CN100346524C - Device and method for preparing solid thin-membrane lithium battery by in-situ deposition - Google Patents
Device and method for preparing solid thin-membrane lithium battery by in-situ deposition Download PDFInfo
- Publication number
- CN100346524C CN100346524C CNB200510028248XA CN200510028248A CN100346524C CN 100346524 C CN100346524 C CN 100346524C CN B200510028248X A CNB200510028248X A CN B200510028248XA CN 200510028248 A CN200510028248 A CN 200510028248A CN 100346524 C CN100346524 C CN 100346524C
- Authority
- CN
- China
- Prior art keywords
- film
- deposition
- chamber
- substrate
- magnetron sputtering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000008021 deposition Effects 0.000 title claims abstract description 109
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 75
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 title claims description 22
- 239000007787 solid Substances 0.000 title abstract 4
- 239000012528 membrane Substances 0.000 title 1
- 238000000151 deposition Methods 0.000 claims abstract description 112
- 238000004544 sputter deposition Methods 0.000 claims abstract description 28
- 238000012546 transfer Methods 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 238000002207 thermal evaporation Methods 0.000 claims abstract description 17
- 239000010408 film Substances 0.000 claims description 96
- 239000010409 thin film Substances 0.000 claims description 85
- 239000000758 substrate Substances 0.000 claims description 51
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000013077 target material Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000005477 sputtering target Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 5
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 239000000428 dust Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract 1
- 239000010931 gold Substances 0.000 description 14
- 229910012305 LiPON Inorganic materials 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000011066 ex-situ storage Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention belongs to the field of electrochemical techniques, particularly to a device of full solid film lithium batteries of IS deposit, and a method for producing the full solid film lithium batteries via the device. The device is composed of four deposit film chambers and a glove box in serial connection, different films are respectively prepared in the four different chambers: a DC magnetic control sputtering chamber is used for preparing electron ensemble fluid films, a DC or radio frequency magnetic control sputtering chamber is used for preparing cathode films, a radio frequency magnetic control sputtering chamber is used for preparing electrolyte films, and a vacuum thermal evaporation chamber is used for preparing lithium anode films. The present invention realizes the IS deposition of various films in the conditions of no breaking vacuum so as to prevent interfaces among the films from being polluted by dust, moisture and other pollutant. The full solid film lithium batteries prepared by the device have the advantages of little interface resistance, little charge transfer resistance and little capacity fade performance in charge and discharge cycle.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to equipment and a method for preparing an all-solid-state thin-film lithium battery in situ.
Background
In recent decades, miniaturization and integration of electronic products have become a great trend of the development of electronic technology in the world. Micro-electro-mechanical systems (MEMS), such as micro-sensors, micro-actuators, etc., have become important research and development fields in recent years in microelectronics, however, the existing energy supply system has been difficult to meet the increasing demand of MEMS systems for miniaturization and integration. The all-solid-state film lithium battery can be prepared by adopting a semiconductor deposition film technology, so that the minimum thickness of the all-solid-state film lithium battery can reach 10 micrometers, the all-solid-state film lithium battery has very excellent charge-discharge cycle performance and high specific energy, and the shape and the size of the all-solid-state film lithium battery can be designed at will. All-solid-state thin-film lithium batteries are therefore considered to be one of the most promising microbatteries in the field of MEMS applications.
