CN107464913A - A kind of method and apparatus for producing all solid-state thin-film lithium battery - Google Patents

A kind of method and apparatus for producing all solid-state thin-film lithium battery Download PDF

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Publication number
CN107464913A
CN107464913A CN201710550041.1A CN201710550041A CN107464913A CN 107464913 A CN107464913 A CN 107464913A CN 201710550041 A CN201710550041 A CN 201710550041A CN 107464913 A CN107464913 A CN 107464913A
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China
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chamber
sample
vacuum
battery
substrate
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CN201710550041.1A
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Chinese (zh)
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陈牧
颜悦
刘伟明
张晓锋
韦友秀
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中国航发北京航空材料研究院
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Priority to CN201710550041.1A priority Critical patent/CN107464913A/en
Publication of CN107464913A publication Critical patent/CN107464913A/en

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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/04Construction or manufacture in general
    • H01M10/0404Machines for assembling batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562Solid materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0404Methods of deposition of the material by coating on electrode collectors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0421Methods of deposition of the material involving vapour deposition

Abstract

The invention belongs to cell manufacturing techniques and technical field of vacuum plating, are related to a kind of method and apparatus for producing all solid-state thin-film lithium battery.Under not exposure air environment, single cell battery is manufactured in surface using vacuum coating equipment by the present invention.Battery structure uses the single cell battery Stacking units that n times repeat, and without additional circuit, self-assembling formation high-voltage thin-film lithium battery in structure, the current actual measurement burning voltage of battery is 6V 100V;The battery is divided into two in structure:First item is the high-voltage battery containing negative pole, and second item is the high-voltage battery of no negative pole.The present invention realizes the reciprocal plated film of sequencing, avoids exposed vacuum and causes film by air pollution, so as to realize the continuity and uniformity of the lithium battery preparation of production high-voltage thin-film.In process of production, each operation step can be continuous, and no mutual interference, relatively conventional production efficiency of equipment improves more than 30%.

Description

A kind of method and apparatus for producing all solid-state thin-film lithium battery

Technical field

The invention belongs to cell manufacturing techniques and technical field of vacuum plating, are related to a kind of production all solid-state thin-film lithium battery Method and apparatus.

Background technology

Conventional lithium ion battery is generally basede on liquid organic electrolyte and barrier film, potential safety hazard in service life be present. Using solid electrolyte alternative electrolyte, development all-solid lithium-ion battery be solve cell safety hidden danger optimal case it One.All solid-state thin-film lithium battery is all-solid lithium-ion battery one of most potential branch at present, the master of single cell battery Film layer structure is wanted to be made up of collector, positive pole, electrolyte, negative pole, the encapsulated layer formed in refractory substrates, its electrolyte Part be based primarily upon phase at beginning of the nineties in last century Oak Ridge National Laboratory Bates J B et al. exploitation with nitrogen doped phosphorus Sour lithium film (LiPON).

Single all solid-state thin-film lithium battery preparation method mainly uses Vacuum Coating method, the film layer that this method makes at present It is fine and close and possess higher degree, deposit plural layers under exposure vacuum condition.For the technique stream of all solid-state thin-film lithium battery The equipment that journey is built has specificity.Such as Japanese Ai Fake companies (Jimbo et al., Energy Procedia 14 (2012) 1574-1579) and Fudan University (CN1747217A) using tandem chamber structure make single cell battery;Cluster tool Method it is public by company of Applied Materials (CN102576898, CN102037586A, CN103608958A) and French ZI Sud (Martin et al., Thin Solid Films 38-399 (2001) 572-574) is taken charge of using making single cell battery.These electricity Pond manufacturing equipment structure is complex, and finished battery is generally the single cell battery of 3-4V low-voltages, can not directly meet most of Electronic product and automobile power cell demand (voltage>6V).On the other hand, automobile power cell, Notebook Battery use mostly High-voltage lithium ion batteries group, its battery pack are often formed by single cell battery by the external circuit series parallel structure of complexity.How Series parallel structure of the inside battery without lead is realized, simplifies production process and reduces the use of raw material, is long-standing problem lithium electricity The problem of pond industry.

The content of the invention

The present invention can only prepare the deficiency of low-voltage battery, and portable power source for existing film lithium cell manufacture method The demand that industry is used high-voltage battery, propose a kind of method and apparatus for producing high voltage all solid-state thin-film lithium battery.

