the activation energy of lithium ion mobility, thus improve lithium ion conductivity.
Above result proves: the present invention " the thin film lithium electricity electrolyte LiSiPON prepared with ion beam assisted deposition " has good electrochemical properties, further optimization manufacture craft, improve film performance, developing in All-solid film batteries further and will have important application prospect.
The present invention further discloses the application of LiSiPON lithium ion battery solid electrolyte film in the miniature solid lithium battery material of preparation.
A large amount of portable consumer electronics device, the such as miniaturization of mobile phone, camera and notebook computer, the hull cell matched therewith is developed in an urgent demand.The comparison of results obtained in thin-film electrode material enriches, and just slightly inferior for the research of electrolyte.The preparation method of LiSiPON provided by the invention can be applied in all solid-state thin-film lithium battery as electrolytic thin-membrane.The method adopts ion beam assisted depositing can effectively avoid easily causing target to be heated inequality and the situation of breaking with magnetron sputtering plating, and adopts electron beam evaporation deposition to need with tungsten boat fusing Li 3pO 4raw material, can introduce the pollution of W elements; And preparation process is easy to control, environmentally safe, this is significant to actual production.Adopt ion beam of low energy N+ bombardment can obtain the higher film of nitrogen content, by mixing element silicon to the simple superposition of target, thus effectively raise the ionic conductivity of electrolytic thin-membrane, it is 6.8 × 10 that ac impedance technology records lithium ion conductivity simultaneously -6s/cm, higher than the ionic conductivity of the LiPON that J.B.Bates et al. uses magnetron sputtering to prepare.Due to mixing of Si, the stability of film is improved, and physical property and chemical property all obtain obvious improvement, and cost is lower, is expected to come into operation in the commercially producing of hull cell afterwards.
Accompanying drawing explanation
Fig. 1: Li in this series 3pO 4and Si 3n 4the composite target schematic diagram of composition;
Fig. 2: Au/ LiSiPON/Au sandwich structure schematic diagram (vertical view and end view) in this series;
Fig. 3: the XRD diffracting spectrum of LiSiPON film in this series;
Fig. 4: the energy dispersion collection of illustrative plates of LiSiPON film and constituent content table in this series;
Fig. 5: the XPS collection of illustrative plates of LiSiPON film in this series;
Fig. 6: the ac impedance spectroscopy of Au/ LiSiPON/Au in this series;
Fig. 7: FJL560CI2 type ultra high vacuum radio frequency magnetron combines sputtering system with ion beam;
Wherein 1. molecular pumps, 2. rotatable water cooled target platform, 3. Li 3pO 4and Si 3n 4target, 4. auxiliary target, 5. plasma sputter source, 6. low energy assists bombardment source, 7. gas access, 8. sample baffle plate, 9. rotatable water-cooled sample stage, 10. sample.
Embodiment:
Below in conjunction with specific embodiment, the present invention will be further described, and following each embodiment is not only limitation of the present invention for illustration of the present invention.
For content of the present invention, Characteristic can be understood further, accompanying drawing is coordinated to be described as follows:
Use equipment: FJL560CI2 type ultra high vacuum radio frequency magnetron is combined sputtering system and is used for synthesizing LiSiPON electrolytic thin-membrane with ion beam, this system is that its structure as shown in Figure 7 by Tianjin Normal University and Shenyang Scientific Instrument Factory, Chinese Academy of Sciences's joint research and development.Sputtering target material is the circular Li of 99.99% high-purity of diameter 50.9 mm, thickness 3 mm 3pO 4the square Si of 99.99% high-purity of target and the length of side 69.5 × 69.5mm, thickness 3mm 3n 4target.By circular Li 3pO 4target is fixed on square Si 3n 4on target, composition composite target.Sample to be placed in vacuum chamber on controlled rotary sample rotating disk sample stage 10; Pumping system is completed by mechanical pump and HTFB turbomolecular pump 1, and atmospheric pressure value is measured by ionization gauge, and Ar enters vacuum chamber through gas air inlet 7, Ar and N 2charge flow rate controlled by mass flowmenter.Computer program accurately controls the sputtering time of each sample.Different sample adopts identical bombarding energy and source parameters.
concrete synthesis technologic parameter:
N 2flow is respectively: 2sccm, 1sccm, 0.4sccm; Ar flow remains on 2sccm; (nitrogen argon ratio is respectively 1:1,1:2,1:5).Background vacuum: 2.8 × 10 -4pa; Operating air pressure: 0.012 Pa; Plasma sputter source technological parameter: sputtering energy 1.1keV, sputtering line 20mA.Its technological parameter: discharge voltage: 40V, discharging current: 0.8A, heater current: 7A, accelerating voltage: 200V, accelerates electric current: 4mA.It should be noted that: ion beam assisted depositing (IBAD) equipment of other models can use.
Embodiment 1
Regulate Ar, N 2flow-rate ratio synthesis LiSiPON electrolytic thin-membrane:
(1) use acetone and absolute alcohol to Si sheet ultrasonic cleaning 15 min successively before experiment, after oven dry, put coating chamber into.