The all-solid-state thin-film lithium battery mainly comprises an electron current collector thin film, a cathode thin film, an electrolyte thin film and a metal lithium anode thin film (as shown in figure 2), and the preparation method of each layer of thin film is different. The electronic current collector film is usually prepared by a direct current sputtering method, the cathode film and the electrolyte film are usually prepared by a radio frequency magnetron sputtering method, and the metallic lithium anode film is prepared by a vacuum thermal evaporation method. The electrochemical performance of the all-solid-state thin-film lithium battery depends on the material properties of a cathode thin film, an electrolyte thin film and an anode thin film, the quality of the interface quality among the thin films has great influence on the cycle performance of the all-solid-state thin-film lithium battery, and the interface quality is determined by equipment and a process for preparing the thin films. Jeon et al respectively prepare the all-solid-state thin-film lithium battery [1] under the conditions of 'ex-situ' and 'in-situ', wherein the 'ex-situ' method is to continuously deposit an electrolyte thin film after the preparation of a cathode thin film is finished and the cathode thin film is transferred in the air; the 'in-situ' method is to maintain the vacuum state of the system all the time during the preparation of the cathode film and the electrolyte film, and avoid the contact between the cathode film and the air. The research results show that the all-solid-state thin-film lithium battery prepared under the two conditions shows different electrochemical cycle performances, and the interface resistance and the charge transfer resistance of the battery prepared under the ex-situ condition are more than 10 times of those of the battery prepared under the in-situ condition, so that the charge-discharge cycle capacity attenuation of the battery is obviously higher than that of the battery prepared under the in-situ condition. It is obvious that the all-solid-state thin film lithium battery prepared under the "ex-situ" condition inevitably adsorbs dust, moisture and other contaminants in the air due to the direct contact of the cathode thin film with the air, and the presence of these contaminants not only reduces the adhesion property of the electrolyte thin film on the cathode thin film but also affects the quality of the interface between the cathode thin film and the electrolyte thin film [2 ]. Therefore, the 'in-situ' preparation method of the all-solid-state thin film lithium battery is beneficial to improving the electrochemical performance of the all-solid-state thin film lithium battery. However, at present, all-solid-state thin film lithium batteries are basically prepared under the condition of "ex-situ" due to the limitation of experimental conditions. Recently, Michel Martin and the like design a set of equipment [3] for preparing an all-solid-state thin-film lithium battery under the condition close to 'in-situ', the equipment consists of three thin-film deposition chambers, the functions of direct-current sputtering, radio-frequency sputtering and vacuum thermal evaporation are respectively completed, and materials are transferred through a central glove box. Obviously, to complete the deposition of the four most basic thin films of an all-solid-state thin-film lithium battery, at least one time during the preparation process, the chamber replacement target material and the corresponding mask (mask) for defining the shape of the deposited thin film need to be opened, which not only causes the pollution of the interface of the all-solid-state thin-film lithium battery, but also causes the mutual pollution of materials when the thin films of different materials are deposited in the same chamber.
The invention provides novel equipment for in-situ deposition of an all-solid-state thin film lithium battery, which is formed by connecting four deposition thin film chambers and a glove box in series, and a method for preparing the all-solid-state thin film lithium battery by adopting the equipment. The four chambers respectively realize the preparation of an electronic current collector film by direct current magnetron sputtering, the preparation of a cathode film by direct current or radio frequency magnetron sputtering, the preparation of an electrolyte film by radio frequency magnetron sputtering and the preparation of a lithium metal anode film by vacuum thermal evaporation. Thus really realizing the preparation of the all-solid-state thin film lithium battery by in-situ deposition under the condition of not damaging vacuum.
Reference to the literature
[1]E.J.Jeon，Y.W.Shin，S.Ch.Nam，W.Cho，and Y.S.Yoon.J.Electrochem.Soc.，148(4)，A318-A322(2001)
[2]J.B.Bates，N.J.Dudney，G.R.Gruzalski，R.A.Zuhr，A.Choudhury，andC.F.Luck，J.Power Sources，43-44，103(1993)
[3]M.Martin，F.Faverjon，Thin Solid Films，398-399，572-574(2001)
Disclosure of Invention
The invention aims to provide equipment and a method for preparing an all-solid-state thin-film lithium battery by in-situ deposition, which can avoid interface pollution and mutual pollution among materials of the battery.
The equipment for preparing the all-solid-state thin-film lithium battery by in-situ deposition is formed by connecting four deposition thin-film chambers, a glove box and a control system, and the structure of the equipment is shown in figure 1. Wherein,
the four deposition film chambers are respectively a direct current magnetron sputtering chamber I, a direct current or radio frequency magnetron sputtering chamber II, a radio frequency magnetron sputtering chamber III and a vacuum thermal evaporation chamber IV, and are respectively used for preparing an electronic current collecting film, a cathode film, an electrolyte film and a metal lithium anode film of the all-solid-state film lithium battery. The four deposition chambers are connected in series with a glove box 11, the glove box is connected with the deposition chambers through a gate valve 6, and the glove box is used for installing substrates and packaging or transferring all-solid-state thin-film lithium batteries. A transfer trolley 1 is arranged in the deposition chamber and used for placing a substrate 2 for depositing a film; the middle part of each deposition chamber is provided with a through track 5 for the transfer trolley 1 to move; the positioning of the transfer trolley 1 is controlled by a light-operated positioning switch 3; the lower part of each deposition chamber is provided with a mask 7; deposition target tables 9 are respectively arranged at the lower parts of the masks 7 in the deposition chambers I, II and III and used for placing corresponding targets, and evaporation boats 8 are arranged at the lower parts of the masks 7 in the deposition chambers II; at least one of the 4 deposition chambers is provided with a substrate heating system 4, for example, the heating system is arranged in the deposition chamber II; the control system 10 is used for controlling the movement of the transmission trolley 1 and the lifting of the mask 7, and controlling the work of a heating system, an exhaust system, an air inlet system and the like.
