CN114709373A - Method and system for preparing SEI film of battery pole piece and supplementing lithium - Google Patents
Method and system for preparing SEI film of battery pole piece and supplementing lithium Download PDFInfo
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- CN114709373A CN114709373A CN202210441572.8A CN202210441572A CN114709373A CN 114709373 A CN114709373 A CN 114709373A CN 202210441572 A CN202210441572 A CN 202210441572A CN 114709373 A CN114709373 A CN 114709373A
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- pole piece
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- sei film
- lithium
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 73
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 54
- 239000012495 reaction gas Substances 0.000 claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 39
- 239000013589 supplement Substances 0.000 claims description 28
- 238000007664 blowing Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000004804 winding Methods 0.000 claims description 9
- 230000005855 radiation Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000009469 supplementation Effects 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001216 Li2S Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910007511 Li2S2O4 Inorganic materials 0.000 description 1
- 229910007505 Li2S2O5 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method and a system for preparing and supplementing an SEI film of a battery pole piece. The invention discloses a method for preparing an SEI film of a battery pole piece and supplementing lithium, which comprises the following steps: immersing a lithium metal block in an electrolyte; immersing the pole piece into electrolyte; connecting the pole piece and the lithium metal block into a power supply for electrifying; and introducing reaction gas into the electrolyte, wherein the reaction gas flows to the pole piece, so that an SEI film is formed on the pole piece, and lithium ions are embedded into the pole piece. Compared with the prior art, the high-efficiency production is realized, and the performance of the battery is greatly improved while the energy density of the battery is improved.
Description
Technical Field
The embodiment of the invention relates to the field of batteries, in particular to a method and a system for preparing and supplementing an SEI film of a battery pole piece.
Background
Along with the increasing demand of people on mobile terminals and new energy automobiles, the requirement on endurance is also higher, and the energy density of a matched battery is required to be greatly improved. However, in the case of a graphite system as the negative electrode, the specific capacity of the negative electrode gradually reaches a bottleneck, which makes it difficult to increase the energy density. In recent years, in order to remarkably improve the energy density of the battery, silicon-doped lithium supplement becomes a great importance of lithium battery enterprises, and a development route is also necessary, namely a silicon negative electrode material system with higher specific capacity is used as a negative electrode active material, and additional lithium supplement is carried out in the battery or the material. However, when the battery is charged for the first time, active lithium extracted from the anode needs to be consumed by the cathode due to the formation of an SEI film at the cathode, so that a large amount of lithium loss is generated, and particularly, the addition of a silicon-based material with lower first efficiency causes more lithium loss during the first charging, so that the energy density of the battery is reduced.
Disclosure of Invention
The invention aims to provide a method and a system for preparing and supplementing an SEI film of a battery pole piece, which realize high-efficiency production and greatly improve the performance of a battery while improving the energy density of the battery.
In order to solve the technical problem, an embodiment of the present invention provides a method for preparing an SEI film of a battery pole piece and supplementing lithium, including the following steps:
immersing a lithium metal block in the electrolyte;
immersing the pole piece in the electrolyte;
connecting the pole piece and the lithium metal block into a power supply for electrifying;
and introducing reaction gas into the electrolyte, wherein the reaction gas flows to the pole piece, so that an SEI film is formed on the pole piece, and lithium ions are embedded into the pole piece.
In one embodiment, the pole piece immersed in the electrolyte is parallel to the lithium metal block, and the pole piece immersed in the electrolyte is located above the lithium metal block.
In one embodiment, the pole piece immersed in the electrolyte is inclined to the horizontal plane by an angle greater than 0 ° and less than 90 °.
In one embodiment, the introduction direction of the reaction gas is opposite to the lower surface of the pole piece immersed in the electrolyte, and is located on the lower side of the pole piece immersed in the electrolyte.
In one embodiment, the method for preparing an SEI film of a battery electrode sheet and supplementing lithium further comprises the following steps: emitting radiation to a pole piece immersed in the electrolyte.
In one embodiment, the radiation is emitted towards the lower surface of a pole piece immersed in the electrolyte.
In one embodiment, the reactant gas includes CO2, CO, SO2、SO3、NO、NO2O2, HF.