The technical solution of the present invention is, using vacuum coating equipment under not exposure air environment, in surface system Single cell battery is made, for the mode of deposition to be one of following, (one) deposits collector, positive pole, electrolyte, negative pole list on substrate successively Core battery, according to the magnitude of voltage of required battery product, the multiple collectors of repeated deposition, positive pole, electrolysis above single cell battery Matter, negative pole single cell battery, (two) deposit collector, positive pole, electrolyte single cell battery on substrate successively, according to required battery The magnitude of voltage of product, the multiple collectors of repeated deposition, positive pole, electrolyte single cell battery, plating steps are on single cell battery:

1) equipment of manufacture production all solid-state thin-film lithium battery, equipment include five chambers and a control calculating first Machine, wherein two chamber are vacuum coating chamber, and the other three is respectively that vacuum annealing chamber, cell package chamber and sample pass Pass chamber;Vacuum coating chamber, vacuum annealing chamber and cell package chamber transmit chamber by vacuum valve and sample and connected Connect, for cell package chamber by anhydrous, anaerobic and inert atmosphere protection, it is vacuum environment that sample, which transmits chamber, and sample transmits chamber In be provided with vacuum mechanical-arm or vacuum robot as transmission system;

2) battery is produced, its process is controlled by computer, and control process is one of following:

Process one is,

Step 1, in the first vacuum coating chamber, carry out substrate surface treatment, the mask plated film and just of plus plate current-collecting body The mask plated film of pole;Next step is determined according to the attribute of positive electrode, when positive electrode needs to be made annealing treatment, entered Enter step 2, when positive electrode need not be made annealing treatment, be directly entered step 3;

Step 2, the vacuum valve between the first vacuum coating chamber and sample transmission chamber is opened, controls sample transmission Transmission system in chamber, substrate is transferred to sample and transmits chamber, closed the first vacuum coating chamber and transmit chamber with sample Between vacuum valve, open vacuum annealing chamber and sample and transmit vacuum valve between chamber, control sample transmits chamber In transmission system, substrate is transferred to vacuum annealing chamber, carries out positive pole the high temperature anneal, open vacuum annealing chamber with Sample transmits the vacuum valve between chamber, and control sample transmits transmission system in chamber, and substrate is transferred into sample transmits chamber Room, the vacuum valve between the first vacuum coating chamber and sample transmission chamber is opened, substrate is transferred to the first vacuum coating Chamber;

Step 3, electrolyte plated film is carried out in the first vacuum coating chamber;

Step 4, the vacuum valve between the first vacuum coating chamber and sample transmission chamber is opened, controls sample transmission Transmission system in chamber, substrate is transferred to sample and transmits chamber, closed the first vacuum coating chamber and transmit chamber with sample Between vacuum valve, open the second vacuum coating chamber and sample and transmit vacuum valve between chamber, control sample transmission Transmission system in chamber, substrate is transferred to the second vacuum coating chamber, carries out the mask plated film of negative pole, open the second vacuum Coating chamber and sample transmit the vacuum valve between chamber, and control sample transmits the transmission system in chamber, substrate is transmitted Chamber is transmitted to sample;Next step is determined according to the attribute of negative material, when negative material needs to be made annealing treatment, Into step 5, when negative material need not be made annealing treatment, step 6 is directly entered;

Step 5, opens the vacuum valve between vacuum annealing chamber and sample transmission chamber, and control sample transmits chamber Middle transmission system, substrate is transferred to vacuum annealing chamber, carries out negative pole the high temperature anneal, opens vacuum annealing chamber and sample Product transmit the vacuum valve between chamber;

Step 6, substrate is transferred to sample and transmits chamber, open the first vacuum coating chamber and sample transmit chamber it Between vacuum valve, substrate is transferred to the first vacuum coating chamber, carries out negative current collector mask plated film;

Step 7, according to the magnitude of voltage of required battery, repeat step one to step 6, the number repeated is cell voltage Value divided by single cell battery magnitude of voltage, numerical value round numbers;

Step 8, the vacuum valve between the first vacuum coating chamber and sample transmission chamber is opened, controls sample transmission Transmission system in chamber, substrate is transferred to sample and transmits chamber, close the first vacuum coating chamber and sample transmit chamber it Between vacuum valve, open sample and transmit valve between chamber and cell package chamber, substrate is transferred to cell package chamber Room, the valve closed between sample transmission chamber and cell package chamber, make battery pole ear, carry out coating protection;Take out electricity Pond, carry out battery testing;