In the deposition equipment, a substrate 2 is placed on a transfer trolley, the transfer trolley moves on a track 5, and the positioning of the trolley is accurately controlled through a light-operated positioning switch 3, so that the substrate 2 can accurately reach the upper surface of a preset mask 7; the mask 7 is raised and lowered by a control system 10 to ensure that the mask 7 is in close contact with the substrate 2.
In the deposition equipment, corresponding target materials are respectively placed on deposition target tables 9 in deposition chambers I, II and III; a metal lithium sheet is placed on the evaporation boat 8 in the deposition chamber IV; the deposition conditions of the respective layers of the thin film are controlled by the control system 10.
In the deposition equipment, at least one deposition chamber is provided with a substrate heating system 4, and the temperature of the substrate 2 can be continuously adjusted at room temperature to 600 ℃ by controlling the heating system 4 through a control system 10, so that the requirement of heating treatment in the film deposition process or after the deposition is finished is met.
In the deposition equipment, a glove box 11 is connected with a deposition chamber IV through a gate valve 6; when the gate valve 6 is closed, the background vacuum degree of the four deposition chambers can reach 1 multiplied by 10-3Pa; when the gate valve 6 is opened, the transfer trolley 1 can reach or leave the glove box 11 through the gate valve 6; the glove box 11 is filled with a dry inert gas such as argon (moisture content less than 10 ppm).
The control system 10 of the invention controls the operation of the exhaust system and the air intake system of the equipment to ensure that the deposited film chamber reaches the required background vacuum degree (1 multiplied by 10)-3Pa) and maintaining the working atmosphere and pressure required for film deposition.
The method for preparing the all-solid-state thin film lithium battery by in-situ deposition comprises the following steps: the deposition equipment is utilized to sequentially deposit an electronic current collector film, a cathode film, an electrolyte film and a metal lithium anode film in deposition chambers I, II, III and IV, and then dry argon is filled into 4 deposition chambers to reach a standard atmospheric pressure; and opening the gate valve 6, controlling the transfer trolley 1 to enter the glove box 11, and taking out the substrate deposited with the all-solid-state thin film lithium battery.
Wherein the thickness of the electron current collector film is controlled to be 50-500nm, the thickness of the cathode film is controlled to be 50nm-3 μm, the thickness of the electrolyte film is controlled to be 1.0-2.5 μm, and the thickness of the metal lithium anode film is controlled to be 1.0-5.0 μm.
The invention has the advantages that the 'in-situ' deposition of the electronic current collector film, the cathode film, the electrolyte film and the metal lithium anode film of the all-solid-state thin film lithium battery is realized under the condition of not damaging vacuum, and the interface between the films is prevented from being polluted by dust, moisture and other pollutants; different films are respectively deposited in different chambers, so that mutual pollution of different film materials is avoided. The all-solid-state thin-film lithium battery deposited by the device under the in-situ condition has smaller interface resistance and charge transfer resistance, and shows smaller capacity attenuation performance in charge-discharge cycles, so that the all-solid-state thin-film lithium battery with excellent electrochemical performance is easier to prepare.
Drawings
FIG. 1 is a schematic view of an in-situ deposition apparatus.
Fig. 2 is a process for preparing an all-solid-state thin film lithium battery.
FIG. 3 shows Au/TiO2The cycling performance of a/LiPON/Li all-solid-state thin film lithium battery.
FIG. 4 shows Au/TiO2The alternating current impedance spectrogram of the/LiPON/Li all-solid-state thin-film lithium battery.
Detailed Description
The preparation sequence and the figure of each layer of the all-solid-state thin film lithium battery are shown in figure 2.
