CN115642316B - Electrochemical lithium supplementing device, electrochemical lithium supplementing method and lithium ion battery - Google Patents
Electrochemical lithium supplementing device, electrochemical lithium supplementing method and lithium ion battery Download PDFInfo
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- CN115642316B CN115642316B CN202110815544.3A CN202110815544A CN115642316B CN 115642316 B CN115642316 B CN 115642316B CN 202110815544 A CN202110815544 A CN 202110815544A CN 115642316 B CN115642316 B CN 115642316B
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- lithium
- gas
- negative electrode
- supplementing
- electrolyte
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- 230000001502 supplementing effect Effects 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 59
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 18
- 238000010926 purge Methods 0.000 claims abstract description 99
- 239000003792 electrolyte Substances 0.000 claims abstract description 89
- 230000008569 process Effects 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims description 198
- 230000009469 supplementation Effects 0.000 claims description 40
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 230000007246 mechanism Effects 0.000 claims description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 15
- -1 ethylene, propylene, butylene, acetylene Chemical group 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000009423 ventilation Methods 0.000 claims description 12
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- 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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- Secondary Cells (AREA)
Abstract
The application provides an electrochemical lithium supplementing device, which comprises an electrolytic tank filled with electrolyte, a lithium source and a negative plate to be supplemented with lithium, wherein the lithium source and the negative plate are arranged in the electrolyte at intervals, and the negative plate and the lithium source are respectively and electrically connected with the positive electrode and the negative electrode of a power supply; the electrochemical lithium supplementing device further comprises a gas purging component, wherein the gas purging component is used for introducing purging gas into the electrolyte in the process of supplementing lithium to the negative plate when the power supply is connected, so as to purge the surface of the negative plate. The electrochemical lithium supplementing device is used for supplementing lithium to the negative electrode plate, so that the uniformity and the lithium supplementing efficiency of the negative electrode lithium supplementing can be improved, and the first-week coulomb efficiency and the cycle life of a lithium battery made of the negative electrode plate after lithium supplementing are improved. The application also provides an electrochemical lithium supplementing method and a lithium ion battery.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to an electrochemical lithium supplementing device, an electrochemical lithium supplementing method and a lithium ion battery.
Background
Lithium ion batteries are one of the most widely used secondary batteries because of their high energy density, long cycle life, no memory effect, and the like. With the development of economy and science, the industries of portable electronic devices (such as mobile phones, tablet computers and the like), electric automobiles and the like have put higher demands on the energy density of lithium ion batteries. The method comprises the steps of carrying out lithium pre-supplementing on the positive electrode or the negative electrode of the battery, and compensating the irreversible consumption of active lithium in the first charging process of the battery, so that the first coulomb efficiency of the battery is improved, and the energy density of the battery is improved.
At present, a method for pre-supplementing lithium to a battery cathode is more common, and one of common practice is to electrochemically supplement lithium to a cathode plate. Referring to fig. 1, in the electrochemical lithium supplementing technology, a battery pole piece A1 to be supplemented with lithium, a diaphragm S1 and a lithium source C1 are generally placed in an electrolyte, wherein A1 and C1 are electrically connected through an external circuit, so that an electronic path and an ion path are established between A1 and C1 when the battery pole piece is electrified, and lithium supplementing of a negative pole piece A1 is realized. However, in the existing electrochemical lithium supplementing technology, the non-uniformity of lithium intercalation of the negative electrode is high, and the first-week coulomb efficiency of a lithium battery prepared by adopting the negative electrode plate after lithium supplementation cannot be effectively improved.
Disclosure of Invention
In view of the above, the application provides an electrochemical lithium supplementing device and a lithium supplementing method for a battery cathode, which are used for solving the problems of low lithium supplementing efficiency and uneven lithium intercalation on the surface of a cathode sheet in the existing electrochemical lithium supplementing technology.
Specifically, the first aspect of the application provides an electrochemical lithium supplementing device, which comprises an electrolytic tank filled with electrolyte, a lithium source arranged in the electrolyte and a negative plate to be supplemented with lithium, wherein the negative plate and the lithium source are arranged at intervals, and the negative plate and the lithium source are respectively electrically connected with the positive electrode and the negative electrode of the power supply; the electrochemical lithium supplementing device further comprises a gas purging component, wherein the gas purging component is used for introducing purging gas into the electrolyte to purge the surface of the negative plate in the process of supplementing lithium to the negative plate by switching on the power supply.
In the electrochemical lithium supplementing device provided by the application, the gas purging component can be used for introducing the purging gas into the electrolyte, the purging gas can be used for increasing the mobility of the electrolyte, improving the convection capability between the negative plate and the electrolyte, ensuring that the concentration of the electrolyte near the negative plate is uniform, removing bubbles adsorbed on the negative plate A2 in the electrochemical lithium supplementing process, enabling the negative plate to fully contact with the electrolyte, improving the uniformity and lithium supplementing efficiency of the negative electrode, and further effectively improving the first-week coulomb efficiency and the cycle life of a lithium battery prepared by the negative plate after lithium supplementing.
Optionally, the purge gas may purge the surface of the negative electrode sheet. At this time, the introduction of the purge gas can better improve the uniformity and the lithium supplementing efficiency of the negative electrode.
In some embodiments of the present application, the gas purging component is provided with a vent pipe inserted into the electrolyte, the vent pipe is immersed into the electrolyte, a plurality of holes are arranged on the pipe wall facing the negative plate at intervals, and the purging gas flows out through the holes and purges the surface of the negative plate.
