CN107464913B - A method of producing all-solid-state thin-film lithium battery - Google Patents

Abstract

The invention belongs to the field of battery manufacturing technology and vacuum coating technology, and relates to a method and equipment for producing an all-solid-state thin-film lithium battery. The invention adopts a vacuum coating machine to manufacture a single-cell battery on the substrate without exposing the air environment. The battery structure adopts single-cell battery stacking units repeated N times, without the need for additional lines, and a high-voltage thin-film lithium battery is naturally formed in the structure. The current measured stable voltage of the battery is 6V‑100V; the battery is divided into two types in structure: One is a high-voltage battery with a negative electrode, and the second is a high-voltage battery without a negative electrode. The invention realizes programmed reciprocating film coating, avoids air pollution of the film caused by exposure to vacuum, and thus realizes continuity and consistency in the production of high-voltage thin film lithium batteries. In the production process, each process step can be continuous without mutual interference, and the production efficiency has been increased by more than 30% compared with traditional equipment.

Description

A method of producing all-solid-state thin-film lithium battery

technical field

The invention belongs to the field of battery manufacturing technology and vacuum coating technology, and relates to a method for producing an all-solid-state thin-film lithium battery.

Background technique

Traditional lithium-ion batteries are generally based on liquid organic electrolytes and separators, which pose safety hazards during their service life. Using solid-state electrolytes instead of electrolytes and developing all-solid-state lithium-ion batteries is one of the best solutions to solve potential battery safety hazards. All-solid-state thin-film lithium batteries are one of the most promising branches of all-solid-state lithium-ion batteries at present. The main thin-film layer structure of a single-cell battery is composed of a current collector, positive electrode, electrolyte, negative electrode, and packaging layer formed on a high-temperature-resistant substrate. Its electrolyte part is mainly based on the nitrogen-doped lithium phosphate film (LiPON) developed by Bates J B of Oak Ridge National Laboratory in the early 1990s.

At present, the preparation method of single-core all-solid-state thin-film lithium battery mainly adopts the vacuum coating method. The thin film layer produced by this method is dense and has high purity, and multi-layer thin films are deposited under exposure to vacuum conditions. The equipment built for the process flow of all-solid-state thin-film lithium batteries is specific. For example, Japan's Aifake Company (Jimbo et al., Energy Procedia 14 (2012) 1574-1579) and Fudan University (CN1747217A) used a series chamber structure to make single-cell batteries; the method of group tools was adopted by the US Applied Materials Corporation ( CN102576898, CN102037586A, CN103608958A) and French ZI Sud company (Martin et al., Thin Solid Films 38-399 (2001) 572-574) are used to make single-cell batteries. The structure of these battery manufacturing equipment is relatively complex, and the finished battery is generally a 3-4V low-voltage single-cell battery, which cannot directly meet the needs of most electronic products and automotive power batteries (voltage >6V). On the other hand, most of the automotive power batteries and notebook batteries use high-voltage lithium-ion battery packs, and the battery packs are often formed by single-cell batteries through complex external circuit series-parallel structures. How to achieve a series-parallel structure without leads inside the battery, simplify the production process and reduce the use of raw materials has long been a problem that has plagued the lithium battery industry.

Contents of the invention

In view of the deficiency that the existing thin-film lithium battery manufacturing method can only prepare low-voltage batteries, and the demand for high-voltage batteries in the mobile power industry, the present invention proposes a method and equipment for producing high-voltage all-solid-state thin-film lithium batteries.

