CN105514530B - Cell lamination, lithium air secondary battery unit and its assemble method - Google Patents

Abstract

The invention discloses a kind of cell lamination, lithium air secondary battery unit and its assemble method, belong to cell art.The cell lamination includes upper gasket seal, upper air cathode, upper diaphragm, lithium anode, lower diaphragm plate, lower air cathode, lower seal pad piece, negative lug.The lithium air secondary battery unit is based on the cell lamination and realized.It can assemble to obtain the lithium air secondary battery unit by the assemble method.The lithium air secondary battery unit can normal discharge and recharge, and capacity is much larger than conventional button cell and Swaglok type batteries.

Description

Cell stack, lithium-air secondary battery unit and assembly method thereof

technical field

The invention relates to the technical field of batteries, in particular to a cell stack, a lithium-air secondary battery unit and an assembly method thereof.

Background technique

With the continuous development of social economy, the shortage of energy resources, environmental pollution and global warming have gradually become social problems that must be faced. In the face of the current international background where energy and environmental issues have attracted much attention, the comprehensive development and utilization of revolutionary energy technology, energy-saving technology and environmental protection technology has become the current primary topic. Research and development of high-performance power supply systems and their Materials are imperative.

Lithium-air battery is a high-specific energy chemical power source that uses lithium metal or lithium-containing alloys as the negative electrode and oxygen in the air as the positive electrode reactant. Its theoretical specific energy is as high as 3505Wh/kg based on Li ₂ O ₂ as the discharge product. , far higher than the traditional lithium-ion battery, is a promising new system battery. The development of lithium-air batteries is of great significance to future new energy vehicles and clean energy storage.

Since the positive electrode reactant of the lithium-air battery is oxygen in the air, when the battery is discharged, the positive electrode needs to get oxygen from the outside to react. At present, lithium-air batteries are mostly tested in the form of buttons or soft packs. Oxygen enters and exits the air positive electrode through the pores on the positive cover plate (button cell) or the openings on the aluminum-plastic film (soft bag). In this form, oxygen is exchanged with the air positive electrode in a free diffusion manner, the rate and efficiency are low, and the utilization rate of the air positive electrode is not high. Especially for large-area air cathodes, it is very important to provide reactive gases evenly, which is not considered in traditional lithium-air batteries, and it is difficult to evenly distribute air to different areas of air cathodes. In addition, traditional lithium-air batteries, such as Swaglok-type lithium-air batteries, have low structural stability and complex assembly.

Contents of the invention

In view of this, the present invention provides a battery stack, a lithium-air secondary battery unit formed based on the battery stack, and a method for assembling the lithium-air secondary battery unit, which are more suitable for practical use.

In order to achieve the above-mentioned first purpose, the battery stack technical solution provided by the present invention is as follows:

The cell stack provided by the present invention includes an upper sealing gasket, an upper air positive electrode, an upper diaphragm, a metal lithium negative electrode, a lower diaphragm, a lower air positive electrode, a lower sealing gasket, and a negative electrode tab.

A first through hole is opened in the center of the upper sealing gasket, the upper air positive electrode is placed in the first through hole, and is closely attached to the upper surface of the upper sealing gasket, and the upper sealing gasket is also provided with an upper sealing gasket The sheet liquid injection hole communicates with the first through hole;

A second through hole is opened in the center of the lower sealing gasket, and the lower positive electrode of the air is placed in the second through hole, close to the lower surface of the lower sealing gasket, and the lower sealing gasket is also provided with a lower sealing gasket The sheet liquid injection hole is connected with the second through hole;

The first through hole and the second through hole have the same specifications and are aligned;

The upper air positive electrode, the upper diaphragm, the metal lithium negative electrode, the lower diaphragm, and the lower air positive electrode are stacked in sequence, and the negative electrode lug is protruded from the metal lithium negative electrode;

The upper sealing gasket is provided with an upper sealing gasket airway hole inlet and an upper sealing gasket airway hole outlet,

The lower sealing gasket is provided with the inlet of the airway hole of the lower sealing gasket and the outlet of the airway hole of the lower sealing gasket,

The inlet of the airway hole of the upper sealing gasket is aligned with the inlet of the airway hole of the lower sealing gasket, and the outlet of the airway hole of the upper sealing gasket is aligned with the outlet of the airway hole of the lower sealing gasket;

The number of the upper sealing gasket liquid injection hole and the lower sealing gasket liquid injection hole is at least 2 respectively.

The cell stack provided by the present invention can also be further realized by the following technical measures.

Preferably, the sum of the thickness of the upper sealing gasket and the thickness of the lower sealing gasket is less than or equal to the sum of the thicknesses of the upper air positive electrode, upper separator, metallic lithium negative electrode, lower separator, and lower air positive electrode.

Preferably, the specification of the metal lithium negative electrode is ≤ the specification of the upper separator, and the specification of the lower separator.

Preferably, the upper air positive electrode and the lower air positive electrode respectively include a collector layer and a reaction layer,

The current collecting layer is made of at least one material selected from carbon paper, carbon cloth, bucky paper, metal mesh and metal foam.

Preferably, the upper diaphragm and the lower diaphragm are respectively made of at least one material selected from glass fiber, polypropylene, and polyethylene.