The embodiment of the invention also provides an SEI film preparation and lithium supplement system for a battery pole piece, which comprises the following steps:
the electrode plate electrode box comprises a closable cabin body, wherein a containing chamber for containing electrolyte and an electrode plate is arranged in the cabin body, the top of the containing chamber is an opening area, and at least one side wall of the containing chamber is separated from at least one cabin wall of the cabin body to form an airflow channel communicated with the opening area; and the containment chamber is operatively vented with a reactant gas; the bin body is provided with an inlet for the pole piece to enter and an outlet for the pole piece to exit; and the number of the first and second groups,
gas circulation means provided on a side wall of the accommodating chamber forming the gas flow passage for drawing the reaction gas discharged from the opening area into the accommodating chamber through the gas flow passage;
the ray emitting device is arranged on the bin body and used for emitting rays into the accommodating chamber; and (c) a second step of,
a delivery device, comprising: the device comprises a releasing component used for releasing the pole piece and a winding component used for winding and retracting the pole piece after reaction in the accommodating chamber.
In one embodiment, the gas circulation device has a gas outlet facing the open area and parallel to the horizontal plane.
In one embodiment, a first conveying shaft and a second conveying shaft for conveying the pole pieces are arranged in the accommodating chamber, the first conveying shaft is higher than the second conveying shaft, and the first conveying shaft is closer to the unwinding member than the second conveying shaft.
In one embodiment, the SEI film preparation and lithium supplementation system for a battery electrode sheet further comprises: the drying device and the cleaning device are arranged outside the bin body, the drying device is located between the cleaning device and the winding part, and the cleaning device is located between the drying device and the second conveying shaft.
In one embodiment, the SEI film preparation and lithium supplementation system for a battery electrode sheet further comprises: the blowing device is used for conveying reaction gas into the accommodating chamber, and a blowing port of the blowing device faces the opening area and is parallel to the horizontal plane; the air blowing port is close to the side wall of the accommodating chamber forming the air flow channel.
Compared with the prior art, the electrochemical lithium supplement method can realize uniform lithium supplement of the pole piece, the lithium supplement amount can be set through a charging system, the lithium supplement requirements of different material systems can be met, and the energy density of the battery is greatly improved. And the reaction gas is also an effective SEI film forming additive, improves SEI components and is beneficial to improving the performance of the battery. The battery core prepared by the method has the advantages that the battery core has lower internal resistance, slower circulating capacity decay rate and obviously improved battery performance because the battery core forms the SEI film with better quality and carries out pre-lithiation activation on the active material in advance.
Drawings
One or more embodiments are illustrated by way of example in the accompanying drawings, which correspond to the figures in which like reference numerals refer to similar elements and which are not to scale unless otherwise specified.
FIG. 1 is a flow chart of a method for preparing an SEI film of a battery electrode plate and supplementing lithium according to a first embodiment of the present invention;
FIG. 2 is a schematic structural diagram of an SEI film preparation and lithium supplement system for a battery electrode plate according to a second embodiment of the present invention.
Wherein, 1, a bin body; 2. a gas circulation device; 21. an air outlet; 3. a radiation emitting device; 5. a housing chamber; 50. an open area; 10. an air flow channel; 41. unwinding the piece; 42. coiling the part; 43. a first transmission shaft; 44. a second transfer shaft; 6. a drying device; 7. a cleaning device; 8. a blowing device; 11. a spring; 12. a seal member; 91. pole pieces; 92. lithium metal block
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, embodiments of the present invention will be described in detail below with reference to the accompanying drawings. However, it will be appreciated by those of ordinary skill in the art that numerous technical details are set forth in order to provide a better understanding of the present application in various embodiments of the present invention. However, the technical solution claimed in the present application can be implemented without these technical details and various changes and modifications based on the following embodiments.
In the following description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the various disclosed embodiments. One skilled in the relevant art will recognize, however, that the embodiments may be practiced without one or more of the specific details. In other instances, well-known devices, structures and techniques associated with this application may not be shown or described in detail to avoid unnecessarily obscuring the description of the embodiments.
Throughout the specification and claims, the word "comprise" and variations thereof, such as "comprises" and "comprising," are to be understood as an open, inclusive meaning, i.e., as being interpreted to mean "including, but not limited to," unless the context requires otherwise.