The technical solution of the present invention is to use a vacuum coating machine to manufacture a single-cell battery above the substrate without exposure to the air. The deposition method is one of the following: (1) deposit the current collector, positive electrode, electrolyte, Negative single-cell battery, according to the voltage value of the required battery product, repeatedly deposit multiple current collectors, positive electrodes, electrolytes, and negative single-cell batteries on the top of the single-cell battery, (2) deposit current collectors, positive electrodes, and electrolyte cells on the substrate in sequence Cell batteries, according to the voltage value of the required battery product, repeatedly deposit multiple current collectors, positive electrodes, and electrolyte single-cell batteries on the single-cell battery. The coating steps are:

1) First manufacture the equipment for the production of all-solid-state thin-film lithium batteries. The equipment includes five chambers and a control computer, two of which are vacuum coating chambers, and the other three are vacuum annealing chambers and battery packaging chambers. and the sample transfer chamber; the vacuum coating chamber, vacuum annealing chamber and battery packaging chamber are all connected to the sample transfer chamber through vacuum valves. The battery packaging chamber is protected by an anhydrous, oxygen-free and inert atmosphere, and the sample transfer chamber It is a vacuum environment, and a vacuum manipulator or a vacuum robot is set in the sample transfer chamber as a transfer system;

2) Production of batteries, the process of which is controlled by a computer, and the control process is one of the following:

Process one is,

Step 1: In the first vacuum coating chamber, the surface treatment of the substrate, the mask coating of the positive electrode current collector and the mask coating of the positive electrode are carried out; the next step is determined according to the properties of the positive electrode material. When the positive electrode material needs to be annealed, Enter step 2, when the positive electrode material does not need to be annealed, directly enter step 3;

Step 2: Open the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, control the transfer system in the sample transfer chamber, transfer the substrate to the sample transfer chamber, and close the first vacuum coating chamber and the sample transfer chamber. The vacuum valve between the transfer chamber, open the vacuum valve between the vacuum annealing chamber and the sample transfer chamber, control the transfer system in the sample transfer chamber, transfer the substrate to the vacuum annealing chamber, and perform positive high-temperature annealing treatment , open the vacuum valve between the vacuum annealing chamber and the sample transfer chamber, control the transfer system in the sample transfer chamber, transfer the substrate to the sample transfer chamber, and open the gap between the first vacuum coating chamber and the sample transfer chamber The vacuum valve is used to transfer the substrate to the first vacuum coating chamber;

Step 3, performing electrolyte coating in the first vacuum coating chamber;

Step 4, open the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, control the transfer system in the sample transfer chamber, transfer the substrate to the sample transfer chamber, and close the first vacuum coating chamber and the sample transfer chamber. The vacuum valve between the transfer chambers, open the vacuum valve between the second vacuum coating chamber and the sample transfer chamber, control the transfer system in the sample transfer chamber, transfer the substrate to the second vacuum coating chamber, and carry out Mask coating of the negative electrode, open the vacuum valve between the second vacuum coating chamber and the sample transfer chamber, control the transfer system in the sample transfer chamber, and transfer the substrate to the sample transfer chamber; determine according to the properties of the negative electrode material In the next step, when the negative electrode material needs to be annealed, enter step five, and when the negative electrode material does not need to be annealed, directly enter step six;

Step five, open the vacuum valve between the vacuum annealing chamber and the sample transfer chamber, control the transfer system in the sample transfer chamber, transfer the substrate to the vacuum annealing chamber, perform negative electrode high-temperature annealing treatment, open the vacuum annealing chamber and Vacuum valves between sample transfer chambers;

Step 6, transfer the substrate to the sample transfer chamber, open the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, transfer the substrate to the first vacuum coating chamber, and carry out the negative electrode current collector mask coating ;

Step 7. Repeat steps 1 to 6 according to the voltage value of the battery required. The number of repetitions is the voltage value of the battery divided by the voltage value of the single-cell battery, and the value is an integer;

Step eight, open the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, control the transfer system in the sample transfer chamber, transfer the substrate to the sample transfer chamber, close the first vacuum coating chamber and the sample transfer chamber The vacuum valve between the chambers, open the valve between the sample transfer chamber and the battery packaging chamber, transfer the substrate to the battery packaging chamber, close the valve between the sample transfer chamber and the battery packaging chamber, and make the battery Tabs, for coating protection; take out the battery, and conduct a battery test;

