CN103268954A - 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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CN103268954A
CN103268954A CN2013101871255A CN201310187125A CN103268954A CN 103268954 A CN103268954 A CN 103268954A CN 2013101871255 A CN2013101871255 A CN 2013101871255A CN 201310187125 A CN201310187125 A CN 201310187125A CN 103268954 A CN103268954 A CN 103268954A
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film
lisipon
lithium
ion battery
solid electrolyte
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CN103268954B (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 the solid-State Thin Film Li-Ion Batteries technical field.Particularly relate to ion beam assisted depositing (IBAD) technology and prepare LiSiPON, utilize the bombardment of low energy nitrogen ion by Li 3PO 4And Si 3N 4The composite target of forming and obtain the high electrolytic thin-membrane of nitrogen content.
Background technology
Along with electronic device constantly develops to microminiaturized, lightweight direction, the minute sized chemical power source of an urgent demand is complementary with it.Particularly (micro cell has caused people's attention to microelectromechanical systems for Micro-Electronic Mechanical Systems, the MEMS) needs of technical development.The micro cell series that has conducted a research at present has: micro zinc-nickel battery, miniature solid lithium battery, miniature solar battery, miniature thermoelectric cell, micro fuel cell etc.Wherein miniature solid lithium battery is considered to one of only power supply, because lithium is the lightest metallic element, the electronegativity maximum can provide high-energy-density simultaneously.This battery is expected to for aspects such as grapefruit satellite, portable electric appts space technology, national defense industry.The total solids film lithium cell becomes the research focus gradually because the advantage of aspects such as its specific energy height, good cycle and fail safe height has adapted to energy microminiaturization, light-weighted requirement.
Critical material as solid-State Thin Film Li-Ion Batteries, the solid electrolyte film is between both positive and negative polarity, it is the medium that transmits ion, therefore must possess high ionic conductivity, low electronic conductivity, wide electrochemical window and have preferably 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 the heavy yoke that the restriction all solid-state thin-film lithium battery further improves and improves and move towards market from the laboratory.Therefore, the development high-performance, electrolytic thin-membrane has very important significance to exploitation full solid thin film battery cheaply.
A kind of more stable indefiniteness inorganic thin film electrolysis material LiPON (LiPON of the reported first such as Bates of U.S.'s Oak Ridge National Laboratory in 1992, Lithium phosphorous oxynitride), this material has play a part very important to the performance that improves film lithium cell.LiPON has good electrochemical stability, and room temperature electrochemical window (VS. Li) can reach more than the 5.5V, and wide like this electrochemical window extremely is convenient to discharging and recharging in actual application; Have very high thermal stability, can not undergoing phase transition in 247～413K scope; Electronic conductivity is lower than 10 -14S/cm, LiPON are that the self discharge when storing 12 months of electrolytical hull cell is insignificant.LiPON is except having very high electrochemical stability, and mechanical stability is also high especially, dendrite or cracking, powdered phenomenon can not occur as cathode material in cyclic process.General LiPON is at N 2Magnetron sputtering Li under the atmosphere 3PO 4Target obtains, the LiPON chemical composition difference that under different experiment conditions, obtains, and the conductivity that draws 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 adopting radio-frequency magnetron sputter method under nitrogen atmosphere, target prepared Li-Si-P-O-N oxynitride thin-film electrolyte.Discover that along with Si content increases, the film ionic conductivity raises, and is up to 1.24 * 10 -5S/cm.Because ion beam assisted depositing can accurately be controlled beam intensity and beam energy, obtains the higher film of nitrogen content, thereby further improves ionic conductivity.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 the design composite target, is the Li of 50.8 mm with diameter 3PO 4The circle 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 the Si element, simultaneously thin film composition not had other influences, and from target, can sputter obtain N, can improve the nitrogen content in the film.Owing to the adding of Si, change the cross-linked structure of LiPON, further improve stability and the ionic conductivity of film.The LiSiPON film has advantages of excellent stability, chemical property, and cost is low, environmentally safe.These excellent performances become it the hull cell of application potential electrolyte very much, has very big social benefit and potential economic benefit in the new energy materials field.