Preferably, the upper sealing gasket and the lower sealing gasket are respectively made of at least one material selected from rubber, polytetrafluoroethylene, pyrex glass, and glass/ceramic composite materials.

In order to achieve the above-mentioned second purpose, the lithium-air secondary battery unit technical solution provided by the present invention is as follows:

The lithium-air secondary battery unit provided by the present invention sequentially includes an upper end plate, an upper gas deflector, a cell stack provided by the present invention, a lower gas deflector, and a lower end plate from top to bottom,

The upper end plate is provided with an upper end plate airway hole inlet and an upper end plate airway hole outlet,

The upper gas deflector is provided with an inlet of an airway hole of the upper gas deflector, an outlet of an airway hole of the upper gas deflector, and the lower surface of the upper gas deflector is provided with a first gas deflector mechanism,

The upper surface of the lower gas deflector is provided with a second gas deflector mechanism,

The inlet of the airway hole of the upper end plate, the inlet of the airway hole of the upper gas guide plate, the first gas guide mechanism, the inlet of the airway hole of the upper sealing gasket, the inlet of the airway hole of the lower sealing gasket, and the second gas guide mechanism , The outlet of the airway hole of the lower sealing gasket, the outlet of the airway hole of the upper sealing gasket, the outlet of the airway hole of the upper gas deflector, and the outlet of the airway hole of the upper end plate are connected;

The upper end plate is provided with an upper end plate liquid injection hole,

The upper gas deflector is provided with a liquid injection hole on the upper gas deflector,

The liquid injection hole of the upper end plate, the liquid injection hole of the upper gas guide plate, the liquid injection hole of the upper sealing gasket, and the liquid injection hole of the lower sealing gasket are sequentially connected;

The upper end plate and the lower end plate are fixedly connected.

The lithium-air secondary battery unit provided by the present invention can be further realized by adopting the following technical measures.

Preferably, protruding tabs are provided on the upper gas deflector and the lower gas deflector.

Preferably, the deflector mechanism includes a first deflector air hole channel, a second deflector air hole channel, and a flow guide groove,

The guide groove is arranged between the first guide plate air channel and the second guide plate air channel,

The air channel of the first deflector has a first protrusion to the left, and the air channel of the second deflector has a second protrusion to the right,

The inlet of the airway hole of the upper end plate, the inlet of the airway hole of the upper gas guide plate, the inlet of the airway hole of the upper sealing gasket, the inlet of the airway hole of the lower sealing gasket, the first protruding part, the second protruding part, the lower The outlet of the airway hole of the sealing gasket, the outlet of the airway hole of the upper sealing gasket, the outlet of the airway hole of the upper gas deflector, and the outlet of the airway hole of the upper end plate are connected in sequence.

Preferably, the upper end plate is provided with a first threaded hole of the upper end plate, a second threaded hole of the upper end plate, a third threaded hole of the upper end plate, and a fourth threaded hole of the upper end plate;

The lower end plate is provided with a first threaded hole of the lower end plate, a second threaded hole of the lower end plate, a third threaded hole of the lower end plate, and a fourth threaded hole of the lower end plate;

The first threaded hole of the upper end plate is aligned with the first threaded hole of the lower end plate,

The second threaded hole of the upper end plate is aligned with the second threaded hole of the lower end plate,

The third threaded hole of the upper end plate is aligned with the third threaded hole of the lower end plate,

The fourth threaded hole of the upper end plate is aligned with the fourth threaded hole of the lower end plate,

The upper end plate and the lower end plate can be fixedly connected by locking bolts.

Preferably, the flow field of the diversion groove between the lower surface of the upper gas deflector and the upper surface of the lower gas deflector is selected from parallel flow field, serpentine flow field, interdigitated flow field, point flow field, One of the bionic flow fields.

As preferably, the electrolyte of the lithium-air secondary battery unit includes an organic solvent and a lithium salt;

The organic solvent is selected from at least one of carbonates, ethers, amides, sulfones, sulfoxides, and ionic liquids;

The lithium salt is at least one selected from LiPF ₆ , LiBF ₄ , LiB(CN) ₄ , LiClO ₄ , LiSO ₃ CF ₃ , and LiN(SO ₂ CF ₃ ) ₂ .

Preferably, the upper end plate and the lower end plate are respectively made of one of metal, plexiglass, engineering plastics, and wood materials.

Preferably, the cross-section of the lithium-air secondary battery unit is selected from one of quadrilateral, circular, triangular, fan-shaped, and irregular shapes.

In order to achieve the above-mentioned third purpose, the technical scheme of the assembly method of the lithium-air secondary battery unit provided by the present invention is as follows:

The assembling method of the lithium-air secondary battery unit provided by the invention comprises the following steps:

Assembling the upper air cathode to the upper sealing gasket;

Assembling the lower air cathode to the lower sealing gasket;

Assembling the negative electrode tab to the metal lithium negative electrode;

The lower end plate, the lower gas deflector, the lower sealing gasket assembled with the lower air positive electrode, the lower diaphragm, the metal lithium electrode assembled with the negative electrode tab, the upper diaphragm, and the assembly are sequentially stacked from the bottom to the top. The upper sealing gasket, the upper gas deflector, and the upper end plate of the upper air positive electrode;

Fixing the upper end plate and the lower end plate together;

Injecting an electrolyte through a liquid injection hole, so that both the upper diaphragm and the lower diaphragm are wetted by the electrolyte;

Connect the external circuit and gas circuit to complete the assembly of the lithium-air secondary battery unit.