The second process is,

Step 1: In the first vacuum coating chamber, the surface treatment of the substrate, the mask coating of the positive electrode current collector and the mask coating of the positive electrode are carried out; the next step is determined according to the properties of the positive electrode material. When the positive electrode material needs to be annealed, Enter step 2, when the positive electrode material does not need to be annealed, directly enter step 3;

Step 2, open the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, control the transfer system in the sample transfer chamber, transfer the substrate to the sample transfer chamber, close the first vacuum coating chamber and the sample transfer chamber The vacuum valve between the chambers, open the vacuum valve between the vacuum annealing chamber and the sample transfer chamber, control the transfer system in the sample transfer chamber, transfer the substrate to the vacuum annealing chamber for positive high temperature annealing, open The vacuum valve between the vacuum annealing chamber and the sample transfer chamber controls the transfer system in the sample transfer chamber, transfers the substrate to the sample transfer chamber, and opens the vacuum between the first vacuum coating chamber and the sample transfer chamber a valve for transferring the substrate to the first vacuum coating chamber;

Step 3, performing electrolyte mask coating in the first vacuum coating chamber;

Step 4, transfer the substrate to the sample transfer chamber, open the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, transfer the substrate to the first vacuum coating chamber, and perform collector mask coating ;

Step 5. Repeat steps 1 to 4 according to the voltage value of the battery required. The number of repetitions is the voltage value of the battery divided by the voltage value of the single-cell battery, and the value is an integer;

Step 6, open the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, control the transfer system in the sample transfer chamber, transfer the substrate to the sample transfer chamber, close the first vacuum coating chamber and the sample transfer chamber The vacuum valve between the chambers, open the valve between the sample transfer chamber and the battery packaging chamber, transfer the substrate to the battery packaging chamber, close the valve between the sample transfer chamber and the battery packaging chamber, and make the battery Tabs, for coating protection; take out the battery, and conduct a battery test.

The number of repeating units of the coating film is not less than 2 times, and the battery voltage is not lower than 6 volts.

The vacuum coating method is one or more of magnetron sputtering, thermal evaporation, electron beam evaporation, multi-arc ion plating and chemical vapor deposition.

The thicknesses of the current collector, the positive electrode, the electrolyte, and the negative electrode are respectively 0.5 microns to 30 microns.

The control process is automatic control or manual control with human intervention.

Advantages and beneficial effects that the present invention has

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

(1) The battery structure adopts single-cell battery stacking units repeated N times, without additional wiring, and a high-voltage thin-film lithium battery is naturally formed in the structure. The current measured stable voltage of the battery is 6V-100V;

(2) The battery is divided into two types in terms of structure: the first type is a high-voltage battery with a negative electrode, which can use annealed positive electrode and annealed negative electrode, and the battery performance is stable; the second type is a high-voltage battery without a negative electrode, which can be annealed The positive electrode saves the process of depositing negative electrode and annealing process, and the efficiency is faster. The negative electrode of the battery is formed by charging the battery after manufacture;

(3) The battery production equipment adopts a central-distributed structure with multiple chambers and transition chambers to realize programmed reciprocating coating, avoiding air pollution of the film caused by exposure to vacuum, thereby realizing the continuity of production of high-voltage thin-film lithium batteries and consistency. In the production process, each process step can be continuous without mutual interference, and the production efficiency has been increased by more than 30% compared with traditional equipment. The function of realizing the sample transfer in the transition chamber can be manual transfer (such as a magnetic rod) or mechanical automatic transfer (such as a vacuum robot).

Description of drawings

Figure 1 is a schematic diagram of the structure of two types of flexible all-solid-state thin-film lithium batteries.

Among them, the substrate 100 ; the positive electrode 101 ; the electrolyte 102 ; the negative electrode 103 ; the current collector 104 ;

Figure 2 is a schematic diagram of the battery manufacturing equipment.

Among them, the first vacuum coating chamber 201 ; the second vacuum coating chamber 202 ; the vacuum annealing chamber 203 ; the battery packaging chamber 204 ; and the sample delivery chamber 205 .

Figure 3 shows the production process of high-voltage thin-film lithium batteries.