The invention discloses a kind of LiSiPON lithium ion battery solid electrolyte film for achieving the above object.The preparation method of LiSiPON film is also disclosed 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: the Ar volume flow ratio is the ion beam bombardment Li of 1:5-1 3PO 4And Si 3N 4, what obtain is thick in the LiSiPON film of 80nm ~ 150nm.
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, with circular Li 3PO 4Target is fixed in square Si 3N 4Above the target, use Ar +Target is synthesized in sputter, uses N simultaneously +Assist bombardment;
(2) deposit film in (100) of single-sided polishing monocrystalline silicon piece substrate adopts mechanical pump and molecular pump, and base vacuum is 2.8 * 10 during the control experiment -4Pa ~ 3.0 * 10 -4Pa, atmospheric pressure value is measured by ionization gauge, and sputter gas is selected pure N for use in the deposition process 2, Ar 2, controlling its flow with mass flow controller is 3 standard ml/min (sccm) ~ 6 standard ml/min (sccm); Total operating air pressure is 1.0 * 10 in the deposition process -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 is used acetone, ethanol ultrasonic cleaning 15 minutes earlier successively, sends in the vacuum deposition chamber immediately after drying up; Before deposit film, use earlier 500eV, the Ar of 5mA +Sample is cleaned 5 min ~ 10min, during deposit film, regulate the nitrogen argon than the sputtering time of also accurately controlling each sample, plasma sputter source technological parameter: sputter energy 0.9keV ~ 1.1keV, sputter line 15mA ~ 20mA.
The preparation method of a preferred LiSiPON lithium ion battery solid electrolyte film of the present invention is as follows:
Utilize the Equipment for Ion Beam Assisted Deposition in FJL560CIZ type ultra high vacuum magnetic control and the ion beam associating sputtering system, before deposit film, with circular Li 3PO 4Be fixed in square Si 3N 4Above the target, place the position of equipment sputtering target.During deposit film, can utilize computer program that the sputtering time of accurate control target is set.Substrate is single-sided polishing (100) monocrystalline silicon piece, uses acetone and absolute ethyl alcohol ultrasonic cleaning 15min before the film processed respectively, and oven dry is placed on the rotating sample platform.Base vacuum reaches 2.8 * 10 during plated film -4Pa, Ar +In the time of sputtering target, use low energy N +Assist bombardment, in the whole deposition process, total operating air pressure remains on 1.2 * 10 -2Pa.Plasma sputter source technological parameter: sputter energy 1.1keV, sputter line 20mA.Control feeds gas flow control N 2With the flow-rate ratio of Ar be respectively 1:1, sputter gas is selected pure N for use 2, Ar 2, control N with mass flow controller 2Flow is 2sccm, and the 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:
Utilize the Equipment for Ion Beam Assisted Deposition in FJL560CIZ type ultra high vacuum magnetic control and the ion beam associating sputtering system, before deposit film, with circular Li 3PO 4Be fixed in square Si 3N 4Above the target, place the position of equipment sputtering target.During deposit film, can utilize computer program that the sputtering time of accurate control target is set.Substrate is single-sided polishing (100) monocrystalline silicon piece, uses acetone and absolute ethyl alcohol ultrasonic cleaning 15min before the film processed respectively, and oven dry is placed on the rotating sample platform.Base vacuum is higher than 3 * 10 during plated film -4Pa, Ar +In the time of sputtering target, use low energy N +Assist bombardment, in the whole deposition process, total operating air pressure remains on 1.2 * 10 -2Pa.Plasma sputter source technological parameter: sputter energy 1.1keV, sputter line 20mA.Control feeds gas flow control N 2With the flow-rate ratio of Ar be respectively 1:2, sputter gas is selected pure N for use 2, Ar 2, control N with mass flow controller 2Flow is 1sccm, and the Ar flow is 2sccm.Sputtering time is 2h, and the thickness of film is about 100nm.