The assembly method of the lithium-air secondary battery unit provided by the present invention can also be further realized by adopting the following technical measures.

Preferably, when the electrolyte is injected through the liquid injection holes, the electrolyte is injected from one group of the liquid injection holes, and at the same time, negative pressure is drawn from the remaining liquid injection holes.

Preferably, the method is carried out in a dry environment.

Preferably, before the lithium-air secondary battery unit is assembled, it also includes the upper end plate, the upper gas deflector, the upper sealing gasket, the lower sealing gasket, the upper air positive electrode, the upper diaphragm, and the lower diaphragm. , the step of drying the lower air positive electrode, the negative electrode tab, the lower gas deflector, and the lower end plate.

Preferably, the step of drying is realized by drying.

Preferably, when performing the step of drying, the temperature of the oven ranges from 60°C to 100°C, and the duration ranges from 2h to 15h.

The gas deflector in contact with the air positive electrode of the lithium-air secondary battery unit with the cell stack assembled by the assembly method provided by the present invention serves as the positive electrode current collector on the one hand, and the gas flow channel on the surface on the other hand. Distributing the reaction gas to the air positive end of the lithium-air battery can achieve uniform gas field distribution and controllable gas flow and pressure; the lamination method of "positive electrode-diaphragm-negative electrode-diaphragm-positive electrode" is adopted, and the lithium negative electrode is used as the common negative electrode; The battery unit has high reliability, good structural stability, high modularization level, no need for soft pack battery heat sealing and other processes, and is easy to assemble. According to the first charge and discharge curve of the lithium-air secondary battery unit, it can be proved that the lithium-air secondary battery unit can be charged and discharged normally, and the capacity is much larger than the conventional button battery and Swaglok battery in the laboratory.

Description of drawings

Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiment. The drawings are only for the purpose of illustrating a preferred embodiment and are not to be considered as limiting the invention. Also throughout the drawings, the same reference numerals are used to designate the same components. In the attached picture:

Fig. 1 is an exploded view of a cell stack provided by Embodiment 1 of the present invention;

2 is an exploded view of a lithium-air secondary battery unit provided in Embodiment 2 of the present invention (wherein, the upper air positive electrode, upper diaphragm, metal lithium negative electrode, lower diaphragm, lower air positive electrode, and negative electrode lugs are not shown);

Fig. 3 is a flow chart of the steps of the assembly method of the lithium-air secondary battery unit provided by the third embodiment of the present invention;

Fig. 4 is the first cycle charge and discharge curves of the lithium-air secondary battery unit provided in Example 2 of the present invention (wherein the charge and discharge current is 0.1 mA/cm ² ).

Detailed ways

In order to solve the problems existing in the prior art, the present invention provides a cell stack, a lithium-air secondary battery unit formed based on the cell stack, and a method for assembling the lithium-air secondary battery unit, thereby more practical.

In order to further explain the technical means and effects of the present invention to achieve the intended purpose of the invention, the following in conjunction with the accompanying drawings and preferred embodiments, the battery stack, lithium-air secondary battery unit and assembly method thereof proposed according to the present invention , its specific implementation, structure, features and effects are described in detail below. In the following description, different "one embodiment" or "embodiment" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.

The term "and/or" in this article is just an association relationship describing associated objects, which means that there can be three relationships, for example, A and/or B. The specific understanding is: A and B can be included at the same time, and A and B can be included separately. A exists, B may exist alone, and any of the above three situations can be met.

Example 1

Referring to Figure 1, the cell stack provided in Example 1 of the present invention includes an upper sealing gasket 3a, an upper air positive electrode 20, an upper diaphragm 21, a metal lithium negative electrode 22, a lower diaphragm 23, a lower air positive electrode 24, and a negative electrode tab 25. , the lower sealing gasket 3b, the center of the upper sealing gasket 3a is provided with a first through hole 27a, the upper air positive electrode 20 is assembled in the first through hole 27a, and the upper air positive electrode 20 and the upper sealing gasket 3a are also provided with a second through hole One upper sealing gasket liquid injection hole 15aa, the second upper sealing gasket liquid injection hole 15ab; the center of the lower sealing gasket 3b is provided with a second through hole 27b, the lower air positive electrode 24 is assembled in the second through hole 27b, and the lower air There are also a first lower sealing gasket liquid injection hole 15ba and a second lower sealing gasket liquid injection hole 15bb between the positive electrode 24 and the lower sealing gasket 3b; the upper air positive electrode 20, the upper diaphragm 21, the metal lithium negative electrode 22, the lower Diaphragm 23 and lower air positive electrode 24 are stacked in sequence, and negative electrode lug 25 protrudes from metal lithium negative electrode 22; upper sealing gasket 3a is provided with upper sealing gasket air channel hole inlet 13a, upper sealing gasket air channel hole outlet 14a , the lower sealing gasket 3b is provided with a lower sealing gasket airway hole inlet 13b, a lower sealing gasket airway hole outlet 14b, an upper sealing gasket airway hole inlet 13a is aligned with a lower sealing gasket airway hole inlet 13b , the airway hole outlet 14a of the upper sealing gasket is aligned with the airway hole outlet 14b of the lower sealing gasket.