The embodiments of the present invention will be described in detail below with reference to the accompanying drawings in order to more clearly understand the objects, features and advantages of the present invention. It should be understood that the embodiments shown in the drawings are not intended to limit the scope of the present invention, but are merely intended to illustrate the spirit of the technical solution of the present invention.
Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. It should be noted that the term "or" is generally employed in its sense including "and/or" unless the context clearly dictates otherwise.
In the following description, for the purposes of clearly illustrating the structure and operation of the present invention, directional terms will be used, but terms such as "front", "rear", "left", "right", "outer", "inner", "outer", "inward", "upper", "lower", etc. should be construed as words of convenience and should not be construed as limiting terms.
Embodiments of the present invention are described below with reference to the drawings.
The first embodiment of the invention relates to a method for preparing an SEI film of a battery pole piece and supplementing lithium, and as shown in figure 1, the method comprises the following steps:
step 100, immersing a lithium metal block into electrolyte; the electrolyte is an organic electrolyte special for electrochemical lithium supplement, and the temperature of the electrolyte in the cell can be controlled to be 10-100 ℃.
Further, the reaction gas comprises CO2, CO, SO2、SO3、NO、NO2O2, HF.
Specifically, the lithium metal block is used as a lithium source, lithium ions are continuously released, and finally the lithium metal block is embedded into an active material of the lithium pole piece to be compensated or an SEI film is formed. The lithium metal block is in a square block shape, is placed in parallel with the pole piece, and forms a certain inclination angle with the horizontal plane, and the inclination angle can be adjusted between 0-90 degrees, preferably 45 degrees or 30 degrees.
Taking the reaction gas as CO2 as an example, when the electrolyte is saturated with CO2, reduction of CO2 at a higher potential to produce Li2CO3 on the carbon negative electrode will greatly improve the performance of the carbon negative electrode such as reversible capacity, cycle efficiency, self-discharge rate, etc. CO2 can be preferentially reduced to Li2CO3 and CO in almost all alkyl carbonate, ether, carboxylate based electrolytes, thereby improving the cycling efficiency of the lithium electrode and suppressing dendrite formation. The presence of CO2 can change the composition of the SEI film inner layer to make the inner layer contain more Li2CO3 component. Thereby smoothing the deposition morphology and having a lower overpotential. CO2 improves the cycle life of the lithium electrode in PC based electrolytes, preventing damage to the lithium electrode from the presence of large amounts of water. CO2 mainly undergoes the following reduction process:
CO2+e－+Li+→·CO2Li
CO2+·CO2Li→·CO2CO2Li
·CO2CO2Li+e－+Li+→Li2CO3+CO
li2SO3 has similar properties to Li2CO3, and its lithium conducting properties are higher than the latter. Therefore, like CO2, SO2 is also an excellent film-forming additive, and the charge and discharge performance of the graphite negative electrode can be greatly improved by the presence of SO2 in the PC-based electrolyte. Unlike CO2, SO2 is more reactive and can form a stable SEI film on graphite anodes before reduction by many other additives or the electrolyte itself. The reduction reaction of SO2 on the carbon negative electrode is more complicated than that of CO2, and the reduction product thereof contains Li2S, Li2S2O4, Li2S2O5, and the like in addition to Li2SO 3. In addition, the organic electrolyte containing SO2 has higher conductivity than the organic electrolyte not containing SO 2. The SO2 concentration in the electrolyte significantly improved the performance of the graphite negative electrode even at very low concentrations. SO2 on the carbon cathode mainly undergoes the following reduction process:
SO2+6Li++6e－→2Li2O+Li2S
li2O + SO2 → (LiO)2SO or Li2O +2SO2 → (LiO) SOSO (LiO)
Usually, CO2 or SO2 participates in film formation by reducing gas dissolution in the electrolyte and injecting the electrolyte into the cell for formation, but CO2 or SO2 has low solubility in the electrolyte, and the electrolyte in the cell is less, SO that more CO2 or SO2 cannot participate in film formation. In the embodiment, before the pole piece is assembled, the electrochemical lithium supplement is performed, and simultaneously, CO2 or SO2 participates in film formation, SO that CO2 or SO2 can fully react to form a film, the film formation quality is good, and the components are uniform, because: firstly, gas is introduced at all times and is continuously and directly contacted with the pole piece, and meanwhile, the electrolyte has large volume and can dissolve sufficient CO2 and SO2, SO that the sufficiency of reaction products is ensured. Secondly, in the process of lithium supplement, high-energy rays are applied, which is beneficial to activating chemical bonds of reaction products, and the SEI electrochemical film forming reaction is easier to carry out.