The method of the LiSiPON films test of the present invention's preparation is as follows:
The present invention takes full advantage of the bombardment effect of ion beam, accurately controls film and forms, and obtains level and smooth fine and close film.This experiment is to prepare film at three kinds of different nitrogen argons than under the situation, carries out structured testing, stability test and electro-chemical test.Draw the experimental result under each condition and carry out a series of performance evaluations, drawn the reasonable nitrogen argon ratio of chemical property.The present invention has carried out X-ray diffraction (XRD) structural analysis to synthetic film, 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 utilize ion beam assisted deposition (IBAD), design utilizes composite target, prepares a kind of novel thin film lithium electricity electrolytic thin-membrane, and lithium ion conductivity can reach 6.8 * 10 -6S/cm utilizes ion beam assisted deposition, and control feeds the GN 2 argon flow-rate ratio, its objective is to finding the relation of nitrogen content in gas flow and the film.Use Ar +Bombardment Li 3PO 4And Si 3N 4The composite target of forming is at the Si(100 of single-sided polishing) deposit film in the 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 sputter gas is selected pure Ar and N for use in the deposition process 2Controlling its flow with mass flow controller is 3sccm ~ 6 sccm; Operating air pressure is about 1.2 * 10 in the deposition process -2Pa, plasma sputter source technological parameter: sputter energy 0.9keV ~ 1.1keV, sputter 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 forming, Fig. 2 is Au/ LiSiPON/Au sandwich structure schematic diagram (vertical view and end view), is used for carrying out the mensuration of ionic conductivity; Fig. 3 is the XRD diffracting spectrum of LiSiPON film, shows that the main form of film is amorphous state, has more space in the skeleton of noncrystal membrane and is convenient to lithium ion transportation and conduction; Fig. 4 is contained elementary analysis in the energy dispersion collection of illustrative plates of LiSiPON film and the three kinds of samples, the figure illustrates the bombardment of low energy nitrogen ion and effectively N and Si is injected film, and wherein the nitrogen argon is than for 1:1 the time, and nitrogen content is the highest in the film, secondly for the nitrogen argon 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 4Divide in the subframe, form the P-N＜structure of staggered interconnection to improving Li +Mobility contribution is arranged; Fig. 6 has represented the ac impedance spectroscopy of 1#, and high relatively nitrogen content is conducive to improve its ionic conductivity.
The performance of the LiSiPON film product of the present invention's preparation is as follows:
N by experiment is improved 2The feeding amount effectively improve nitrogen content in the film, all contain a large amount of Si in the film under the different condition.And in best proportioning: nitrogen argon flow-rate ratio is measured its ionic conductivity during for 1:1, can reach 6.8 * 10 -6S/cm.The LiSiPON film of preparation is because the introducing of Si and N changes distribution and the staggered interconnection structure of formation of orthophosphates anion, have more space in the skeleton of noncrystal membrane and be convenient to lithium ion motion and conduction, reduce the activation energy of lithium ion migration, thereby improve lithium ion conductivity.
Above result proves: the present invention's " with the thin film lithium electricity electrolyte LiSiPON of ion beam assisted deposition preparation " has good electrochemical properties, further optimize manufacture craft, improve film performance, further in the exploitation full solid thin film battery important application prospects will arranged.
The present invention further discloses the application of LiSiPON lithium ion battery solid electrolyte film aspect the miniature solid lithium battery material of preparation.
A large amount of portable consumer electronic devices, such as the miniaturization of mobile phone, camera and notebook computer, the hull cell that an urgent demand exploitation is complementary therewith.The achievement that obtains aspect thin-film electrode material is abundanter, 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 the electron beam evaporation deposition need be with tungsten boat fusing Li 3PO 4Raw material can be introduced the pollution of W elements; And preparation process is easy to control, environmentally safe, and this is significant to actual production.Adopt the bombardment of low energy nitrogen ion beam can obtain the higher film of nitrogen content simultaneously, mix element silicon by the simple superposition to target, thereby effectively raise the ionic conductivity of electrolytic thin-membrane, it is 6.8 * 10 that ac impedance technology records lithium ion conductivity -6S/cm is higher than the ionic conductivity that J.B.Bates et al. uses the LiPON of magnetron sputtering preparation.Because the mixing of Si, the stability of film is improved, and physical property and chemical property have all obtained obvious improvement, and cost is lower, is expected to come into operation in the commercially producing of hull cell afterwards.