The preparation of the electronic current collector film adopts metal Pt (or other suitable metals such as Au, Ti, V and the like) as a target material, and deposits the electronic current collector film on the electrically insulated substrate 2 by a direct current magnetron sputtering method. The sputtering conditions were: the background pressure of the deposition chamber reaches 1 x 10-3After Pa, the control system (10) moves the transfer trolley 1 to a direct current sputtering deposition chamber I, and automatically or manually controls a mask of the deposition chamber to ascend to a position where the distance between the mask and the substrate is less than 3mm (such as 0.1-3 mm), wherein the distance between a target and the substrate is 4-8 cm; the target material is sputtered for 30-60min before the film is deposited, the sputtering atmosphere is pure argon, the working pressure is 0.5-2.5 Pa, and the deposition power is 30-150W. The substrate can be ceramic wafer, quartz wafer, glass wafer or silicon wafer, and the temperature of the substrate is room temperature during deposition. The thickness of the electron current collector film is 50nm to 500nm, preferably about 300 nm.
Preparing a cathode film, and adopting corresponding materials as sputtering targets of the cathode film, such as: deposition of V2O5A cathode film of metal V or V2O5As a target material; deposition of LiCoO2Cathode film, optionally LiCoO2As a target material. The deposition of the cathode film is finished by a deposition chamber II, the deposition chamber can respectively carry out direct current or radio frequency magnetron sputtering, and the sputtering mode is adjusted according to the selected target material. When the electron current collector film sputtering is finished, the system background vacuum state (1X 10) is still kept-3Pa), the transfer trolley 1 is moved to a direct current or radio frequency sputtering deposition chamber II through a control system 10, and a mask of the deposition chamber is automatically or manually controlled to be lifted to a position (such as a position of 0.1-3 mm) which is less than 3mm away from the substrate; the deposition conditions vary from sputtering target to sputtering target. The temperature of the substrate can be controlled by the heating system 4 to be continuously adjustable within the range of room temperature to 600 ℃ during the deposition of the cathode film; after the deposition of the cathode film is finished, the substrate temperature can be controlled by the heating system 4 to carry out in-situ annealing treatment at the temperature lower than 600 ℃, and the annealing atmosphere can be selected from inert gas or oxygen. The thickness of the cathode film is 50nm to 3 μm, preferably less than 1 μm.
In the preparation of the electrolyte film, at present, the nitrogen-containing lithium phosphate LiPON film is the electrolyte film with the best lithium ion conductivity in the all-solid-state thin-film lithium battery. When the cathode film sputtering is finished, the vacuum state (1X 10) of the system background is still kept-3Pa), the transfer trolley 1 is moved to a radio frequency magnetron sputtering deposition chamber (c) by a control system 10, and a mask of the deposition chamber is automatically or manually controlled to be lifted to a position (such as a position of 0.1-3 mm) which is less than 3mm away from the substrate; the sputtering conditions were: the distance between the target and the substrate is 4-8 cm, the target needs to be sputtered for 30-60min before the film is deposited, the sputtering atmosphere is pure nitrogen, the working pressure is 0.5-2.5 Pa, and the deposition power is 30-150W. The substrate temperature during deposition is less than 150 ℃. The thickness of the electrolyte thin film is 1.0 μm to 2.5 μm, preferably about 1.5 μm.
Preparing a lithium metal anode (Li anode) film, and depositing the lithium metal film by adopting a vacuum thermal evaporation method. The metal lithium sheet is used as evaporation material, the molybdenum boat or iron boat is used as heating evaporator, and the vacuum thermal evaporation process is completed by the chamber. When the electrolyte film sputtering is finished, the system background is still keptEmpty state (1 × 10)-3Pa), the transfer trolley 1 is moved to a vacuum thermal evaporation deposition chamber (r) through a control system 10, and a mask of the deposition chamber is automatically or manually controlled to ascend to a position (such as a position 0.1-3 mm) which is less than 3mm away from the substrate; the thermal evaporation conditions were: pressure below 1X 10-3Pa, the temperature of the substrate is room temperature, the distance from the heating evaporator to the substrate is 6-15 cm, and the film deposition rate is about 50-500 nm/min. The thickness of the lithium metal anode thin film is 1.0 μm to 5.0. mu.m, preferably about 3.0. mu.m.
Transferring an all-solid-state thin film lithium battery, after the deposition of a metal lithium anode thin film is finished, controlling an air inlet valve to charge dry argon (the moisture content is lower than 10ppm) into four deposition chambers to reach 1 standard atmospheric pressure through a control system (10); and opening the gate valve 6 to control the transfer trolley 1 to move into the glove box 11. The substrate on which the all-solid-state thin-film lithium battery was deposited was taken out of the glove box 11, placed in a sealed container, and transferred to another glove box filled with dry argon (moisture content less than 10ppm) to perform an electrochemical test.