Process two is,

Step 1, in the first vacuum coating chamber, carry out substrate surface treatment, the mask plated film and just of plus plate current-collecting body The mask plated film of pole;Next step is determined according to the attribute of positive electrode, when positive electrode needs to be made annealing treatment, entered Enter step 2, when positive electrode need not be made annealing treatment, be directly entered step 3;

Step 2, the vacuum valve between the first vacuum coating chamber and sample transmission chamber is opened, controls sample transmission Transmission system in chamber, substrate is transferred to sample and transmits chamber, close the first vacuum coating chamber and sample transmit chamber it Between vacuum valve, open vacuum annealing chamber and sample and transmit vacuum valve between chamber, control sample is transmitted in chamber Transmission system, substrate is transferred to vacuum annealing chamber, carries out positive pole the high temperature anneal, opens vacuum annealing chamber and sample The vacuum valve between chamber is transmitted, control sample transmits transmission system in chamber, and substrate is transferred into sample transmits chamber, beats The vacuum valve between the first vacuum coating chamber and sample transmission chamber is opened, substrate is transferred to the first vacuum coating chamber;

Step 3, electrolyte mask plated film is carried out in the first vacuum coating chamber;

Step 4, substrate is transferred to sample and transmits chamber, open the first vacuum coating chamber and sample transmit chamber it Between vacuum valve, substrate is transferred to first vacuum coating chamber, carries out collector mask plated film;

Step 5, according to the magnitude of voltage of required battery, repeat step one to step 4, the number repeated is the electricity of battery Pressure value divided by single cell battery magnitude of voltage, numerical value round numbers;

Step 6, the vacuum valve between the first vacuum coating chamber and sample transmission chamber is opened, controls sample transmission Transmission system in chamber, substrate is transferred to sample and transmits chamber, close the first vacuum coating chamber and sample transmit chamber it Between vacuum valve, open sample and transmit valve between chamber and cell package chamber, substrate is transferred to cell package chamber Room, the valve closed between sample transmission chamber and cell package chamber, make battery pole ear, carry out coating protection;Take out electricity Pond, carry out battery testing.

The number of described plated film repeat unit is no less than 2 times, and cell voltage is not less than 6 volts.

Described vacuum coating method is magnetron sputtering, thermal evaporation, electron beam evaporation, multi-arc ion coating, chemical vapor deposition Long-pending one or several kinds.

Described collector, positive pole, electrolyte, the thickness of negative pole are respectively 0.5 micron to 30 microns.

Described control process is to automatically control or the manual control of manual intervention.

The present invention has the advantage that and beneficial effect

Compared with traditional single core all solid-state thin-film lithium battery production method and equipment, innovative point of the present invention and advantage are:

(1) battery structure uses the single cell battery Stacking units that n times repeat, without additional circuit, self-assembling formation in structure High-voltage thin-film lithium battery, the current actual measurement burning voltage of battery are 6V-100V;

(2) battery is divided into two in structure:First item is the high-voltage battery containing negative pole, can use annealing positive pole It is stable with annealing negative pole, battery performance;Second item is the high-voltage battery of no negative pole, can use annealing positive pole, eliminate deposition Negative pole technique and annealing process, efficiency is faster.The negative pole of battery is after finalization of the manufacture, to be formed by charging the battery;

(3) battery production equipment realizes that sequencing is back and forth plated using multi-chamber and maincenter-distributed structure of transition chamber thereof Film, avoid exposed vacuum and cause film by air pollution, so as to realize the company of production high-voltage thin-film lithium battery preparation Continuous property and uniformity.In process of production, each operation step can be continuous, and no mutual interference, relatively conventional production efficiency of equipment improves More than 30%.Manual delivery (such as magnetic rod) or mechanical automation transmission can be used by realizing the function of transition chamber thereof sample transmission (such as vacuum robot).

Brief description of the drawings

Fig. 1 is two class flexibility all solid-state thin-film lithium battery structural representations.

Wherein, substrate 100;Positive pole 101;Electrolyte 102;Negative pole 103;Collector 104;Barrier layer 105.

Fig. 2 is battery manufacturing equipment schematic diagram.

Wherein, first vacuum coating chamber 201;Second vacuum coating chamber 202;Vacuum annealing chamber 203;Battery Package cavity 204;Sample transmits chamber 205.