In addition, in the process of first charging and film forming of a conventional battery, a plurality of byproducts such as alkane, CO2, CO, H2 and H2O are generated, so that not only are the electrolyte solvent and additive components consumed, but also the repair of the later-stage additive to the SEI film is influenced, and a plurality of side effects such as electrolyte deterioration, lithium salt hydrolysis, high viscosity, poor conductivity and the like are generated.
According to the electrochemical lithium supplement method, the uniform lithium supplement of the pole piece can be realized, the lithium supplement amount can be set through a charging system, the lithium supplement requirements of different material systems can be met, and the energy density of the battery is greatly improved. And the reaction gas is also an effective SEI film forming additive, improves SEI components and is beneficial to improving the performance of the battery. The battery core prepared by the method has the advantages that the battery core has lower internal resistance, slower circulating capacity decay rate and obviously improved battery performance because the battery core forms the SEI film with better quality and carries out pre-lithiation activation on the active material in advance.
Furthermore, the introducing direction of the reaction gas is opposite to the lower surface of the pole piece immersed in the electrolyte and is positioned on the lower side of the bottom of the accommodating chamber from the pole piece immersed in the electrolyte. Can set up gas blowing device in storehouse body below, and gas blowing device can be the air pump, lets in gas to electrolyte, and gas can be constantly come out from gas blowing device and flow along the pole piece under the buoyancy to can even effect to the pole piece, and form the bubble when gas flows, the clearance between the bubble can let the lithium ion pass to the pole piece.
In addition, as shown in fig. 1, the method for preparing the SEI film of the battery electrode plate and supplementing lithium further comprises the following steps: step 500: the radiation is emitted to a pole piece immersed in the electrolyte. This step may be performed in synchronization with step 400, or before or after step 400. The rays can be high-energy X rays, the high-energy X rays intervene in situ in the SEI film, the activity of chemical bonds is activated by introducing gases such as CO2 and SO2 under the intervention of the high-energy X rays, the reaction of the gases such as CO2 and SO2 is promoted, the components of the SEI film are improved, the improvement of the performance of the battery is facilitated, the recycling of the gases is realized, and the environmental hazard is small.
Further, the radiation is emitted towards the lower surface of the pole piece immersed in the electrolyte.
The steps of the above methods are divided for clarity, and the implementation may be combined into one step or split some steps, and the steps are divided into multiple steps, so long as the same logical relationship is included, which are all within the protection scope of the present patent; it is within the scope of the patent to add insignificant modifications to the flow or to introduce insignificant design, but not to change the core design of its algorithms and flow.
The second embodiment of the invention relates to an SEI film preparation and lithium supplement system for a battery pole piece. As shown in fig. 2, the system is used for the SEI film preparation and lithium supplement of the battery electrode sheet 91 in the first embodiment, and comprises: a closable cabin body 1, a gas circulating device 2, a ray emitting device 3 and a conveying device. The cartridge body 1 has a chamber 5 for containing electrolyte and the electrode sheet 91 therein, the top of the chamber 5 is an opening area 50, at least one sidewall of the chamber 5 is separated from at least one wall of the cartridge body 1 to form a gas flow channel 10 communicated with the opening area 50, and the chamber 5 is operatively filled with reaction gas. The export that the import that is used for pole piece 91 to get into and pole piece 91 go out has on the storehouse body 1, import and exit all establish and are provided with a pair of seal assembly, seal assembly has the spring 11 of connection on the storehouse body 1 and the sealing member 12 that links to each other with spring 11, when pole piece 91 slides in the roll-off storehouse body 1 from a pair of seal assembly, pole piece 91 is being held to a pair of sealing member 12, and spring 11 provides elasticity to its continuous sealing member 12, let sealing member 12 paste tight pole piece 91 for the gas in the storehouse body 1 can not leak outward. The bin body 1 comprises a body and a cover plate, wherein an inlet and an outlet are formed in the cover plate, the cover plate can open the closed body, and electrolyte and the lithium metal block 92 can be conveniently put into or taken out of the accommodating chamber 5. The gas circulation device 2 is provided on a side wall of the housing chamber 5 forming the gas flow path 10 for drawing the reaction gas discharged from the opening area 50 into the housing chamber 5 through the gas flow path 10, wherein an arrow a in fig. 2 is a flow direction in which the reaction gas flows into the housing chamber 5 in the gas flow path 10 after flowing out from the opening area 50. Ray emitter 3 sets up on the storehouse body 1, and the storehouse body 1 pastes radiation protection film, and ray emitter 3 is used for launching the ray to holding in the room 5, and wherein the arrow B in figure 2 is the ray irradiation direction. The conveying device comprises: an unwinding member 41 for unwinding the pole piece 91 and a winding member 42 for winding and retracting the pole piece 91 after the reaction in the housing 5.