Wherein, the specification of the first through hole 27 a is the same as that of the upper air positive electrode 20 , and the specification of the second through hole 27 b is the same as that of the lower air positive electrode 24 . In this case, the sealing between the upper positive air electrode 20 and the upper sealing gasket 3 a and the sealing between the lower air positive electrode 24 and the lower sealing gasket 3 b can be ensured.

Wherein, the specifications of the upper diaphragm 24 ≥ the specifications of the upper air positive electrode 20, the specifications of the lower diaphragm 23 ≥ the specifications of the lower air positive electrode 24, the specifications of the metal lithium negative electrode 22 are smaller than the upper diaphragm 21, and the specifications of the lower diaphragm 23. In this case, it can be ensured that the upper air positive electrode 20 , the metal lithium negative electrode 22 , and the lower air electrode 24 are insulated from each other.

Wherein, the upper air positive electrode 20 and the lower air positive electrode 24 respectively include a current collecting layer and a reaction layer, and the current collecting layer is made of at least one material selected from carbon paper, carbon cloth, bucky paper, metal mesh, and metal foam.

Wherein, the upper diaphragm 21 and the lower diaphragm 23 are respectively made of at least one material selected from fiber diaphragm, polypropylene and polyethylene.

Wherein, the upper sealing gasket 3a and the lower sealing gasket 3b are respectively made of at least one material selected from rubber, polytetrafluoroethylene, pyrex glass, glass, and ceramic composite materials.

Example 2

Referring to Figure 2, the lithium-air secondary battery unit provided by Embodiment 2 of the present invention includes an upper end plate 1, an upper gas deflector 2, a cell stack provided by Embodiment 1 of the present invention, and a lower gas deflector from top to bottom. Flow plate 4, lower end plate 5, upper end plate 1 is provided with upper end plate airway hole inlet 7, upper end plate airway hole outlet 8, upper gas deflector 2 is provided with upper gas deflector airway hole inlet 10, The upper gas deflector airway hole outlet 11, the upper gas deflector 2 lower surface and the lower gas deflector 4 upper surface are all provided with a gas deflector mechanism, the upper end plate airway hole inlet 7, the upper gas deflector gas Channel hole inlet 10, upper sealing gasket airway hole inlet 13a, lower sealing gasket airway hole inlet 13b, diversion mechanism, lower sealing gasket airway hole outlet 14b, upper sealing gasket airway hole outlet 14a, upper The air channel hole outlet 11 of the gas deflector plate and the air channel hole outlet 8 of the upper end plate are sequentially connected; The first upper gas deflector liquid injection hole 12a, the second upper gas deflector liquid injection hole 12b, the first upper end plate liquid injection hole 9a, the first upper gas deflector liquid injection hole 12a, the first The liquid injection hole 15aa of the upper sealing gasket and the liquid injection hole 15ba of the first lower sealing gasket are sequentially connected, the liquid injection hole 9b of the second upper end plate, the liquid injection hole 12b of the second upper gas guide plate, and the injection hole 12b of the second upper sealing gasket The liquid hole 15ab and the second lower sealing gasket liquid injection hole 15bb are sequentially connected; the upper end plate 1 and the lower end plate 5 are fixedly connected.

Wherein, protruding tabs 19b are provided on the lower gas deflector 4 . In this case, the upper gas deflector 2 is also provided with a protruding tab 19a, the tab 19a is provided with a connection hole 26a, and the tab 19b is provided with a connection hole 26b, and the upper gas deflector 2 can be locked by locking the bolt. The gas deflector 2 and the lower gas deflector 4 are fixedly connected together.

Wherein, the flow guide mechanism includes a first air guide plate air channel 16, a second air guide plate air channel 17, and a guide groove 18, and the flow guide groove 18 is arranged on the first air guide plate air channel 16 and the second air guide plate air hole Between the roads 17, the first deflector air channel 16 has a first protrusion to the left, the second deflector air channel 17 has a second protrusion to the right, and the upper end plate air channel hole inlet 7, upper Airway hole inlet 10 of gas deflector, upper sealing gasket airway hole inlet 13a, lower sealing gasket airway hole inlet 13b, first protrusion, second protrusion, lower sealing gasket airway hole outlet 14b, the upper sealing gasket airway hole outlet 14a, the upper gas deflector airway hole outlet 11, and the upper end plate airway hole outlet 8 are connected in sequence.

Wherein, the upper end plate 1 is provided with the first threaded hole 1a of the upper end plate, the second threaded hole 1b of the upper end plate, the third threaded hole 1c of the upper end plate, and the fourth threaded hole 1d of the upper end plate; the lower end plate is provided with the first threaded hole of the lower end plate Hole 6a, the second threaded hole 6b of the lower end plate, the third threaded hole 6c of the lower end plate, the fourth threaded hole 6d of the lower end plate; the first threaded hole 1a of the upper end plate is aligned with the first threaded hole 6a of the lower end plate, and the second threaded hole of the upper end plate The hole 1b is aligned with the second threaded hole 6b of the lower end plate, the third threaded hole 1c of the upper end plate is aligned with the third threaded hole 6c of the lower end plate, the fourth threaded hole 1d of the upper end plate is aligned with the fourth threaded hole 6d of the lower end plate, and passed The locking bolts can fix the upper end plate 1 and the lower end plate 5 .