In order to better clarify the invention, the following detailed description is given with reference to the examples and the accompanying drawings.
In this example, Al is used2O3Ceramic as substrate, gold (Au) film as electronic current collector, and titanium dioxide (TiO)2) Au/TiO was prepared using a thin film as a cathode, a nitrogen-containing lithium phosphate (LiPON) thin film as an electrolyte, and a metallic lithium (Li) thin film as an anode2The lithium battery comprises a solid-state thin film lithium battery body and a lithium ion battery body.
The preparation process of the Au thin film comprises the following steps: the background pressure of the system reaches 1 x 10-3After Pa, the transfer trolley (1) is moved to a direct current magnetron sputtering deposition chamber (I) through a control system (10), and a mask of the deposition chamber is automatically controlled to rise to a position with a distance of 0.3mm from the substrate; selecting an Au sheet with the diameter of 50mm as a sputtering target material, wherein the distance from the target to a substrate is 5cm, the target material is sputtered for 30min in advance before the film is deposited, the sputtering atmosphere is pure argon, the working pressure is 0.5Pa, the deposition power is 150W, and the temperature of the substrate is room temperature during deposition. After 2 minutes of deposition, a gold (Au) film was obtainedThe thickness was 50 nm.
TiO2The preparation process of the film comprises the following steps: when the sputtering of the gold (Au) film is finished, the vacuum state (1 multiplied by 10) of the system background is still kept-3Pa), the transfer trolley (1) is moved to a direct current or radio frequency sputtering deposition chamber II through a control system (10), and a mask of the deposition chamber is manually controlled to rise to a position with the distance of 0.3mm from the substrate; selecting a metal titanium (Ti) sheet with the diameter of 50mm as a sputtering target material, and depositing a film by utilizing direct-current magnetron sputtering; the distance from the target to the substrate is 5cm, the target is sputtered for 30min before the film is deposited, the working pressure is 1.5Pa, the working gas consists of the mixed gas of argon and oxygen (the volume ratio is 3: 1), the deposition power is 50W, and the substrate temperature is 100 ℃ during deposition. After 10 minutes of deposition, TiO was obtained2The thickness of the film was 70 nm.
The preparation process of the LiPON film comprises the following steps: when TiO is present2After the film sputtering is finished, the vacuum state (1 multiplied by 10) of the system background is still kept-3Pa), the transfer trolley (1) is moved to a radio frequency magnetron sputtering deposition chamber (c) through a control system (10), and a mask of the deposition chamber is manually controlled to rise to a position with a distance of 0.3mm from the substrate; selecting a lithium phosphate target with the diameter of 50mm as a sputtering target material; the distance from the target to the substrate is 7cm, the target material needs to be sputtered for 30min before the film is deposited, the sputtering atmosphere is pure nitrogen, the working pressure is 1.5Pa, the deposition power is 70W, and the electrolyte film with the thickness of about 2.0 mu m can be obtained after continuous deposition for 15 h.
The preparation process of the Li film comprises the following steps: when the LiPON film sputtering is finished, the vacuum state (1 multiplied by 10) of the system background is still kept-3Pa), the transfer trolley (1) is moved to a vacuum thermal evaporation deposition chamber (iv) through a control system (10), and a mask of the deposition chamber is manually controlled to rise to a position with a distance of 0.3mm from the substrate; a1 g metal lithium plate was used as a vapor deposition material, and a molybdenum boat was used as a heating evaporator. The thermal evaporation conditions were: pressure of 1X 10-3Pa, the temperature of the substrate is room temperature, the distance from the evaporator to the substrate is 15cm, the evaporation power is 300W, and the deposition rate of the film is about 200 nm/min. The thickness of the lithium metal anode film was 3.0. mu.m.
After the deposition of the lithium metal anode film is finished, dry argon (the moisture content is lower than 10ppm) with 1 standard atmospheric pressure is filled into the four deposition chambers by controlling an air inlet valve through a control system (10), a gate valve (6) is opened, and a transfer trolley (1) is controlled to move into a glove box (11). The all-solid-state thin-film lithium battery was taken out in a glove box (11), placed in a sealed container, transferred to another glove box filled with dry argon (moisture content less than 10ppm) and subjected to electrochemical testing.