Further, as shown in fig. 2, the gas circulation device 2 includes a gas pump and has a gas outlet 21, and the gas outlet 21 faces the opening area 50 and is parallel to the horizontal plane.
In addition, as shown in fig. 2, a first conveying shaft 43 and a second conveying shaft 44 for conveying the pole piece 91 are provided in the housing chamber 5, and the first conveying shaft 43 is higher than the second conveying shaft 44, and the first conveying shaft 43 is closer to the unwinding member 41 than the second conveying shaft 44.
Further, as shown in fig. 2, the SEI film preparation and lithium supplement system for the battery electrode sheet 91 further includes: a drying device 6 and a cleaning device 7 which are arranged outside the bin body 1, wherein the drying device 6 is positioned between the cleaning device 7 and the rolling piece 42, and the cleaning device 7 is positioned between the drying device 6 and the second conveying shaft 44. The cleaning device 7 can clean the electrolyte and lithium salt remained in the pole piece 91 after lithium supplement by using a volatile non-aqueous solvent, such as DMC and the like. The drying device 6 can dry the residual solvent in the pole piece 91 to obtain the dried pole piece 91 after lithium supplement, and the drying temperature can be adjusted according to the requirement and is in the range of 25-200 ℃.
Further, as shown in fig. 2, the SEI film preparation and lithium supplement system for the battery electrode sheet 91 further includes: and a blowing means 8 for supplying a reaction gas into the accommodating chamber 5, and a blowing port of the blowing means 8 is directed toward the opening area 50 and is parallel to the horizontal plane, the blowing port being adjacent to a side wall of the accommodating chamber 5 forming the gas flow passage 10.
Specifically, as shown in fig. 2, the unwinding member 41 unwinds the pole piece 91, the winding member 42 winds the pole piece 91, the pole piece 91 passes through the electrolyte in the accommodating chamber 5, and the pole piece 91 is continuously immersed in the electrolyte to form an SEI film and supplement lithium. The lithium metal block 92 is parallel to the horizontal plane and keeps a certain included angle and distance with the horizontal plane, the pole piece 91 and the lithium metal block 92 are connected with a power supply through pole lugs, and the power is turned on to carry out electrochemical pre-lithium, wherein the current magnitude, the time and the voltage can be set as required. Meanwhile, the blowing device 8 leads the reaction gas to the pole piece 91, and increases the energy of the electrochemical reaction under the action of the rays, so that the reaction gas also participates in the formation of the SEI film. The reaction gas can continuously flow out of the blowing device 8 and along the pole piece 91 under the action of buoyancy, flow out of the opening area 50 of the accommodating chamber 5 and enter the gas flow channel 10, and is sent into the electrolyte again by the gas circulation device 2 for further recycling. After the SEI film and the lithium supplement of the pole piece 91 are finished, the pole piece is further conveyed to the cleaning device 7 and the drying device 6 by the rolling piece 42, and finally rolled for standby. The whole process is continuous production, the production efficiency is high, automation is realized, and in-situ intervention and improvement of the SEI film are realized.