Wherein, the flow field between the lower surface of the upper gas deflector 2 and the upper surface of the lower gas deflector 4 is selected from parallel flow field, serpentine flow field, interdigitated flow field, point flow field and bionic flow field. kind of.

Wherein, the electrolyte solution of the lithium-air secondary battery unit includes an organic solvent and a lithium salt; the organic solvent is selected from at least one of carbonates, ethers, amides, sulfones, sulfoxides, and ionic liquids; the lithium salt is selected from At least one of LiPF ₆ , LiBF ₄ , LiB(CN) ₄ , LiClO ₄ , LiSO ₃ CF ₃ , LiN(SO ₂ CF ₃ ) ₂ .

Wherein, the upper end plate 1 and the lower end plate 5 are respectively made of one of metal, plexiglass, engineering plastics and wood materials.

Wherein, the cross-section of the lithium-air secondary battery unit is selected from one of quadrilateral, circular, triangular, fan-shaped, and irregular shapes.

Example 3

Referring to accompanying drawing 3, the assembling method of the lithium-air secondary battery unit provided by embodiment 3 of the present invention comprises the following steps:

Step 1: Assemble the upper air positive electrode 20 to the upper sealing gasket 3a; assemble the lower air positive electrode 24 to the lower sealing gasket 3b; assemble the negative electrode tab 25 to the metal lithium negative electrode 22;

Step 2: stack the lower end plate 5, the lower gas deflector 4, the lower sealing gasket 3b assembled with the lower air positive electrode 24, the lower diaphragm 23, and the metal lithium electrode 22 assembled with the negative electrode tab 25 from the bottom to the top. The upper diaphragm 21, the upper sealing gasket 3a assembled with the upper air positive electrode 20, the upper gas deflector 2, and the upper end plate 1;

Step 3: Fix the upper end plate 2 and the lower end plate 5 together;

Step 4: Inject the electrolyte through one of the groups of liquid injection holes 9a-12a-15aa-15ba, so that both the upper diaphragm 21 and the lower diaphragm 23 are wetted by the electrolyte; in this embodiment, through one of the group of liquid injection holes 9a- 12a-15aa-15ba inject the electrolyte while drawing negative pressure from the remaining liquid injection holes 15bb-15ab-12b-9b. In this way, the liquid injection efficiency can be improved and the upper diaphragm 21 and the lower diaphragm 23 can be wetted by the electrolyte Effect.

Step 5: Connect the external circuit and air circuit to complete the assembly of the lithium-air secondary battery unit.

Wherein, the method is carried out in a dry environment.

Wherein, before the lithium-air secondary battery unit is assembled, it also includes the upper end plate 1, the upper gas guide plate 2, the upper sealing gasket 3a, the lower sealing gasket 3b, the upper air positive electrode 20, the upper diaphragm 21,, The lower diaphragm 23, the lower air positive electrode 24, the negative electrode tab 25, the lower gas guide plate 4, and the lower end plate 5 are dried.

Wherein, the step of drying is realized by drying.

Wherein, when performing the step of drying, the temperature of the oven ranges from 60° C. to 90° C., and the duration ranges from 2 hours to 15 hours.

Example 4

The upper end plate 1, the upper gas guide plate 2, the upper sealing gasket 3a, the lower sealing gasket 3b, the lower gas guide plate 4, the lower end plate 5, the upper air positive electrode 20, the lower air electrode 24, the glass fiber diaphragm 21, 23. Put the negative electrode tab 25, etc. into an oven to dry at 80°C for 12 hours, then take it out. Among them, the upper end plate 1 and the lower end plate 5 are made of plexiglass plate, the upper gas deflector 2 and the lower gas deflector 4 are processed by graphite plate, and there is a serpentine flow field on one side surface. In the drying room or in the glove box, stack the lower end plate 5, the lower gas deflector 4, and the first sealing gasket 3b sequentially, and stack the lower air positive electrode 24, glass fiber diaphragm 23, The metal lithium negative electrode 22, the glass fiber separator 21, the upper air positive electrode 20, and then the second sealing gasket 3a, the upper gas guide plate 2, and the upper end plate 1 are placed in sequence. Among them, the upper air positive electrode 20 and the lower air positive electrode 24 are prepared by coating XC-72:PTFE (mass ratio 8:2) slurry on hydrophobic carbon paper, and the carbon load is 5 mg/cm ² ; the upper and lower The sides of the gas deflectors 2 and 4 that have flow channels dug are in contact with the upper air positive electrode 20 and the lower air positive electrode 24 respectively, and the negative electrode tab 25 is drawn from between the upper sealing gasket 3a and the lower sealing gasket 3b to avoid contact with the upper air positive electrode 20 and the lower air positive electrode 24 respectively. The gas deflector 2 and the lower gas deflector 4 are short-circuited in contact. When assembling, ensure that the centers of each layer are on a straight line, and ensure that the airway hole inlet 7-10-13a-13b-16 is aligned, the airway hole outlet 17-14b-14a-11-8 is aligned, and the liquid injection hole 9a-12a -15aa-15ba alignment, liquid injection hole 15bb-15ab-12b-9b alignment. Screw rods are inserted into the four corresponding angles 1a-6a, 1b-6b, 1c-6c, 1d-6d of the upper end plate 1 and the lower end plate 5, and the assembly is completed after fastening with screws. Inject 1MLiN(SO ₂ CF ₃ ) ₂ /TEGDME electrolyte into the device through one of the liquid injection holes 9a-12a-15aa-15ba, and at the same time draw negative pressure from the liquid injection holes 15bb-15ab-12b-9b to make the upper glass fiber The diaphragm 21 and the lower glass fiber diaphragm 23 are wetted, and the final assembly is completed after standing still. When measuring the battery, connect the tab 19 protruding from the upper gas deflector and the lower gas deflector in parallel as the positive terminal, and the protruding negative pole tab 25 as the negative terminal, and pass into the battery through the inlet 7 of the air passage hole. pure oxygen.