(2) by circular Li 3pO 4target is fixed on square Si 3n 4on target, be placed on the target platform A in vacuum chamber, chamber is vacuumized, make background vacuum in chamber 2.8 × 10 -4pa.
(3) with mass flow flowmeter control Ar charge flow rate, make it to remain on about 20sccm, open ion gun power supply, sputtering energy 500eV, sputtering line 20mA, accelerates electric current 5mA.To sample at least Bombardment and cleaning 5 min.Close ion gun power supply.
(4) open plasma sputter source, with mass flow flowmeter control Ar charge flow rate, make it to remain on about 2sccm, open N 2intake valve, controlling flow is respectively 2sccm, 1sccm, 0.4sccm, and counter sample is 1#, 2#, 3#.Sputtering energy is 1.1keV, and sputtering line is 20mA.Accelerating voltage is 200V, and acceleration electric current is 4mA.
(5) now keep operating air pressure at about 0.012 Pa.It is 2 hours with the sputtering time of each sample of computer program control.The film that gas flow ratio can obtain different sample is passed into by what change each sample.
(6) film is in high vacuum chamber, until temperature drops to less than 100 DEG C just open chamber taking-up.
Regulate Ar, N 2flow-rate ratio synthesis LiSiPON electrolytic thin-membrane:
Deposition parameter: N 2flow is respectively: 2sccm, 1sccm, 0.4sccm; Ar flow remains on 2sccm; Background vacuum: 2.8 × 10 -4pa; Operating air pressure: 0.012 Pa; Plasma sputter source technological parameter: sputtering energy 1.1keV, sputtering line 20mA.Its technological parameter: discharge voltage: 40V, discharging current: 0.8A, heater current: 7A, accelerating voltage: 200V, accelerates electric current: 4mA.Sedimentation time controls at about 7200s.
For optimum condition, in the preparation before experiment as described in step (1) ~ (3), later by shown in step (4), change nitrogen argon than the film depositing different nitrogen contents.The film obtained is placed in drying box and preserves, in order to carrying out the test of thickness, structure, constituent content etc.
Embodiment 2
For the object of the ionic conductivity of measurement thin-film electrolyte, Si (100) substrate deposited Au, LiSiPON film and Au successively, form Au/LiSiPON/Au " sandwich " structure (as Fig. 2).Concrete implementation step is as follows:
(1) before experiment, sputtering target position is adjusted to Au target, uses acetone and absolute alcohol to Si sheet ultrasonic cleaning 15 min successively, after oven dry, put coating chamber into.
(2) chamber is vacuumized, make background vacuum in chamber 2.8 × 10 -4pa.
(3) with mass flow flowmeter control Ar charge flow rate, make it to remain on about 20sccm, open ion gun power supply, sputtering energy 500eV, sputtering line 20mA, accelerates electric current 5mA.To sample at least Bombardment and cleaning 5 min.Close ion gun power supply.
(4) open plasma sputter source, with mass flow flowmeter control Ar charge flow rate, make it to remain on about 20sccm.Sputtering energy is 1keV, and sputtering line is 20mA.Accelerating voltage is 200V, and acceleration electric current is 2mA.Sputtering time is 1h.
(5) sputtering target position is adjusted to Li 3pO 4and Si 3n 4composite target (as described in Example 1), opens plasma sputter source, regulates Ar flow to be 2sccm, N 2flow is 2sccm, and sputtering energy is 1.1keV, and sputtering line is 20mA.Accelerating voltage is 200V, and acceleration electric current is 4mA.Sputtering time is 2h.
(6) sputtering target position is adjusted to Au target by conputer controlled, opens plasma sputter source, and control Ar flow is 20sccm.Sputtering energy is 1keV, and sputtering line is 20mA.Accelerating voltage is 200V, and acceleration electric current is 2mA.Sputtering time is 1h.
(7) film is in high vacuum chamber, until temperature drops to less than 100 DEG C just open chamber taking-up.
The present invention make use of the nanometer mechanics test macro of American MTS respectively to the film synthesized under various process conditions, X-ray diffraction (XRD) instrument, X-ray energy dispersion spectrum (EDS) analyzer, x-ray photoelectron power spectrum (XPS) analyzer have carried out comprising the physical propertys such as film thickness, structure, chemical composition, constituent content and characterized.Utilize Princeton VersaSTAT4 multifunction electric chem workstation to carry out ac resistance analysis to LiSiPON film in an experiment, measuring frequency is 0.1Hz to 100KHz.The data result of test sees the following form, and main result is as follows:
1, with regard to physical property: LiSiPON film is the same with LiPON, presents amorphous structure.Improve N 2intake effectively improve nitrogen content in film, all containing a large amount of Si in the film under different condition.XPS collection of illustrative plates display N presents two kinds of different structures in the film.
2, with regard to chemical property: the film that nitrogen content is relatively high has higher ionic conductivity, be 6.8 × 10 -6the introducing of S/cm, N improves the ionic conductivity of original system, along with N 2the increase of flow, the N content in electrolytic thin-membrane and the synchronous increase of ionic conductivity, further demonstrate that the nitrogen content in film affects transport and the migration of lithium ion, thus affect conductivity.