Description of drawings
Fig. 1: Li in this series 3PO 4And Si 3N 4The composite target schematic diagram of forming;
Fig. 2: Au/ LiSiPON in this series/Au sandwich structure schematic diagram (vertical view and end view);
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 and ion beam associating sputtering system;
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. auxiliary bombardment source, 7. gas access, 8. sample baffle plate, 9. rotatable water-cooled sample platform, 10. sample of low energy.
Embodiment:
The present invention will be further described below in conjunction with specific embodiment, and following each embodiment only is used for explanation the present invention and is not limitation of the present invention.
For further understanding content of the present invention, characteristics and effect, conjunction with figs. is described as follows:
Use equipment: FJL560CI2 type ultra high vacuum radio frequency magnetron and ion beam associating sputtering system are used for synthesizing the LiSiPON electrolytic thin-membrane, and 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.With circular Li 3PO 4Target is fixed in square Si 3N 4On the target, form composite target.Sample is placed on the interior controlled sample rotary turnplate sample platform 10 of vacuum chamber; Pumping system is finished 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 control by mass flowmenter.Computer program is accurately controlled the sputtering time of each sample.Different samples adopt identical bombarding energy and source parameters.
Concrete synthesis technologic parameter:
N 2Flow is respectively: 2sccm, 1sccm, 0.4sccm; The Ar flow remains on 2sccm; (nitrogen argon ratio is respectively 1:1,1:2,1:5).Base vacuum degree: 2.8 * 10 -4Pa; Operating air pressure: 0.012 Pa; Plasma sputter source technological parameter: sputter energy 1.1keV, sputter line 20mA.Its technological parameter: discharge voltage: 40V, discharging current: 0.8A, heater current: 7A, accelerating voltage: 200V accelerates electric current: 4mA.Need to prove: the ion beam assisted depositing of other models (IBAD) equipment can use.
Embodiment 1
Regulate Ar, N 2Flow-rate ratio is synthesized the LiSiPON electrolytic thin-membrane:
(1) uses acetone and absolute alcohol to Si sheet ultrasonic cleaning 15 min successively before the experiment, put coating chamber after the oven dry into.
(2) with circular Li 3PO 4Target is fixed in square Si 3N 4On the target, place on the target platform A in the vacuum chamber, chamber is vacuumized, make the interior base vacuum degree of chamber 2.8 * 10 -4Pa.
(3) with mass flow flowmeter control Ar charge flow rate, make it to remain on about 20sccm, open the ion gun power supply, sputter energy 500eV, sputter line 20mA accelerates electric current 5mA.Sample is bombarded cleaning 5 min at least.Close the ion gun power supply.
(4) open the 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 respectively is 2sccm, 1sccm, 0.4sccm, counter sample is 1#, 2#, 3#.The sputter energy is 1.1keV, and the sputter line is 20mA.Accelerating voltage is 200V, and the acceleration electric current is 4mA.
(5) keep operating air pressure about 0.012 Pa this moment.Sputtering time with each sample of computer program control is 2 hours.Can obtain the film of different samples by the feeding gas flow ratio that changes each sample.
(6) film is in high vacuum chamber, drops to up to temperature and just opens chamber below 100 ℃ and take out.
Regulate Ar, N 2Flow-rate ratio is synthesized the LiSiPON electrolytic thin-membrane:
Deposition parameter: N 2Flow is respectively: 2sccm, 1sccm, 0.4sccm; The Ar flow remains on 2sccm; Base vacuum degree: 2.8 * 10 -4Pa; Operating air pressure: 0.012 Pa; Plasma sputter source technological parameter: sputter energy 1.1keV, sputter line 20mA.Its technological parameter: discharge voltage: 40V, discharging current: 0.8A, heater current: 7A, accelerating voltage: 200V accelerates electric current: 4mA.Sedimentation time control is about 7200s.