Example 5

The upper end plate 1, the upper gas guide plate 2, the upper sealing gasket 3a, the lower sealing gasket 3b, the lower gas guide plate 4, the lower end plate 5, the upper air positive electrode 20, the lower air electrode 24, and the upper glass fiber diaphragm 21 , the lower glass fiber diaphragm 23, the negative electrode lug 25, etc. were put into an oven to dry at 80° C. for 12 hours, and then taken out. The upper end plate 1 and the lower end plate 5 are made of stainless steel, the upper gas deflector 2 and the lower gas deflector 4 are processed by metal plates, and there is a parallel flow field on one side surface. In the drying room or in the glove box, stack the lower end plate 5, the lower gas deflector 4, the lower sealing gasket 3b sequentially, and stack the lower air positive electrode 24, the lower glass fiber diaphragm 23, The metal lithium negative electrode 22, the glass fiber separator 21, the upper air positive electrode 20, and then the upper sealing gasket 3a, the upper gas guide plate 2, and the upper end plate 1 are placed in sequence. Among them, the upper air positive electrode 20 and the lower air positive electrode 24 are prepared by coating Super P:PTFE (mass ratio 8:2) slurry on a stainless steel mesh, with a carbon load of 3 mg/cm ² ; the upper and lower gas deflectors 2, 4 The side where the flow channel is dug is in contact with the upper air positive electrode 20 and the lower air positive electrode 24, and the negative electrode tab 25 is drawn out from the upper sealing gasket 3a and the lower sealing gasket 3b to avoid contact with the upper gas guide plate 2, The lower gas deflector 4 is contacted and short-circuited, and an insulating gasket is placed between the upper end plate 1, the lower end plate 5, the upper gas deflector 2, and the lower gas deflector 4. When assembling, ensure that the centers of each layer are on a straight line, and ensure that the airway hole inlet 7-10-13a-13b-16 is aligned, the airway hole outlet 17-14b-14a-11-8 is aligned, and the liquid injection hole 9a-12a -15aa-15ba alignment, liquid injection hole 15bb-15ab-12b-9b alignment. Screw rods are inserted into the four corresponding angles 1a-6a, 1b-6b, 1c-6c, 1d-6d of the upper end plate 1 and the lower end plate 5, and the assembly is completed after fastening with screws. Inject 1M LiClO ₄ /DMSO electrolyte into the mold through one of the liquid injection holes 9a-12a-15aa-15ba, and at the same time draw negative pressure from the liquid injection holes 15bb-15ab-12b-9b to make the upper glass fiber diaphragm 21, the lower glass fiber The diaphragm 23 is wetted and allowed to stand to complete the final assembly. When measuring the battery, connect the tab 19 protruding from the upper gas deflector and the lower gas deflector in parallel as the positive terminal, and the protruding negative pole tab 25 as the negative terminal, and pass the dry air into the battery through the inlet 7 of the air passage hole. High purity oxygen.