Figure 4 shows the production process of anode-free and extremely high-voltage thin-film lithium batteries.

Figure 5 is a supporting illustration of Example 1, a in Figure 5 is a specific schematic diagram of the battery, the structure is: Si/[Pt/LCO/LiPON/Li] × 3 repeated stacking structures/Pt, b in Figure 5 is The relationship between the measured voltage and capacity during the first and 1000th charging and discharging processes.

Figure 6 is a supporting illustration of Example 2, and a in Figure 6 is a specific schematic diagram of the battery, the structure of which is: polyimide (PI) /Mo/LiFeWO ₄ /LiPON/Li/Mo/LiFeWO ₄ /LiPON/Li/Mo , b in Figure 6 is the relationship between the voltage and the capacity during the first and 100th charging and discharging processes measured.

Figure 7 is a supporting illustration of Example 3, a in Figure 7 is a specific schematic diagram of the battery, the structure is: mica/[Au/LiMn ₂ O ₄ /LiPON]×5 stacking structure/Au, b in Figure 7 is The relationship between voltage and capacity during the first and 900th charging and discharging processes measured.

Detailed ways

The basic idea of the present invention is (1) to make a thin film lithium battery by laminating multiple repeating units (positive electrode/electrolyte/negative electrode) on the substrate, and the battery has a high voltage (>6V) from the structural design; (2) for this A stacking method, and invented a comprehensive equipment that integrates multiple vacuum chambers, so as to realize the continuous operation of coating, annealing, packaging, and substrate transfer, and facilitate the rapid and efficient production of thin-film lithium batteries.

The technical solutions of the present invention will be further described in detail below with reference to the drawings and embodiments, but it should be understood that the present invention is not limited thereto.

Without exposure to vacuum, the substrate is transferred through the central transition chamber, and thin film layers are deposited multiple times in different chambers on the substrate to realize the stacking and series structure of the battery (as shown in Figure 1). The completed battery voltage is not lower than 6V , It also has the characteristics of long cycle life and high rate charge and discharge, which is more suitable for electronic products.

The process flow method and equipment for battery production are described in detail below, but the present invention can be operated without completely relying on these details. Although the embodiments do not explicitly disclose other configurations and structures, they are still considered within the protection scope of the present invention.

Five chambers as shown in Figure 2, the first vacuum coating chamber 201 and the second vacuum coating chamber 202 are used for vacuum coating, and the vacuum annealing chamber 203 is used for conventional annealing or rapid annealing of positive pole/negative pole, The battery packaging chamber 204 is used for packaging such as tab bonding and protective coating coating. The sample transfer chamber 205 is used as a chamber for reliable and repeated vacuum transfer of the substrate between the aforementioned four chambers. The substrate includes but Not limited to ceramic substrates (such as Si, Ge, mica, sapphire), glass substrates (ultra-thin inorganic glass, organic glass), metal substrates (such as Ti, Al, Cu, Ag, Pt). Using this equipment, the production process of the battery is divided into two categories, the first is the production process of thin-film lithium battery with negative electrode, and the second is the production process of thin-film lithium battery without negative electrode.

The production process of the first type of battery (as shown in Figure 3) is as follows:

In 201, substrate surface treatment (step 301), positive electrode current collector mask deposition (302), and positive electrode mask deposition (303) are performed respectively;

In 203, annealing the positive electrode (303-1);

In 201, electrolyte mask deposition (304);

In 202, negative electrode mask deposition (305);

In 203, negative electrode annealing (305-1);

In 202, perform negative electrode current collector mask deposition (306);

Then return to step 303, and perform N repeated iterations to realize the series connection of N single-cell batteries;

After completing step 306 for the Nth time, in 204, make tabs and perform coating protection (307);

Finally, the high-voltage battery is taken out for a battery test (308). The battery structure is shown in a in FIG. 1 .