For optimum condition, on the preparation before the experiment as described in step (1)～(3), later on set by step shown in (4), change nitrogen argon recently deposits the film of different nitrogen contents.The film that obtains places drying box to preserve, in order to carrying out the test of thickness, structure, constituent content etc.
Embodiment 2
For the purpose of the electrolytical ionic conductivity of MEASUREMENTS OF THIN, on 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 the experiment sputter target position is adjusted to the Au target, uses acetone and absolute alcohol to Si sheet ultrasonic cleaning 15 min successively, put coating chamber after the oven dry into.
(2) chamber is vacuumized, make the interior base vacuum degree of chamber 2.8 * 10 -4Pa.
(3) with mass flow flowmeter control Ar charge flow rate, make it to remain on about 20sccm, open the ion gun power supply, sputter energy 500eV, sputter line 20mA accelerates electric current 5mA.Sample is bombarded cleaning 5 min at least.Close the ion gun power supply.
(4) open the plasma sputter source, with mass flow flowmeter control Ar charge flow rate, make it to remain on about 20sccm.The sputter energy is 1keV, and the sputter line is 20mA.Accelerating voltage is 200V, and the acceleration electric current is 2mA.Sputtering time is 1h.
(5) the sputter target position is adjusted to Li 3PO 4And Si 3N 4Composite target (as described in embodiment 1) is opened the plasma sputter source, and regulating the Ar flow is 2sccm, N 2Flow is 2sccm, and the sputter energy is 1.1keV, and the sputter line is 20mA.Accelerating voltage is 200V, and the acceleration electric current is 4mA.Sputtering time is 2h.
(6) computer control is adjusted to the Au target with the sputter target position, opens the plasma sputter source, and control Ar flow is 20sccm.The sputter energy is 1keV, and the sputter line is 20mA.Accelerating voltage is 200V, and the acceleration electric current is 2mA.Sputtering time is 1h.
(7) film is in high vacuum chamber, drops to up to temperature and just opens chamber below 100 ℃ and take out.
The present invention has utilized nanometer mechanics test macro, X-ray diffraction (XRD) instrument, X ray energy dispersion spectrum (EDS) analyzer, x-ray photoelectron power spectrum (XPS) analyzer of American MTS to carry out comprising that physical propertys such as film thickness, structure, chemical composition, constituent content characterize respectively to film synthetic under the various process conditions.Utilize Princeton VersaSTAT4 multifunction electric chem workstation that the LiSiPON film is carried out ac resistance analysis in experiment, measuring frequency is that 0.1Hz is to 100KHz.The data result of test sees the following form, and main result is as follows:
1, with regard to physical property: the LiSiPON film is the same with LiPON, presents amorphous structure.Improve N 2The feeding amount effectively improve nitrogen content in the film, all contain a large amount of Si in the film under the different condition.The XPS collection of illustrative plates shows that N presents two kinds of different structures in film.
2, with regard to chemical property: the higher relatively film of nitrogen content has than higher ionic conductivity, is 6.8 * 10 -6S/cm, the introducing of N has improved the ionic conductivity of original system, along with N 2The increase of flow, the N content in the electrolytic thin-membrane and the synchronous increase of ionic conductivity have confirmed that further the nitrogen content in the film influences transportation and the migration of lithium ion, thereby have influenced conductivity.
Generally speaking: utilize low energy nitrogen ion bombardment Li 3PO 4And Si 3N 4The composite target of forming can obtain fine and close thin-film electrolyte LiSiPON uniformly, and the N that contains in the test proof film of constituent and chemical composition measures and N 2Flow is directly proportional, and N and Si are mixed with the raising that is beneficial to conductivity.N 2: when Ar was 1:1, nitrogen content was the highest in the film, and this moment, ionic conductivity can reach 6.8 * 10 -6S/cm is for coming into operation of film lithium ion battery provides the foundation.Further can prepare by the control technological parameter and have good 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
Full solid thin film battery LiCoO 2The preparation of/LiSiPON/Li
(1) before the experiment with rf magnetron sputtering at Si(110) substrate plates LiCoO 2Membrane electrode, sputtering time are 4h.