While the preferred embodiments of the present invention have been described in detail above, it should be understood that aspects of the embodiments can be modified, if necessary, to employ aspects, features and concepts of the various patents, applications and publications to provide yet further embodiments.
These and other changes can be made to the embodiments in light of the above detailed description. In general, in the claims, the terms used should not be construed to be limited to the specific embodiments disclosed in the specification and the claims, but should be construed to include all possible embodiments along with the full scope of equivalents to which such claims are entitled.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
Claims (12)
1. A method for preparing an SEI film of a battery pole piece and supplementing lithium is characterized by comprising the following steps:
immersing a lithium metal block in an electrolyte;
immersing the pole piece in the electrolyte;
connecting the pole piece and the lithium metal block into a power supply for electrifying;
and introducing reaction gas into the electrolyte, wherein the reaction gas flows to the pole piece, so that an SEI film is formed on the pole piece, and lithium ions are embedded into the pole piece.
2. The method for preparing and supplementing the SEI film of the battery pole piece according to claim 1, wherein the pole piece immersed in the electrolyte is parallel to the lithium metal block, and the pole piece immersed in the electrolyte is positioned above the lithium metal block.
3. The method for preparing and supplementing the SEI film of the battery pole piece according to claim 1, wherein the pole piece immersed in the electrolyte is inclined with respect to the horizontal plane by an angle greater than 0 ° and less than 90 °.
4. The method for preparing and supplementing the SEI film of the battery pole piece according to claim 3, wherein the introduction direction of the reaction gas is opposite to the lower surface of the pole piece immersed in the electrolyte and is positioned on the lower side of the pole piece immersed in the electrolyte.
5. The method for preparing and supplementing the SEI film of the battery pole piece according to claim 1, which further comprises the following steps: emitting radiation to a pole piece immersed in the electrolyte.
6. The SEI film production and lithium supplement method of the battery pole piece according to claim 5, wherein the radiation is emitted toward the lower surface of the pole piece immersed in the electrolyte.
7. The SEI film preparation and lithium supplement method for the battery pole piece according to claim 1, wherein the reaction gas comprises CO2, CO and SO2、SO3、NO、NO2O2, HF.
8. A SEI film preparation and lithium supplement system for a battery pole piece is characterized by comprising:
the electrode plate electrode box comprises a closable cabin body, wherein a containing chamber for containing electrolyte and an electrode plate is arranged in the cabin body, the top of the containing chamber is an opening area, and at least one side wall of the containing chamber is separated from at least one cabin wall of the cabin body to form an airflow channel communicated with the opening area; and the containment chamber is operatively vented with a reactant gas; the bin body is provided with an inlet for the pole piece to enter and an outlet for the pole piece to exit; and the number of the first and second groups,
gas circulation means provided on a side wall of the accommodating chamber forming the gas flow passage for drawing the reaction gas discharged from the opening area into the accommodating chamber through the gas flow passage;
the ray emitting device is arranged on the bin body and used for emitting rays into the accommodating chamber; and the number of the first and second groups,
a delivery device, comprising: the device comprises a releasing component used for releasing the pole piece and a winding component used for winding and retracting the pole piece after reaction in the accommodating chamber.
9. The SEI film preparation and lithium supplement system for battery pole pieces according to claim 8, wherein the gas circulation device is provided with a gas outlet facing the open area and parallel to a horizontal plane.
10. The SEI film preparation and lithium supplement system for battery pole pieces according to claim 8, wherein a first conveying shaft and a second conveying shaft for conveying the pole pieces are arranged in the accommodating chamber, the first conveying shaft is higher than the second conveying shaft, and the first conveying shaft is closer to the unwinding member than the second conveying shaft.
11. The SEI film preparation and lithium supplementation system for the battery pole piece according to claim 10, further comprising: the drying device and the cleaning device are arranged outside the bin body, the drying device is located between the cleaning device and the winding part, and the cleaning device is located between the drying device and the second conveying shaft.
12. The SEI film preparation and lithium supplementation system for the battery pole piece according to claim 8, further comprising: the blowing device is used for conveying reaction gas into the accommodating chamber, and a blowing port of the blowing device faces the opening area and is parallel to the horizontal plane; the air blowing port is close to the side wall of the accommodating chamber forming the air flow channel.
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