In the above steps, the annealing of the positive electrode in 303-1 and the annealing of the negative electrode in 305-1 are the selected processes, and whether to use it is determined according to different materials of the positive and negative electrodes. Refer to Example 1 and Example 2 for details. In the whole process, multiple batches of substrates can be processed in parallel in time, which greatly improves production efficiency. For example, when the second batch of substrates 301-303 steps are carried out in the 201 chamber, the first batch can be carried out in the 203 chamber 303-1 Operation of substrates. In addition, chamber 205 is a transition chamber for substrates to be transferred between workpieces 201-204, and manual transfer (such as magnetic rods) and automatic transfer (such as robots) can be used, but not limited to.

The second type of battery production process (as shown in Figure 4) is as follows:

In 201, substrate surface treatment (step 401), positive electrode current collector mask deposition (402), and positive electrode mask deposition (403) are performed respectively;

In 203, annealing the positive electrode (403-1);

In 201, an electrolyte mask deposition is performed (404);

In 202, perform negative electrode current collector mask deposition (406);

Then return to step 403, and perform N repeated operations to realize the series connection of N single-cell batteries;

After completing step 406 for the Nth time, in 204, make tabs and perform coating protection (407);

Finally, the high-voltage battery is taken out for a battery test (408). The battery structure is shown in b in FIG. 1 .

In this production process, the process of negative electrode deposition and negative electrode annealing is omitted, and the corresponding battery lacks a negative electrode, which is formed during the first charging process of the battery. In the above steps, the positive electrode annealing of 403-1 is selected as the process, and whether to use it is determined according to different positive and negative electrode materials. See Example 3 for details. In the whole process, multiple batches of substrates can be processed in parallel in different chambers. Compared with the traditional sheet-to-sheet production method, the production efficiency has increased by more than 30%. In addition, chamber 205 is a transition chamber for substrates to be transferred between workpieces 201-204, and manual transfer (such as magnetic rods) and automatic transfer (such as robots) can be used, but not limited to.

The invented battery production equipment is compatible with the production of the above two types of batteries, and the production of the above two types of batteries has been tested and meets the requirements of use.

Example 1

The unit structure of the battery is the traditional thin-film lithium battery structure LiCoO ₂ /LiPON/Li. After LiCoO ₂ is prepared, heat treatment is required. The battery is called a high-voltage thin-film lithium battery.

After ten cleaned 4-inch silicon wafers are placed in the battery packaging chamber 204 of the equipment, each chamber of the equipment is evacuated to a vacuum degree better than 5×10 ^-4 Pa, and the three-axis vacuum cleaning of the sample delivery chamber 205 is used. The robot starts the coating step (structure shown in a in Figure 5):

(1) A piece of silicon wafer is sent into the first vacuum coating chamber 201, utilizes the direct current pulse magnetron sputtering method, directly deposits 500nm thick, the Pt thin film of square resistance 0.5 ohm/square on the silicon wafer of covering mask;

(2) On top of this, use DC pulse sputtering to deposit a 1000nm thick LiCoO ₂ film with a mask, with a power density of 2W/cm ² and an air pressure of 1.5Pa;

(3) Transfer the above samples to the vacuum annealing chamber 203 through the sample transfer chamber 205, and perform high-temperature annealing at 750°C for 1 hour, the atmosphere is pure oxygen 2 sccm, and the vacuum degree is 1×10 ^-3 Pa;

(4) Pass the above sample through the sample transfer chamber 205 and transfer it to the first vacuum coating chamber 201, and use radio frequency magnetron sputtering to deposit a 2000nm thick LiPON film with a power density of 1W/cm ² and an air pressure of 2.0 Pa ;

(5) Transfer the above sample to the second vacuum coating chamber 202, and evaporate a Li film with a thickness of 500nm under the condition of a vacuum degree of 1×10 ^-3 Pa;

(6) Transfer the above samples to the first vacuum coating chamber 201, and after repeating steps (1)-(5) three times, transfer the samples to the battery packaging chamber 204 for bonding positive and negative electrodes , take out after coating the encapsulation layer. The whole preparation process is controlled by PLC program, realizing two preparation functions of automatic/manual intervention.