Example 6

The upper end plate 1, the upper gas guide plate 2, the upper sealing gasket 3a, the lower sealing gasket 3b, the lower gas guide plate 4, the lower end plate 5, the upper air positive electrode 20, the lower air electrode 24, and the upper glass fiber diaphragm 21 , the lower glass fiber diaphragm 23, the negative electrode lug 25, etc. were put into an oven to dry at 80° C. for 12 hours, and then taken out. The upper end plate 1 and the lower end plate 5 are made of hardwood, the upper gas deflector 2 and the lower gas deflector 4 are processed by metal plates, and there is a parallel flow field on one side surface. In the drying room or glove box, stack the lower end plate 5, the lower gas guide plate 4, the lower sealing gasket 3b in sequence, and stack the lower air positive electrode 24, glass fiber diaphragm 23, metal The lithium negative electrode 22, the upper glass fiber separator 21, the upper air positive electrode 20, and then the upper sealing gasket 3a, the upper gas guide plate 2, and the upper end plate 1 are placed in sequence. Among them, the upper air positive electrode 20 and the lower air positive electrode 24 are prepared by coating KejtenBlack:PTFE:MnO ₂ (mass ratio 7:1:2) slurry on nickel foam and rolling, with a carbon load of 3 mg/cm ² ; The side of the upper gas deflector 2 and the lower gas deflector 4 with flow channels dug is in contact with the upper air positive electrode 20 and the lower air positive electrode 24, and the negative electrode tab 25 is drawn out from the two sealing gaskets 3 to avoid contact with the upper gas The deflector 2 and the lower gas deflector 4 are contacted and short-circuited, and an insulating gasket is placed between the upper end plate 1 , the lower end plate 5 and the upper gas deflector 2 and the lower gas deflector 4 . When assembling, ensure that the centers of each layer are on a straight line, and ensure that the airway hole inlet 7-10-13a-13b-16 is aligned, the airway hole outlet 17-14b-14a-11-8 is aligned, and the liquid injection hole 9a-12a -15aa-15ba alignment, liquid injection hole 15bb-15ab-12b-9b alignment. Screw rods are inserted into the four corresponding angles 1a-6a, 1b-6b, 1c-6c, 1d-6d of the upper end plate 1 and the lower end plate 5, and the assembly is completed after fastening with screws. Inject 1M LiCF ₃ SO ₃ /TEGDME electrolyte into the mold through one of the injection holes 9a-12a-15aa-15ba, and at the same time draw negative pressure from the injection holes 15bb-15ab-12b-9b to make the upper glass fiber diaphragm 21, The lower glass fiber diaphragm 23 is wetted and left to stand to complete the final assembly. When measuring the battery, connect the tabs 19 protruding from the upper gas deflector 2 and the lower gas deflector 4 in parallel as the positive terminal, and the protruding negative pole tab 25 as the negative terminal, and pass through the airway hole inlet 7-10-13a -13b-16 Introduce dry high-purity oxygen into the battery.

While preferred embodiments of the invention have been described, additional changes and modifications to these embodiments can be made by those skilled in the art once the basic inventive concept is appreciated. Therefore, it is intended that the appended claims be construed to cover the preferred embodiment as well as all changes and modifications which fall within the scope of the invention.

Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention also intends to include these modifications and variations.

Claims (20)

1. A kind of 1. cell lamination, it is characterised in that including upper gasket seal, upper air cathode, upper diaphragm, lithium anode, under Barrier film, lower air cathode, lower seal pad piece, negative lug,

   The upper gasket seal center offers first through hole, and the upper air cathode is positioned in the first through hole, is close to Upper gasket seal upper surface, the upper gasket seal is further opened with gasket seal liquid injection hole, and is communicated with first through hole；

   The lower seal pad piece center offers the second through hole, and the lower air cathode is positioned in second through hole, is close to Lower seal pad piece lower surface, the lower seal pad piece is further opened with lower seal pad piece liquid injection hole, and is connected with the second through hole；

   The first through hole is identical with the second through hole specification and is aligned；

   The upper air cathode, upper diaphragm, lithium anode, lower diaphragm plate, lower air cathode are sequentially stacked, the negative lug by The lithium anode stretches out；

   The upper gasket seal is provided with upper gasket seal air flue hole import, upper gasket seal air flue hole exits,

   The lower seal pad piece is provided with the hole import of lower seal pad piece air flue, lower seal pad piece air flue hole exits,

   The upper gasket seal air flue hole import is aligned with lower seal pad piece air flue hole import, and the upper gasket seal air flue hole goes out Mouth is aligned with lower seal pad piece air flue hole exits；

   The upper gasket seal liquid injection hole, the quantity of lower seal pad piece liquid injection hole are at least corresponding 2 respectively.
2. 2. cell lamination according to claim 1, it is characterised in that the upper gasket seal thickness is thick with lower seal pad piece Spend sum≤upper air cathode, upper diaphragm, lithium anode, lower diaphragm plate, lower air cathode thickness sum.
3. 3. cell lamination according to claim 1, it is characterised in that

   The specification of the specification of the lithium anode≤upper diaphragm and the lower diaphragm plate.
4. 4. cell lamination according to claim 1, it is characterised in that

   The upper air cathode, lower air cathode include current collector layer and conversion zone respectively,

   The current collector layer is selected from least one of carbon paper, carbon cloth, Buckie paper, wire netting, foam metal material and is made.
5. 5. cell lamination according to claim 1, it is characterised in that the upper diaphragm, lower diaphragm plate are respectively selected from glass fibers At least one of dimension, polypropylene, polyethylene material is made.
6. 6. cell lamination according to claim 1, it is characterised in that the upper gasket seal, lower seal pad piece select respectively It is made from least one of rubber, polytetrafluoroethylene (PTFE), Pyrex glass, glass/ceramic composite material.
7. A kind of 7. lithium air secondary battery unit, it is characterised in that from top to bottom successively include upper head plate, upper gas guide board, Any described cell lamination, lower gas guide board, bottom plate in claim 1~6,

   The upper head plate is provided with the hole import of upper head plate air flue, upper head plate air flue hole exits,

   The upper gas guide board is provided with upper gas guide board air flue hole import, upper gas guide board air flue hole exits, upper gas Body deflector lower surface is provided with first gas deflector,

   The lower gas guide board upper surface is provided with second gas deflector,

   The upper head plate air flue hole import, upper gas guide board air flue hole import, first gas deflector, upper gasket seal gas The import of road hole, the hole import of lower seal pad piece air flue, second gas deflector, lower seal pad piece air flue hole exits, upper sealing gasket Piece air flue hole exits, upper gas guide board air flue hole exits, the connection of upper head plate air flue hole exits；