Fig. 3 is high-voltage thin-film lithium battery production procedure.

Fig. 4 is the production procedure without negative pole high-voltage thin-film lithium battery.

Fig. 5 is the supporting explanation figure of embodiment 1, and Fig. 5 a are the specific schematic diagram of battery, and structure is:Si/[Pt/LCO/LiPON/ Li] × 3 repetition stacking provisions/Pt, Fig. 5 b be actual measurement the charge and discharge process of the 1st time and the 1000th time in voltage with capacity Variation relation.

Fig. 6 is the supporting explanation figure of embodiment 2, and Fig. 6 a are the specific schematic diagram of battery, and structure is:Polyimides (PI)/Mo/ LiFeWO4/LiPON/Li/Mo/LiFeWO4/ LiPON/Li/Mo, Fig. 6 b are the 1st time of actual measurement, the charge and discharge process of the 100th time Middle voltage with capacity variation relation.

Fig. 7 is the supporting explanation figure of embodiment 3, and Fig. 7 a are the specific schematic diagram of battery, and structure is:Mica/[Au/LiMn2O4/ LiPON] × 5 stacking provisions/Au, Fig. 7 b are the 1st time of actual measurement, in the charge and discharge process of the 900th time voltage with capacity change Change relation.

Embodiment

The basic thought of the present invention is (1) using multiple repeat unit stacked systems (positive pole/electrolyte/negative pole) on substrate Make film lithium cell, battery just possess from structure design high voltage (>6V);(2) this stacked system is directed to, has invented one Kind integrate the integrated facility of multiple vacuum chambers, so as to realize plated film, annealing, encapsulation, substrate transmission continuity grasp Make, be easy to quick, the efficient production of film lithium cell.

Technical solution of the present invention is further described below with reference to drawings and examples, it is to be understood that of the invention It is not limited to this.

In the case where not exposing vacuum condition, substrate, the different chamber Multiple depositions on substrate are transmitted by maincenter transition chamber thereof Film layer, realizes the stacking and cascaded structure (such as Fig. 1) of battery, and the cell voltage of completion is not less than 6V, is also equipped with the long circulating longevity Life, the characteristic of high power charging-discharging, is particularly suited for electronic product.

The technological process method and apparatus of battery production is described in detailed below, but the present invention can not exclusively rely on these details To operate.Though the embodiment, which is not known, discloses other configurations and construction, but still is considered as within protection scope of the present invention.

Five chambers as shown in Figure 2, first vacuum coating chamber 201 and second vacuum coating chamber 202 are used for Vacuum coating, vacuum annealing chamber 203 is used for the conventional annealing of positive pole/negative pole or short annealing, cell package chamber 204 are used In encapsulation such as lug bonding, protective coating coatings, sample transmit chamber 205 as carry out substrate between foregoing four chambers can Lean on, chamber is repeatedly transmitted in vacuum, substrate includes but is not limited to ceramic substrate (such as Si, Ge, mica, sapphire), glass base Piece (ultra-thin unorganic glass, lucite), metal substrate (such as Ti, Al, Cu, Ag, Pt).Utilize the equipment, the production stream of battery Journey is divided into two classes, and the first kind is the film lithium cell production procedure with negative pole, and the second class is the film lithium cell life without negative pole Produce flow.

First kind battery production flow (such as Fig. 3) is followed successively by:

In 201, substrate surface treatment (step 301) is carried out respectively, plus plate current-collecting body mask deposition (302), positive pole is covered Film deposits (303);

In 203, positive pole annealing (303-1) is carried out;

In 201, electrolyte mask deposition (304) is carried out;

In 202, negative pole mask deposition (305) is carried out;

In 203, negative pole annealing (305-1) is carried out;

In 202, negative current collector mask deposition (306) is carried out;

Step 303 is returned to afterwards, is carried out n times iteration, is realized the series connection of N number of single cell battery;

After n-th completes step 306, in 204, make lug, carry out coating protection (307);

High-voltage battery is finally taken out, carries out battery testing (308), battery structure is as shown in Figure 1a.

In above step, 303-1 positive pole annealing and 305-1 negative pole are annealed into and are elected to be flow, according to different positive and negative Pole material and decide whether to use, referring in detail to embodiment 1 and embodiment 2.In whole flow process, multiple batches of substrate can be carried out and existed Temporal parallel processing, greatly improves production efficiency, can be with when such as 201 chambers carry out second lot substrate 301-303 steps The 303-1 operations of first batch substrate are carried out in 203 chambers.Passed in addition, 205 chambers are substrates in 201-204 products The transition chamber passed, it can use but be not limited to using manual delivery (such as magnetic rod), automatic transmission (such as robot).