Test the open-circuit voltage of the thin-film lithium battery, take out the finished battery and conduct a charge-discharge test, as shown in Figure 5 b charge-discharge curve, the charge-discharge platform is about 12V, after 1000 cycles, the discharge capacity decays to 88.7% of the initial value (100% DoD) .

In the above battery production process, another 9 silicon wafers are interspersed with coating and battery assembly process.

Example 2

The unit structure of the battery is LiFeWO ₄ /LiPON/Li. The positive electrode LiFeWO ₄ does not require heat treatment after preparation, and the electrolyte LiPON is directly deposited, which saves the coating and transfer process. The battery is called a high-voltage thin-film lithium battery without annealing.

After cleaning the fixed ten pieces of polyimide foil (PI foil), place them in the battery packaging chamber 204 of the equipment, vacuumize each chamber of the equipment until the vacuum degree is better than 5×10 ^-4 Pa, and use the sample transfer chamber The three-axis vacuum cleaning robot in chamber 205 starts the coating step (structure shown in a in Figure 6):

(1) Send a piece of PI foil into the first vacuum coating chamber 201, and use argon ions (0.09Pa, 800-1000V, 0.1-0.3A) ionized by the anode layer ion source to evenly bombard the PI foil for 10-20 minutes, and then During the process, the PI film is rotated against the ion source at 5 rpm, and then a 500nm thick Mo film with a square resistance of 2 ohms/square is directly deposited on the PI foil covering the mask by using the DC pulse magnetron sputtering method;

(2) On top of this, use DC pulse sputtering to deposit a 500nm thick LiFeWO ₄ film with a mask, with a power density of 4W/cm ² and an air pressure of 0.3Pa;

(3) Deposit a 2000nm-thick LiPON thin film by radio frequency magnetron sputtering, with a power density of 1W/cm ² and an air pressure of 2.0Pa;

(4) Transfer the above sample to the second vacuum coating chamber 202, and evaporate a Li thin film with a thickness of 500nm under the condition of a vacuum degree of 1×10 ^-3 Pa;

(5) Transfer the above samples to the first vacuum coating chamber (201). After repeating steps (1) to (4) three times, transfer the samples to the battery packaging chamber 204 for positive and negative electrode lugs. Bonding, coating the packaging layer, testing the open circuit voltage, taking out the finished battery for charge and discharge test, as shown in Figure 5 b charge and discharge curve, the two charge and discharge platforms are about 9V and 5V, after 100 cycles, the discharge capacity decays to the initial 85.8% of the value (100% DoD).

In the above battery production process, the coating and assembly process of another 9 pieces of PI foil is interspersed.

Example 3

The unit structure of the battery is LiMn ₂ O ₄ /LiPON. The positive electrode LiMn ₂ O ₄ does not need to deposit the negative electrode after preparation, which saves the coating and transfer process. The negative electrode is formed during the first charging process after the battery is completed. The battery is called a high-voltage lithium-free thin-film lithium battery.

After ten cleaned 2-inch mica sheets are placed in the battery packaging chamber 204 of the device, each chamber of the device is evacuated to a vacuum degree better than 5×10 ^-4 Pa, and the three-axis vacuum cleaning of the sample delivery chamber 205 is used. The robot starts the coating step (structure shown in a in Figure 5):

(1) A piece of mica sheet is sent into the first vacuum coating chamber 201, and the direct current pulse magnetron sputtering method is used to directly deposit a 200nm thick Au film with a square resistance of 2 ohms/square on the mica sheet covering the mask;

(2) On top of this, a 2000nm-thick LiMn ₂ O ₄ thin film was deposited using a DC pulse sputtering mask, with a power density of 4W/cm ² and an air pressure of 2Pa;

(3) Transfer the above samples to the vacuum annealing chamber 203 through the sample transfer chamber 205, and perform high-temperature annealing at 500°C for 3 hours with a vacuum degree of 3×10 ^-4 Pa;