Electrochemical performance testing of the thin film battery was performed by the CHI electrochemical workstation. Au/TiO2The LiPON/Li all-solid-state thin-film lithium battery shows good charge-discharge cycle performance (figure 3): at 5. mu.A/cm2The discharge capacity was almost stably maintained at 0.27. mu.Ah in the first 50 cycles of the current density of (1); at a rate of 10. mu.A/cm2The discharge capacity is hardly attenuated even in 50-550 cycles of the current density of (1), and is kept at about 0.25 muAh; from the 1 st and 50 th AC impedance spectrograms (FIG. 4) of the thin film battery, Au/TiO prepared by the 'in-situ' deposition equipment2The internal resistance of the/LiPON/Li all-solid-state thin-film lithium battery hardly changes. This indicates that the all-solid-state thin film lithium battery has very stable electrochemical cycling performance.
Claims (6)
1. The equipment for preparing the all-solid-state thin-film lithium battery by in-situ deposition is characterized by comprising four deposition thin-film chambers, a glove box (11) and a control system (10), wherein the four deposition thin-film chambers are respectively a direct-current magnetron sputtering chamber I, a direct-current or radio-frequency magnetron sputtering chamber II, a radio-frequency magnetron sputtering chamber III and a vacuum thermal evaporation chamber IV which are respectively used for preparing an electronic current collecting thin film, a cathode thin film, an electrolyte thin film and a metal lithium anode thin film of the all-solid-state thin-film lithium battery, the four deposition chambers are connected with the glove box (11) in series, and the glove box is connected with the vacuum thermal evaporation chamber IV through a gate valve (6); a transfer trolley (1) for placing a substrate (2) for depositing a film is arranged in the deposition chamber; the middle part of each deposition chamber is provided with a through track (5) for the transfer trolley (1) to move; the positioning of the transfer trolley (1) in the deposition chamber is controlled by a light-operated positioning switch (3); the lower part of each deposition chamber is provided with a mask (7); the lower parts of the masks (7) in the direct current magnetron sputtering chamber I, the direct current or radio frequency magnetron sputtering chamber II and the radio frequency magnetron sputtering chamber III are respectively provided with a deposition target platform (9), and the lower parts of the masks (7) in the vacuum thermal evaporation chamber IV are provided with evaporation boats (8); at least one of the 4 deposition chambers is provided with a substrate heating system (4); the control system (10) is used for controlling the movement of the transmission trolley (1) and the lifting of the mask (7) and controlling the work of the heating system, the exhaust system and the air inlet system.
2. A method for preparing an all-solid-state thin film lithium battery by in-situ deposition by using the device of claim 1, which is characterized by comprising the following specific steps: by utilizing the deposition equipment, a direct current magnetron sputtering chamber I, a direct current or radio frequency magnetron sputtering chamber II, a radio frequency magnetron sputtering chamber III and a vacuum thermal evaporation chamber IV are sequentially deposited on an electric insulation substrate to form an all-solid-state thin film lithium battery, and then dry argon is filled into 4 deposition chambers to reach a standard atmospheric pressure; opening the gate valve (6), controlling the transfer trolley (1) to enter the glove box (11), and taking out the manufactured all-solid-state thin-film lithium battery;
wherein the thickness of the electron current collector film is controlled to be 50-500nm, the thickness of the cathode film is controlled to be 50nm-3 μm, the thickness of the electrolyte film is controlled to be 1.0-2.5 μm, and the thickness of the metal lithium anode film is controlled to be 1.0-5.0 μm.
3. The method according to claim 2, characterized in that the preparation of the electron collector thin film, using metal Pt, Au, Ti or V as target, deposits the electron collector thin film on the electrically insulating substrate (2) by means of dc magnetron sputtering; the sputtering process and conditions were: the background pressure of the deposition chamber reaches 1 x 10-3After PaThe control system (10) moves the transfer trolley (1) to a direct current magnetron sputtering chamber I, and automatically or manually controls a mask of the deposition chamber to ascend to a position where the distance between the mask and the substrate is less than 3 mm; the distance from the target to the substrate is 4-8 cm; the target material is sputtered for 30-60min before the film is deposited, the sputtering atmosphere is pure argon, the working pressure is 0.5-2.5 Pa, and the deposition power is 30-150W.
4. The method according to claim 2, characterized in that the preparation of the cathode film, adopt the corresponding material as the sputtering target material of the cathode film, after the electron current collector film sputters and finishes, still keep the system background vacuum state control system (10) to move the transfer car (1) to the direct current or radio frequency magnetron sputtering chamber (c), and rise to the distance of less than 3mm with the substrate through the mask of automatic or manual control this deposition chamber; the temperature of the substrate can be controlled within the range of room temperature to 600 ℃ by the heating system (4) during the deposition of the cathode film; after the deposition of the cathode film is finished, the temperature of the substrate is controlled to be lower than 600 ℃ through a heating system (4) to carry out in-situ annealing treatment, and inert gas or oxygen is selected as the annealing atmosphere.