Generally speaking: utilize Low energy nitrogen ions to bombard Li 3pO 4and Si 3n 4the composite target of composition can obtain the thin-film electrolyte LiSiPON of dense uniform, the leaded wastewater in the test proof film of constituent and chemical composition and N 2flow is directly proportional, N and Si is mixed with the raising being beneficial to conductivity.N 2: when Ar is 1:1, in film, nitrogen content is the highest, and now ionic conductivity can reach 6.8 × 10 -6s/cm, for coming into operation of film lithium ion battery provides the foundation.Can prepare further by Controlling Technology parameter and there is excellent physical characteristic and the electrolytic thin-membrane of electrochemical properties.
Embodiment 3
LiSiPON in all solid-state thin-film lithium battery as the application of electrolytic thin-membrane
All-solid film batteries LiCoO 2the preparation of/LiSiPON/Li
(1) front rf magnetron sputtering is tested at Si(110) substrate plates LiCoO 2membrane electrode, sputtering time is 4h.
(2) use equipment for Ion Beam Assisted Deposition plating thin-film electrolyte, sputtering target position is adjusted to Li 3pO 4and Si 3n 4composite target (as described in Example 1), vacuumizes chamber, makes background vacuum in chamber 2.8 × 10 -4pa.
(3) open plasma sputter source, regulate Ar flow to be 2sccm, N 2flow is 2sccm, and sputtering energy is 1.1keV, and sputtering line is 20mA.Accelerating voltage is 200V, and acceleration electric current is 4mA.Sputtering time is 5h.
(4) film is in high vacuum chamber, until temperature drops to less than 100 DEG C just open chamber taking-up.
(5) film is placed in vacuum thermal evaporation equipment, evaporation metal lithium membrane electrode, the evaporation time is 1h.
(6) rf magnetron sputtering is adopted to sputter Li on film 3pO 4film as protective layer, about 1h.So far complete solid-State Thin Film Li-Ion Batteries is assembled into.
Open and ion beam assisted depositing (IBAD) legal system that proposes of the present invention is for LiSiPON film, and under the condition of suitable nitrogen argon gas stream flow ratio, can obtain the good electrolytic thin-membrane of chemical property, ionic conductivity can reach 6.8 × 10 -6s/cm, can be applied to the preparation of film lithium ion battery.
Those skilled in the art are by using for reference present disclosure, and the links such as appropriate change raw material, technological parameter realize.Method of the present invention and product are described by preferred embodiment, person skilled obviously can not depart from content of the present invention, spirit and scope method as herein described and product are changed or suitably change with combination, realize the technology of the present invention.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.

Claims (3)

1. a preparation method for LiSiPON lithium ion battery solid electrolyte film, is characterized in that being undertaken by following step:
(1) before deposit film, by circular Li 3pO 4target is fixed on square Si 3n 4above target, use Ar +sputtering synthesis target, uses N simultaneously +carry out auxiliary bombardment;
(2) deposit film in (100) monocrystalline silicon piece substrate of single-sided polishing, adopt mechanical pump and molecular pump, during Control release, base vacuum is 2.8 × 10 -4pa ~ 3.0 × 10 -4pa, atmospheric pressure value is measured by ionization gauge, and in deposition process, sputter gas selects pure N 2, Ar, controlling its flow with mass flow controller is 3 standard milliliters/minute (sccm) ~ 6 standard milliliters/minute (sccm); Operating air pressure total in deposition process is 1.0 × 10 -2pa ~ 1.2 × 10 -2pa;
(3) experiment control N 2be 1:1 with the flow-rate ratio of Ar, obtain the LiSiPON film that thickness is 80nm ~ 150nm, form staggered interconnection structure; The Main Morphology of film is amorphous state, has more space and be convenient to lithium ion transport and conduction in the skeleton of noncrystal membrane; Described ion beam bombardment Li 3pO 4and Si 3n 4refer to Li 3pO 4and Si 3n 4composite target.
2. the preparation method of LiSiPON lithium ion battery solid electrolyte film described in claim 1, (100) monocrystalline silicon piece of single-sided polishing wherein, first cleans 15 minutes with acetone, EtOH Sonicate successively, sends into immediately in vacuum deposition chamber after drying up; Before deposit film, first use 500eV, the Ar of 5mA +cleaning 5 min ~ 10min is carried out to sample, during deposit film, regulates nitrogen argon than the sputtering time also accurately controlling each sample, plasma sputter source technological parameter: sputtering energy 0.9keV ~ 1.1keV, sputtering line 15mA ~ 20mA.
3. the application of LiSiPON lithium ion battery solid electrolyte film described in claim 1 in the miniature solid lithium battery material of preparation.
CN201310187125.5A 2013-05-20 2013-05-20 LiSiPON (lithium silicon phosphorus) lithium-ion battery solid electrolyte film, and preparation method and application thereof Expired - Fee Related CN103268954B (en)

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