Second class battery production flow (such as Fig. 4) is followed successively by:

In 201, substrate surface treatment (step 401) is carried out respectively, plus plate current-collecting body mask deposition (402), positive pole is covered Film deposits (403);

In 203, positive pole annealing (403-1) is carried out;

In 201, electrolyte mask deposition (404) is carried out;

In 202, negative current collector mask deposition (406) is carried out;

Step 403 is returned to afterwards, is carried out n times and is repeated, realizes the series connection of N number of single cell battery;

After n-th completes step 406, in 204, make lug, carry out coating protection (407);

High-voltage battery is finally taken out, carries out battery testing (408), battery structure is as shown in Figure 1 b.

In the production technology, cathode deposition, negative pole annealing process are eliminated, corresponding battery has lacked negative pole, the battery Negative pole is formed during battery initial charge.In above step, 403-1 positive pole annealing is elected to be flow, according to difference Positive and negative pole material and decide whether to use, referring particularly to embodiment 3.In whole flow process, multiple batches of base can be carried out in different chamber Piece parallel processing, more than 30% is improved to the piece mode of production, production efficiency relative to traditional piece.In addition, 205 chambers are substrates In the transition chamber that 201-204 products are transmitted, it can use but be not limited to using manual delivery (such as magnetic rod), automatic transmission (such as robot).

The battery production equipment invented can compatible above-mentioned two classes battery production, the production of the class battery of the above two passes through Detection, meets use demand.

Embodiment 1

The cellular construction of the battery is traditional film lithium cell structure LiCoO2/ LiPON/Li, LiCoO2After preparation, Need to be heat-treated, the battery is referred to as high-voltage thin-film lithium battery.

By 4 inch silicon wafers after ten cleanings, after being positioned over device battery package cavity 204, each chamber of equipment vacuumizes It is better than 5 × 10 to vacuum-4Pa, three axle vacuum clean-room robots of chamber 205 are transmitted using sample, start plating steps (such as Structure shown in Fig. 5 a):

(1) a piece of silicon chip is sent into first vacuum coating chamber 201, using DC pulse magnetically controlled sputter method, directly It is thick that 500nm is deposited on the silicon chip of mask film covering, the Pt films of the ohm-sq of sheet resistance 0.5;

(2) on herein, sputtered using DC pulse, LiCoO thick mask deposition 1000nm2Film, power density 2W/ cm2, air pressure 1.5Pa;

(3) above sample is transmitted into chamber 205 by sample, is transferred to vacuum annealing chamber 203, carry out 750 DEG C of high temperature Annealing 1 hour, atmosphere are purity oxygen 2sccm, vacuum 1 × 10-3Pa;

(4) above sample is transmitted into chamber 205 by sample, is transferred to first vacuum coating chamber 201, utilizes radio frequency Magnetron sputtering, LiPON films thick mask deposition 2000nm, power density 1W/cm2, air pressure 2.0Pa;

(5) above sample is transferred to second vacuum coating chamber 202, in vacuum 1 × 10-3Under the conditions of Pa, mask Evaporate Li films, thickness 500nm;

(6) above sample is transferred to first vacuum coating chamber 201, repeats step (1)-(5) operation three After secondary, sample is transferred to cell package chamber 204, carries out both positive and negative polarity lug bonding, is taken out after coating encapsulated layer.It is whole to prepare Process is controlled by PLC program, realizes that full-automatic/two kinds of manual intervention prepares function.

Testing film lithium battery open-circuit voltage, take out finished battery and carry out charge-discharge test, such as Fig. 5 b charging and discharging curves, fill Discharge platform about 12V, after 1000 circulations, discharge capacity decays to 88.7% (100%DoD) of initial value.

In above cell production process, intert and carry out other 9 silicon chip film-coated and assembled battery processes.

Embodiment 2

The cellular construction of the battery is LiFeWO4/ LiPON/Li, positive pole LiFeWO4Without being heat-treated after preparation, directly Deposition electrolyte LiPON, plated film and crimping and transfer processes flow are saved, the battery is referred to as high voltage without annealing thin film lithium electricity Pond.