5. The method according to claim 2, wherein the electrolyte thin film is prepared by using lithium phosphate as a target material when preparing the nitrogen-containing lithium phosphate as an electrolyte; after the sputtering of the cathode film is finished, the system background vacuum state is still kept, the transfer trolley (1) is moved to a radio frequency magnetron sputtering chamber (c) through a control system (10), and the mask of the deposition chamber is automatically or manually controlled to rise to a position where the distance between the mask and the substrate is less than 3 mm; the sputtering conditions were: the distance from the target to the substrate is 4-8 cm, the target needs to be sputtered for 30-60min before the film is deposited, the sputtering atmosphere is pure nitrogen, the working pressure is 0.5-2.5 Pa, the deposition power is 30-150W, and the temperature of the substrate is less than 150 ℃ during deposition.
6. The method of claim 2, wherein the lithium metal anode film is prepared by using a lithium metal sheet as a vapor deposition material, and a molybdenum boat or an iron boat as a heating evaporator; as an electrolyteAfter the film sputtering is finished, the system background vacuum state is still kept, the control system (10) moves the transfer trolley (1) to a vacuum thermal evaporation chamber IV, and the mask of the deposition chamber is automatically or manually controlled to ascend to a position where the distance between the mask and the substrate is less than 3 mm; the thermal evaporation conditions were: pressure below 1X 10-3Pa, the temperature of the substrate is room temperature, the distance from the heating evaporator to the substrate is 6-15 cm, and the film deposition rate is about 50-500 nm/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510028248XA CN100346524C (en) | 2005-07-28 | 2005-07-28 | Device and method for preparing solid thin-membrane lithium battery by in-situ deposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510028248XA CN100346524C (en) | 2005-07-28 | 2005-07-28 | Device and method for preparing solid thin-membrane lithium battery by in-situ deposition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1747217A CN1747217A (en) | 2006-03-15 |
| CN100346524C true CN100346524C (en) | 2007-10-31 |
Family
ID=36166629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510028248XA Expired - Fee Related CN100346524C (en) | 2005-07-28 | 2005-07-28 | Device and method for preparing solid thin-membrane lithium battery by in-situ deposition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100346524C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101771168B (en) * | 2010-02-11 | 2012-05-23 | 厦门大学 | Method for preparing miniature lithium battery |
| CN103358326A (en) * | 2012-03-28 | 2013-10-23 | 绿种子科技(潍坊)有限公司 | Glove box and thin film deposition equipment with same |
| FR2995454B1 (en) * | 2012-09-07 | 2014-08-22 | Commissariat Energie Atomique | PROCESS FOR PRODUCING LITHIUM ELECTROLYTE FOR SOLID MICRO-BATTERY |
| CN103057212B (en) * | 2013-01-10 | 2015-06-17 | 中亨新型材料科技有限公司 | Barrier film and vacuum insulating board adopting same |
| US9890449B2 (en) * | 2015-04-29 | 2018-02-13 | Seagate Technology Llc | Methods of forming MgO barrier layer |
| CN107069075A (en) * | 2017-05-20 | 2017-08-18 | 复旦大学 | A kind of Prussian blue/nitridation lithium phosphate/lithium solid state secondary battery and preparation method thereof |
| CN107464913B (en) * | 2017-07-07 | 2019-12-06 | 中国航发北京航空材料研究院 | Method for producing all-solid-state thin film lithium battery |
| CN110352264A (en) * | 2018-02-07 | 2019-10-18 | 株式会社爱发科 | Film forming method, film forming device and lithium battery |
| CN110838597A (en) * | 2018-08-15 | 2020-02-25 | 广州市思创信息技术有限公司 | Preparation method of thin film lithium battery |
| CN111276749B (en) * | 2018-12-04 | 2021-01-26 | 有研工程技术研究院有限公司 | Method for preparing high-performance all-solid-state thin-film lithium battery by radio frequency magnetron sputtering method |
| CN109609910B (en) * | 2019-01-10 | 2021-04-13 | 深圳市致远动力科技有限公司 | Thin film battery preparation device and method |
| WO2020168517A1 (en) * | 2019-02-21 | 2020-08-27 | 京东方科技集团股份有限公司 | Lithium ion battery and preparation method therefor |