   The upper head plate is provided with upper head plate liquid injection hole,

   The upper gas guide board is provided with upper gas guide board liquid injection hole,

   The upper head plate liquid injection hole, upper gas guide board liquid injection hole, upper gasket seal liquid injection hole, lower seal pad piece liquid injection hole are successively Connection；

   It is fixedly connected between the upper head plate and bottom plate.
8. 8. lithium air secondary battery unit according to claim 7, it is characterised in that the upper gas guide board and lower gas Body deflector is provided with the lug of protrusion.
9. 9. lithium air secondary battery unit according to claim 7, it is characterised in that the deflector is led including first Flowing plate stomata road, the second deflector stomata road, guiding gutter,

   The guiding gutter is arranged between the first deflector stomata road and the second deflector stomata road,

   The first deflector stomata road has the first protuberance to the left, and the second deflector stomata road has the to the right Two protuberances,

   The upper head plate air flue hole import, upper gas guide board air flue hole import, upper gasket seal air flue hole import, lower seal pad The hole import of piece air flue, the first protuberance, the second protuberance, lower seal pad piece air flue hole exits, upper gasket seal air flue hole exits, Upper gas guide board air flue hole exits, upper head plate air flue hole exits are sequentially communicated.
10. 10. lithium air secondary battery unit according to claim 7, it is characterised in that

    The upper head plate is provided with the screwed hole of upper head plate first, the screwed hole of upper head plate second, the screwed hole of upper head plate the 3rd, upper head plate 4th screwed hole；

    The bottom plate is provided with the screwed hole of bottom plate first, the screwed hole of bottom plate second, the screwed hole of bottom plate the 3rd, bottom plate 4th screwed hole；

    The screwed hole of upper head plate first is aligned with the screwed hole of bottom plate first,

    The screwed hole of upper head plate second is aligned with the screwed hole of bottom plate second,

    The screwed hole of upper head plate the 3rd is aligned with the screwed hole of bottom plate the 3rd,

    The screwed hole of upper head plate the 4th is aligned with the screwed hole of bottom plate the 4th,

    The upper head plate can be fixedly connected with the bottom plate by clamping screw.
11. 11. lithium air secondary battery unit according to claim 7, it is characterised in that the upper gas guide board following table Guiding gutter flow field between face, lower gas guide board upper surface is selected from parallel flow field, serpentine flow, interdigitated flow field, point-like stream One kind in field, bionical flow field.
12. 12. lithium air secondary battery unit according to claim 7, it is characterised in that the lithium air secondary battery list The electrolyte of member includes organic solvent and lithium salts；

    The organic solvent is selected from least one of carbonates, ethers, amide-type, sulfone class, sulfoxide type, ionic liquid；

    The lithium salts is selected from LiPF₆,LiBF₄,LiB(CN)₄,LiClO₄,LiSO₃CF₃,LiN(SO₂CF₃)₂At least one of.
13. 13. lithium air secondary battery unit according to claim 7, it is characterised in that the upper head plate, bottom plate difference One kind in metal, lucite, engineering plastics, wood materials is made.
14. 14. lithium air secondary battery unit according to claim 7, it is characterised in that the lithium air secondary battery list The one kind of the cross section of member in quadrangle, circle, triangle, sector, irregular figure.
15. 15. the assemble method of any described lithium air secondary battery unit in claim 7~14, it is characterised in that including Following steps：

    The upper air cathode is assembled to the upper gasket seal；

    The lower air cathode is assembled to the lower seal pad piece；

    The negative lug is assembled to the lithium anode；

    Stack successively on lower the bottom plate, lower gas guide board, the lower seal pad piece for being assembled with the lower air cathode, Lower diaphragm plate, the metal lithium electrode for being assembled with negative lug, upper diaphragm, the upper gasket seal for being assembled with the upper air cathode, on Gas guide board, upper head plate；

    The upper head plate, bottom plate are fixed together；

    Electrolyte is injected by liquid injection hole so that the upper diaphragm and lower diaphragm plate are soaked by the electrolyte；

    External circuit and gas circuit are connected, completes the assembling of the lithium air secondary battery unit.
16. 16. the assemble method of lithium air secondary battery unit according to claim 15, it is characterised in that pass through liquid injection hole When injecting electrolyte, one group of liquid injection hole injects electrolyte therefrom, meanwhile, take out negative pressure from remaining liquid injection hole.
17. 17. the assemble method of lithium air secondary battery unit according to claim 15, it is characterised in that methods described is Carry out in a dry environment.
18. 18. the assemble method of lithium air secondary battery unit according to claim 15, it is characterised in that to the lithium Before air secondary battery unit is assembled, in addition to the upper head plate, upper gas guide board, upper gasket seal, overhead Gas positive pole, upper diaphragm, lower seal pad piece, lower diaphragm plate, lower air cathode, negative lug, lower gas guide board, bottom plate are done Dry step.
19. 19. the assemble method of lithium air secondary battery unit according to claim 18, it is characterised in that the drying Step is realized by drying.
20. 20. the assemble method of lithium air secondary battery unit according to claim 19, it is characterised in that described in execution During the step of drying, the temperature span of baking oven is 60 DEG C~100 DEG C, and the span of duration is 2h~15h.