Ten polyimide foils (PI paper tinsels) after fixation are cleaned, after being positioned over device battery package cavity 204, if Standby each chamber is evacuated to vacuum better than 5 × 10-4Pa, three axle vacuum clean-room robots of chamber 205 are transmitted using sample, are opened Beginning plating steps (structure as shown in Figure 6 a):

(1) a piece of PI paper tinsels are sent into first vacuum coating chamber 201, the argon ion ionized using anode layer ion source (0.09Pa, 800~1000V, 0.1~0.3A) uniformly bombards PI paper tinsels 10~20 minutes, and PI films are with 5 revs/min during bombardment Face ion gun rotates, and then using DC pulse magnetically controlled sputter method, directly deposits 500nm on the PI paper tinsels of mask film covering Thickness, the Mo films of the ohm-sq of sheet resistance 2;

(2) on herein, sputtered using DC pulse, LiFeWO thick mask deposition 500nm4Film, power density 4W/ cm2, air pressure 0.3Pa;

(3) rf magnetron sputtering, LiPON films thick mask deposition 2000nm, power density 1W/cm are utilized2, air pressure 2.0Pa;

(4) above sample is transferred to second vacuum coating chamber 202, in vacuum 1 × 10-3Under the conditions of Pa, evaporation Li films, thickness 500nm;

(5) above sample is transferred to first vacuum coating chamber (201), repeats step (1) to (4) operation After three times, sample is transferred to cell package chamber 204, carries out both positive and negative polarity lug bonding, coat encapsulated layer, test open circuit electricity Pressure, take out finished battery and carry out charge-discharge test, such as Fig. 5 b charging and discharging curves, two charge and discharge platform about 9V and 5V are followed for 100 times After ring, discharge capacity decays to 85.8% (100%DoD) of initial value.

In above cell production process, intert the plated film and assembling process for carrying out other 9 PI paper tinsels.

Embodiment 3

The cellular construction of the battery is LiMn2O4/ LiPON, positive pole LiMn2O4Negative pole need not be deposited after preparation, is saved Plated film and crimping and transfer processes flow, negative pole are formed during the initial charge after the completion of battery.The battery is referred to as high electricity Pressure is without lithium film lithium cell.

By 2 inches of mica sheets after ten cleanings, after being positioned over device battery package cavity 204, each chamber of equipment is taken out very Sky to vacuum is better than 5 × 10-4Pa, three axle vacuum clean-room robots of chamber 205 are transmitted using sample, start plating steps (structure as shown in Figure 5 a):

(1) a piece of mica sheet is sent into first vacuum coating chamber 201, using DC pulse magnetically controlled sputter method, directly It is connected on the mica sheet of mask film covering and deposits 200nm thickness, the Au films of the ohm-sq of sheet resistance 2;

(2) on herein, sputtered using DC pulse, LiMn thick mask deposition 2000nm2O4Film, power density 4W/ cm2, air pressure 2Pa;

(3) above sample is transmitted into chamber 205 by sample, is transferred to vacuum annealing chamber 203, carry out 500 DEG C of high temperature Annealing 3 hours, vacuum 3 × 10-4Pa;

(4) above sample is transmitted into chamber 205 by sample, is transferred to first vacuum coating chamber 201, utilizes radio frequency Magnetron sputtering, LiPON films thick mask deposition 2000nm, power density 1W/cm2, air pressure 2.0Pa;

(5) after repeating step (1) to (4) and operating five times, sample is transferred to cell package chamber 204, carried out Both positive and negative polarity lug is bonded, and coats encapsulated layer, tests open-circuit voltage, is taken out finished battery and is carried out charge-discharge test, such as Fig. 7 b charge and discharges Electric curve, two charge and discharge platforms are respectively 10V and 20V, and after 900 circulations, discharge capacity decays to the 93.4% of initial value (100%DoD).

In above cell production process, intert the plated film and assembling process for carrying out other 9 cloudlet master slice.

Although describing the present invention with reference to preferably specific embodiment of the invention, it will be understood by a person skilled in the art that, can Various modifications and modification are carried out in external form and details, without departing from the spirit and scope of the present invention.Subsidiary claim ought to Include all such modifications and modification.