| CN114373937B (en) * | 2022-01-13 | 2024-07-16 | 上海空间电源研究所 | Preparation method of high-stability all-solid-state thin film lithium battery current collector thin film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6203941B1 (en) * | 1998-12-18 | 2001-03-20 | Eveready Battery Company, Inc. | Formed in situ separator for a battery |
| CN1389946A (en) * | 2002-05-23 | 2003-01-08 | 上海交通大学 | In-situ making process of nano Al2O3 particvle reinforced porous nickel anode |
| CN1447473A (en) * | 2003-03-06 | 2003-10-08 | 复旦大学 | Method for preparing lithium ion solid electrolyte film with large area |
| CN1601791A (en) * | 2004-10-21 | 2005-03-30 | 复旦大学 | Full solid film lithium cell and its prepn process |
-
2005
- 2005-07-28 CN CNB200510028248XA patent/CN100346524C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6203941B1 (en) * | 1998-12-18 | 2001-03-20 | Eveready Battery Company, Inc. | Formed in situ separator for a battery |
| CN1389946A (en) * | 2002-05-23 | 2003-01-08 | 上海交通大学 | In-situ making process of nano Al2O3 particvle reinforced porous nickel anode |
| CN1447473A (en) * | 2003-03-06 | 2003-10-08 | 复旦大学 | Method for preparing lithium ion solid electrolyte film with large area |
| CN1601791A (en) * | 2004-10-21 | 2005-03-30 | 复旦大学 | Full solid film lithium cell and its prepn process |
Non-Patent Citations (1)
| Title |
|---|
| 锂磷氧氮(LIPON)薄膜电解质和全固态薄膜锂电池研究 刘文元，傅正文，秦启宗，化学学报，第62卷第22期 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1747217A (en) | 2006-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100346524C (en) | Device and method for preparing solid thin-membrane lithium battery by in-situ deposition | |
| CN101035924B (en) | Method of fabricating an electrochemical device using ultrafast pulsed laser deposition | |
| KR101010716B1 (en) | Method for depositing ceramic thin film by sputtering using non-conductive target and its apparatus therefor | |
| CN106099201B (en) | A kind of preparation method of the All-solid film batteries of high-energy density | |
| CN114300733B (en) | All-solid-state thin-film lithium battery and preparation method thereof | |
| CN113564524B (en) | Method for preparing carbon-coated three-dimensional porous copper current collector | |
| CN107464913A (en) | A kind of method and apparatus for producing all solid-state thin-film lithium battery | |
| CN1870325A (en) | Lithium ion secondary battery negative plate material with three-layer cell structure and preparation method | |
| CN118064831A (en) | Gradient nickel oxide film and preparation method and application thereof | |
| CN101174687A (en) | Production method for nickel oxide anode thin film used for full solid-state thin-film lithium ion battery | |
| CN116845333A (en) | All-solid-state thin-film lithium ion battery and preparation method thereof | |
| CN109148826B (en) | Negative electrode, preparation method thereof and lithium battery | |
| CN113151790B (en) | Ion/electron common conductor film, preparation method thereof, solid-state battery and electric vehicle | |
| CN115386837B (en) | Preparation method of lead-free high-energy-storage-density ferroelectric film | |
| CN106058305A (en) | Method for preparing miniature all-solid-state thin-film lithium ion battery in situ by using PLD (pulsed laser deposition) | |
| KR20150042011A (en) | Preparation method of a film comprising nanowires, the film comprising nanowires and a thin film battery conprsing the same | |
| CN102751381A (en) | Preparation method for copper indium selenium base film solar cell molybdenum electrode | |
| Zhang et al. | Characterization of all solid state batteries with LiPON thin films obtained with different substrates and RF sputtering times | |
| CN110438449A (en) | A kind of cobalt acid lithium composite film electrode and preparation method thereof | |
| CN111020504A (en) | Li1+xAlxGe2-x(PO4)3Preparation method and application of solid electrolyte film | |
| CN116169244B (en) | Solid-state battery cathode and preparation method thereof | |
| CN117230424A (en) | Vacuum film plating equipment and method for thin film battery | |
| CN110311163A (en) | A kind of lithium ion battery and preparation method thereof based on LiPON electrolyte | |
| WO2010115062A2 (en) | Electrode compositions and processes | |
| CN117364042A (en) | Preparation method of oxide film, oxide film and application of oxide film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071031 Termination date: 20100728 |