(4) Pass the above sample through the sample transfer chamber 205 and transfer it to the first vacuum coating chamber 201, and use radio frequency magnetron sputtering to deposit a 2000nm thick LiPON film with a power density of 1W/cm ² and an air pressure of 2.0 Pa ;

(5) After repeating steps (1) to (4) five times, the sample is transferred to the battery packaging chamber 204, the positive and negative tabs are bonded, the packaging layer is coated, the open circuit voltage is tested, and the finished battery is taken out Carry out the charge and discharge test, as shown in the charge and discharge curve b in Figure 7, the two charge and discharge platforms are 10V and 20V respectively, and after 900 cycles, the discharge capacity decays to 93.4% of the initial value (100% DoD).

In the above battery production process, the coating and assembly process of the other 9 mica sheets are interspersed.

Although the present invention has been described with reference to preferred embodiments thereof, those skilled in the art will understand that various changes and modifications can be made in appearance and detail without departing from the spirit and scope of the invention. The appended claims are intended to cover all such modifications and modifications.

Claims (5)

1. A method for producing all solid state film lithium battery is characterized in that a single cell battery is manufactured above a substrate by adopting a vacuum coating machine under the condition of not exposing air, the deposition mode is one of the following modes, (A) a current collector, a positive electrode, an electrolyte and a negative electrode single cell battery are sequentially deposited on the substrate, a plurality of single cell batteries consisting of the current collector, the positive electrode, the electrolyte and the negative electrode are repeatedly deposited above the single cell battery according to the voltage value of a required battery product, (B) the current collector, the positive electrode and the electrolyte single cell battery are sequentially deposited on the substrate, and a plurality of single cell batteries consisting of the current collector, the positive electrode and the electrolyte are repeatedly deposited on the single cell battery according to the voltage value of the required battery product, and the steps are as follows:

1) Firstly, manufacturing equipment for producing an all-solid-state thin-film lithium battery, wherein the equipment comprises five chambers and a control computer, wherein two chambers are vacuum coating chambers, and the other three chambers are a vacuum annealing chamber, a battery packaging chamber and a sample transfer chamber respectively; the vacuum coating chamber, the vacuum annealing chamber and the battery packaging chamber are all connected with the sample transfer chamber through vacuum valves, the battery packaging chamber is protected by anhydrous, anaerobic and inert atmosphere, the sample transfer chamber is in a vacuum environment, and a vacuum manipulator or a vacuum robot is arranged in the sample transfer chamber and serves as a transfer system;

2) producing the battery, wherein the process is controlled by a computer, and the control process is one of the following processes:

In the first process, the first step is that,

Step one, performing substrate surface treatment, mask coating of a positive current collector and mask coating of a positive electrode in a first vacuum coating chamber; determining the next step according to the attribute of the anode material, entering the second step when the anode material needs to be annealed, and directly entering the third step when the anode material does not need to be annealed;

opening a vacuum valve between the first vacuum coating chamber and the sample transfer chamber, controlling a transfer system in the sample transfer chamber, transferring the substrate to the sample transfer chamber, closing the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, opening the vacuum valve between the vacuum annealing chamber and the sample transfer chamber, controlling the transfer system in the sample transfer chamber, transferring the substrate to the vacuum annealing chamber, performing anode high-temperature annealing treatment, opening the vacuum valve between the vacuum annealing chamber and the sample transfer chamber, controlling the transfer system in the sample transfer chamber, transferring the substrate to the sample transfer chamber, opening the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, and transferring the substrate to the first vacuum coating chamber;

step three, performing electrolyte coating in the first vacuum coating chamber;

opening a vacuum valve between the first vacuum coating chamber and the sample transfer chamber, controlling a transfer system in the sample transfer chamber, transferring the substrate to the sample transfer chamber, closing the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, opening a vacuum valve between the second vacuum coating chamber and the sample transfer chamber, controlling the transfer system in the sample transfer chamber, transferring the substrate to the second vacuum coating chamber, performing mask coating of a negative electrode, opening the vacuum valve between the second vacuum coating chamber and the sample transfer chamber, controlling the transfer system in the sample transfer chamber, and transferring the substrate to the sample transfer chamber; determining the next step according to the attributes of the negative electrode material, entering the fifth step when the negative electrode material needs to be annealed, and directly entering the sixth step when the negative electrode material does not need to be annealed;