Claims (5)

1. a kind of method for producing all solid-state thin-film lithium battery, it is characterized in that, using vacuum coating equipment in not exposure air environment Under, single cell battery is manufactured in surface, to be one of following, (one) deposits collector, just on substrate successively for the mode of deposition Pole, electrolyte, negative pole single cell battery, according to the magnitude of voltage of required battery product, repeated deposition is multiple above single cell battery Collector, positive pole, electrolyte, negative pole single cell battery, (two) deposit collector, positive pole, electrolyte single electricity on substrate successively Pond, according to the magnitude of voltage of required battery product, the multiple collectors of repeated deposition, positive pole, electrolyte single on single cell battery Battery, plating steps are:
1) equipment of manufacture production all solid-state thin-film lithium battery, equipment include five chambers and a control computer first, its In two chambers be vacuum coating chamber, the other three is respectively that vacuum annealing chamber, cell package chamber and sample transmit chamber Room;Vacuum coating chamber, vacuum annealing chamber and cell package chamber transmit chamber with sample by vacuum valve and are connected, electricity For pond package cavity by anhydrous, anaerobic and inert atmosphere protection, it is vacuum environment that sample, which transmits chamber, and sample transmits to be set in chamber There are vacuum mechanical-arm or vacuum robot as transmission system;
2) battery is produced, its process is controlled by computer, and control process is one of following:
Process one is,
Step 1, in the first vacuum coating chamber, carry out substrate surface treatment, the mask plated film of plus plate current-collecting body and positive pole Mask plated film;Next step is determined according to the attribute of positive electrode, when positive electrode needs to be made annealing treatment, into step Rapid two, when positive electrode need not be made annealing treatment, it is directly entered step 3;
Step 2, opens the vacuum valve between the first vacuum coating chamber and sample transmission chamber, and control sample transmits chamber In transmission system, substrate is transferred to sample and transmits chamber, the first vacuum coating chamber and sample is closed and transmits between chamber Vacuum valve, open vacuum annealing chamber and sample and transmit vacuum valve between chamber, control sample is transmitted in chamber Transmission system, substrate is transferred to vacuum annealing chamber, carries out positive pole the high temperature anneal, opens vacuum annealing chamber and sample The vacuum valve between chamber is transmitted, control sample transmits transmission system in chamber, and substrate is transferred into sample transmits chamber, beats The vacuum valve between the first vacuum coating chamber and sample transmission chamber is opened, substrate is transferred to the first vacuum coating chamber;
Step 3, electrolyte plated film is carried out in the first vacuum coating chamber;
Step 4, opens the vacuum valve between the first vacuum coating chamber and sample transmission chamber, and control sample transmits chamber In transmission system, substrate is transferred to sample and transmits chamber, the first vacuum coating chamber and sample is closed and transmits between chamber Vacuum valve, open the second vacuum coating chamber and sample and transmit vacuum valve between chamber, control sample transmits chamber In transmission system, substrate is transferred to the second vacuum coating chamber, carries out the mask plated film of negative pole, opens the second vacuum coating Chamber and sample transmit the vacuum valve between chamber, and control sample transmits the transmission system in chamber, substrate is transferred into sample Product transmit chamber;Next step is determined according to the attribute of negative material, when negative material needs to be made annealing treatment, entered Step 5, when negative material need not be made annealing treatment, it is directly entered step 6;
Step 5, the vacuum valve between vacuum annealing chamber and sample transmission chamber is opened, control sample transmits to be passed in chamber Delivery system, substrate is transferred to vacuum annealing chamber, carries out negative pole the high temperature anneal, opened vacuum annealing chamber and passed with sample Pass the vacuum valve between chamber;
Step 6, substrate is transferred to sample and transmits chamber, opened between the first vacuum coating chamber and sample transmission chamber Vacuum valve, substrate is transferred to the first vacuum coating chamber, carries out negative current collector mask plated film;
Step 7, according to the magnitude of voltage of required battery, repeat step one to step 6, the number repeated removes for battery voltage value With single cell battery magnitude of voltage, numerical value round numbers;
Step 8, opens the vacuum valve between the first vacuum coating chamber and sample transmission chamber, and control sample transmits chamber Middle transmission system, substrate is transferred to sample and transmits chamber, closed between the first vacuum coating chamber and sample transmission chamber Vacuum valve, the valve between sample transmission chamber and cell package chamber is opened, substrate is transferred to cell package chamber, is closed The valve closed between sample transmission chamber and cell package chamber, make battery pole ear, carry out coating protection;Battery is taken out, is entered Row battery testing;
Process two is,
Step 1, in the first vacuum coating chamber, carry out substrate surface treatment, the mask plated film of plus plate current-collecting body and positive pole Mask plated film;Next step is determined according to the attribute of positive electrode, when positive electrode needs to be made annealing treatment, into step Rapid two, when positive electrode need not be made annealing treatment, it is directly entered step 3;
Step 2, opens the vacuum valve between the first vacuum coating chamber and sample transmission chamber, and control sample transmits chamber Middle transmission system, substrate is transferred to sample and transmits chamber, closed between the first vacuum coating chamber and sample transmission chamber Vacuum valve, the vacuum valve between vacuum annealing chamber and sample transmission chamber is opened, control sample transmits to be transmitted in chamber System, substrate is transferred to vacuum annealing chamber, carries out positive pole the high temperature anneal, opens vacuum annealing chamber and sample transmission Vacuum valve between chamber, control sample transmit transmission system in chamber, and substrate is transferred into sample transmits chamber, opens the One vacuum coating chamber and sample transmit the vacuum valve between chamber, and substrate is transferred into the first vacuum coating chamber;
Step 3, electrolyte mask plated film is carried out in the first vacuum coating chamber;
Step 4, substrate is transferred to sample and transmits chamber, opened between the first vacuum coating chamber and sample transmission chamber Vacuum valve, substrate is transferred to first vacuum coating chamber, carries out collector mask plated film;
Step 5, according to the magnitude of voltage of required battery, repeat step one to step 4, the number repeated is the magnitude of voltage of battery Divided by single cell battery magnitude of voltage, numerical value round numbers;
Step 6, opens the vacuum valve between the first vacuum coating chamber and sample transmission chamber, and control sample transmits chamber Middle transmission system, substrate is transferred to sample and transmits chamber, closed between the first vacuum coating chamber and sample transmission chamber Vacuum valve, the valve between sample transmission chamber and cell package chamber is opened, substrate is transferred to cell package chamber, is closed The valve closed between sample transmission chamber and cell package chamber, make battery pole ear, carry out coating protection;Battery is taken out, is entered Row battery testing.
2. a kind of method for producing all solid-state thin-film lithium battery according to claim 1, it is characterized in that, described plated film weight The number of multiple unit is no less than 2 times, and cell voltage is not less than 6 volts.
3. a kind of method for producing all solid-state thin-film lithium battery according to claim 1, it is characterized in that, described Vacuum Deposition Film method is magnetron sputtering, thermal evaporation, electron beam evaporation, multi-arc ion coating, the one or several kinds of chemical vapor deposition.
4. a kind of method for producing all solid-state thin-film lithium battery according to claim 1, it is characterized in that, described afflux Body, positive pole, electrolyte, the thickness of negative pole are respectively 0.5 micron to 30 microns.
5. a kind of method for producing all solid-state thin-film lithium battery according to claim 1, it is characterized in that, described control Journey is to automatically control or the manual control of manual intervention.
CN201710550041.1A 2017-07-07 2017-07-07 A kind of method and apparatus for producing all solid-state thin-film lithium battery CN107464913A (en)