(2) use Equipment for Ion Beam Assisted Deposition plating thin-film electrolyte, the sputter target position is adjusted to Li 3PO 4And Si 3N 4Composite target (as described in embodiment 1) vacuumizes chamber, makes the interior base vacuum degree of chamber 2.8 * 10 -4Pa.
(3) open the plasma sputter source, regulating the Ar flow is 2sccm, N 2Flow is 2sccm, and the sputter energy is 1.1keV, and the sputter line is 20mA.Accelerating voltage is 200V, and the acceleration electric current is 4mA.Sputtering time is 5h.
(4) film is in high vacuum chamber, drops to up to temperature and just opens chamber below 100 ℃ and take out.
(5) film is placed vacuum thermal evaporation equipment, evaporation metal lithium membrane electrode, the evaporation time is 1h.
(6) adopt rf magnetron sputtering sputter Li on film 3PO 4Film is as protective layer, about 1h.So far be assembled into complete solid-State Thin Film Li-Ion Batteries.
The present invention's ion beam assisted depositing (IBAD) legal system open and that propose is equipped with the LiSiPON film, under the condition of suitable nitrogen argon gas stream flow ratio, can obtain chemical property electrolytic thin-membrane preferably, and 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 can be by using for reference this paper content, and 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 be in not breaking away from content of the present invention, spirit and scope to method as herein described with product is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.

Claims (5)

1. a LiSiPON lithium ion battery solid electrolyte film is characterized in that it is by N 2: the Ar volume flow ratio is the ion beam bombardment Li of 1:5-1 3PO 4And Si 3N 4, what obtain is thick in the LiSiPON film of 80nm ~ 150nm.
2. the described LiSiPON lithium ion battery of claim 1 solid electrolyte film, wherein the volume ratio of nitrogen argon flow is 1:1.
3. the preparation method of the described LiSiPON lithium ion battery of claim 1 solid electrolyte film is characterized in that being undertaken by following step:
(1) before deposit film, with circular Li 3PO 4Target is fixed in square Si 3N 4Above the target, use Ar +Target is synthesized in sputter, uses N simultaneously +Assist bombardment;
(2) deposit film in (100) of single-sided polishing monocrystalline silicon piece substrate adopts mechanical pump and molecular pump, and base vacuum is 2.8 * 10 during the control experiment -4Pa ~ 3.0 * 10 -4Pa, atmospheric pressure value is measured by ionization gauge, and sputter gas is selected pure N for use in the deposition process 2, Ar 2, controlling its flow with mass flow controller is 3 standard ml/min (sccm) ~ 6 standard ml/min (sccm); Total operating air pressure is 1.0 * 10 in the deposition process -2Pa ~ 1.2 * 10 -2Pa;
(3) experiment control N 2With the flow-rate ratio of Ar be 1:5-1.
4. the preparation method of the described LiSiPON of claim 3, (100) monocrystalline silicon piece of single-sided polishing is wherein used acetone, ethanol ultrasonic cleaning 15 minutes earlier successively, sends in the vacuum deposition chamber immediately after drying up; Before deposit film, use earlier 500eV, the Ar of 5mA +Sample is cleaned 5 min ~ 10min, during deposit film, regulate the nitrogen argon than the sputtering time of also accurately controlling each sample, plasma sputter source technological parameter: sputter energy 0.9keV ~ 1.1keV, sputter line 15mA ~ 20mA.
5. the application of the described LiSiPON lithium ion battery of claim 1 solid electrolyte film aspect 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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CN105862012A (en) * 2016-05-27 2016-08-17 上海交通大学 Solid electrolyte thin film and preparation method and ion device thereof
CN110120547A (en) * 2019-05-20 2019-08-13 新乡芯蕴智能科技有限公司 Preparation method and dielectric film for all-solid lithium-ion battery dielectric film

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