opening a vacuum valve between the vacuum annealing chamber and the sample transfer chamber, controlling a transfer system in the sample transfer chamber, transferring the substrate to the vacuum annealing chamber, performing negative electrode high-temperature annealing treatment, and opening the vacuum valve between the vacuum annealing chamber and the sample transfer chamber;

step six, transferring the substrate to a sample transfer chamber, opening a vacuum valve between the first vacuum coating chamber and the sample transfer chamber, transferring the substrate to the first vacuum coating chamber, and performing negative current collector mask coating;

step seven, repeating the step one to the step six according to the voltage value of the required battery, wherein the repetition frequency is the voltage value of the battery divided by the voltage value of the single-core battery, and the numerical value is an integer;

step eight, opening a vacuum valve between the first vacuum coating chamber and the sample transfer chamber, controlling a transfer system in the sample transfer chamber, transferring the substrate to the sample transfer chamber, closing the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, opening a valve between the sample transfer chamber and the battery packaging chamber, transferring the substrate to the battery packaging chamber, closing the valve between the sample transfer chamber and the battery packaging chamber, manufacturing a battery tab and performing coating protection; taking out the battery and testing the battery;

In the second process, the first step is carried out,

step one, performing substrate surface treatment, mask coating of a positive current collector and mask coating of a positive electrode in a first vacuum coating chamber; determining the next step according to the attribute of the anode material, entering the second step when the anode material needs to be annealed, and directly entering the third step when the anode material does not need to be annealed;

opening a vacuum valve between the first vacuum coating chamber and the sample transfer chamber, controlling a transfer system in the sample transfer chamber, transferring the substrate to the sample transfer chamber, closing the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, opening the vacuum valve between the vacuum annealing chamber and the sample transfer chamber, controlling the transfer system in the sample transfer chamber, transferring the substrate to the vacuum annealing chamber, performing anode high-temperature annealing treatment, opening the vacuum valve between the vacuum annealing chamber and the sample transfer chamber, controlling the transfer system in the sample transfer chamber, transferring the substrate to the sample transfer chamber, opening the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, and transferring the substrate to the first vacuum coating chamber;

step three, performing electrolyte mask coating in the first vacuum coating chamber;

Transferring the substrate to a sample transfer chamber, opening a vacuum valve between the first vacuum coating chamber and the sample transfer chamber, transferring the substrate to the first vacuum coating chamber, and performing current collector mask coating;

step five, repeating the step one to the step four according to the voltage value of the required battery, wherein the repetition frequency is the voltage value of the battery divided by the voltage value of the single-core battery, and the numerical value is an integer;

opening a vacuum valve between the first vacuum coating chamber and the sample transfer chamber, controlling a transfer system in the sample transfer chamber, transferring the substrate to the sample transfer chamber, closing the vacuum valve between the first vacuum coating chamber and the sample transfer chamber, opening a valve between the sample transfer chamber and the battery packaging chamber, transferring the substrate to the battery packaging chamber, closing the valve between the sample transfer chamber and the battery packaging chamber, manufacturing a battery tab and performing coating protection; and taking out the battery and carrying out battery test.

2. The method of claim 1, wherein the number of coating repeating units is not less than 2 and the cell voltage is not less than 6 v.

3. The method of claim 1, wherein the vacuum coating method is one or more of magnetron sputtering, thermal evaporation, electron beam evaporation, multi-arc ion plating, and chemical vapor deposition.

4. the method of claim 1, wherein the current collector, the positive electrode, the electrolyte and the negative electrode have a thickness of 0.5 to 30 μm, respectively.

5. the method of claim 1, wherein the controlling process is an automatic control or a manual control with manual intervention.