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Publication number Priority date Publication date Assignee Title
CN1747217A (en) * 2005-07-28 2006-03-15 复旦大学 Device and method for preparing solid thin-membrane lithium battery by in-situ deposition
WO2011037867A2 (en) * 2009-09-22 2011-03-31 Applied Materials, Inc. Thin-film battery methods for complexity reduction
CN102066607A (en) * 2008-06-20 2011-05-18 Sakti3有限公司 High volume manufacture of electrochecmicals cells using physical vapor deposition
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CN105027332A (en) * 2013-01-25 2015-11-04 苹果杰克199有限合伙公司 System, method and apparatus for forming a thin film lithium ion battery
CN106784988A (en) * 2015-11-24 2017-05-31 中国航空工业集团公司北京航空材料研究院 A kind of flexible all solid-state thin-film lithium battery and its production method
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1747217A (en) * 2005-07-28 2006-03-15 复旦大学 Device and method for preparing solid thin-membrane lithium battery by in-situ deposition
CN102066607A (en) * 2008-06-20 2011-05-18 Sakti3有限公司 High volume manufacture of electrochecmicals cells using physical vapor deposition
WO2011037867A2 (en) * 2009-09-22 2011-03-31 Applied Materials, Inc. Thin-film battery methods for complexity reduction
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