Optionally, the part of the ventilation pipeline immersed in the electrolyte comprises a first pipe section, a second pipe section and a third pipe section which are sequentially connected, the first pipe section, the second pipe section and the third pipe section enclose an accommodating space, the opening direction of the accommodating space faces to the top cover of the electrolytic tank, and the negative electrode plate to be subjected to lithium supplementation, the diaphragm and the lithium source are all located in the accommodating space. Further, the second tube section is perpendicular to the first tube section and the third tube section. In some embodiments, the part of the ventilation pipeline immersed in the electrolyte is arranged along the bottom and the side wall of the electrolytic tank, and a plurality of holes are arranged on the pipe wall facing the negative plate.
Optionally, the gas purging component comprises a gas supply source communicated with the ventilation pipeline, a pump and a flow regulating valve are arranged on a pipeline communicated with the gas supply source, and the flow regulating valve is used for regulating the flow of purge gas flowing into the electrolytic tank.
Optionally, the electrochemical lithium supplementing device further comprises a gas treatment device communicated with the electrolytic tank, wherein the gas treatment device is used for treating the gas escaping from the electrolytic tank to obtain waste gas and recycle gas capable of being used as purge gas respectively. In some embodiments, one outlet of the gas treatment device is in communication with an exhaust gas collector and the other outlet is in communication with the gas supply.
Wherein the purge gas comprises an inert gas comprising at least one of argon and helium. The inert gas does not participate in the electrochemical lithium supplementing process.
Further, the purge gas further includes a gas that can participate in forming an SEI film (solid electrolyte film), and the gas that can participate in forming a negative electrode SEI film includes at least one of a sulfur-containing gas, a nitrogen-containing gas, an oxygen-containing gas, a fluorine-containing gas, and a reducing hydrocarbon gas.
Wherein the sulfur-containing gas comprises at least one of hydrogen sulfide, sulfur dioxide, and sulfur trioxide. The nitrogen-containing gas includes at least one of nitrogen, nitric oxide, and nitrogen dioxide. The oxygen-containing gas includes at least one of oxygen, carbon monoxide, and carbon dioxide. The fluorine-containing gas comprises at least one of fluorine gas, carbon tetrafluoride, perfluorobutadiene, nitrogen trifluoride, hexafluoroethane, perfluoropropane, trifluoromethane and sulfur hexafluoride. The reducing hydrocarbon gas comprises at least one of ethylene, propylene, butylene, acetylene, propyne and butyne.
Optionally, when the purge gas contains both inert gas and gas that can participate in forming the negative electrode SEI film, the volume ratio of the gas that can participate in forming the negative electrode SEI film in the purge gas is 0.1 to 50%. Specifically, the volume ratio may be 1%, 2%, 5%, 10%, 20%, 30%, 40%, 45%, or the like.
Optionally, the electrochemical lithium supplementing device further comprises a pole piece unreeling mechanism and a pole piece winding mechanism, the negative pole piece to be supplemented with lithium is arranged on the pole piece unreeling mechanism, and the pole piece winding mechanism is configured to pull the negative pole piece to be supplemented with lithium to be carried out tape feeding, so that the negative pole piece to be supplemented with lithium can be soaked in electrolyte to supplement with lithium, and the negative pole piece after being supplemented with lithium is wound.
In a second aspect, the present invention provides an electrochemical lithium supplementing method for a negative electrode of a battery, comprising the steps of:
Placing a negative plate to be subjected to lithium supplementation and a lithium source in electrolyte, placing the negative plate to be subjected to lithium supplementation and the lithium source at intervals, respectively electrically connecting the negative plate and the lithium source with the positive electrode and the negative electrode of a power supply, switching on the power supply to supplement lithium to the negative plate, and obtaining the negative plate after lithium supplementation after the lithium supplementation is finished;
And in the process of supplementing lithium to the negative electrode plate, introducing a purge gas into the electrolyte.
Optionally, a vent pipeline communicated with a gas supply source is inserted into the electrolyte; and a plurality of holes are formed in the pipe wall of the ventilation pipe, which faces the negative electrode plate, at intervals in the part immersed in the electrolyte, so that the purge gas flows out of the holes and is blown to the surface of the negative electrode plate. As for the specific kind of the purge gas, as described in the foregoing description of the present application, the description thereof will not be repeated here.
Further, the part of the ventilation pipeline immersed in the electrolyte comprises a first pipe section, a second pipe section and a third pipe section which are sequentially connected, the first pipe section, the second pipe section and the third pipe section enclose an accommodating space, the opening direction of the accommodating space faces to the top cover of the electrolytic tank, and the negative plate to be subjected to lithium supplementation, the diaphragm and the lithium source are all located in the accommodating space.
Optionally, the electrolyte is contained in an electrolytic cell, which is also in communication with a gas treatment device that treats the gases escaping from the electrolytic cell, obtaining respectively an exhaust gas and a recycle gas that can be used as a purge gas.
According to the electrochemical lithium supplementing method provided by the second aspect of the application, the scavenging gas is introduced into the electrolyte in the lithium supplementing process, so that the convection capability between the negative electrode plate and the electrolyte can be increased, the concentration of the electrolyte near the negative electrode plate is ensured to be uniform, bubbles adsorbed on the negative electrode plate A2 in the electrochemical lithium supplementing process can be removed, the negative electrode plate is fully contacted with the electrolyte, and the uniformity and the lithium supplementing efficiency of the negative electrode lithium supplementing are improved.
In a third aspect, the present application provides a lithium ion battery, including a negative electrode sheet after lithium supplementation, where the negative electrode sheet after lithium supplementation is made by using the electrochemical lithium supplementation method according to the second aspect of the present application, or is obtained by using the electrochemical lithium supplementation device according to the first aspect of the present application.
In some embodiments of the application, the lithium ion battery comprises a negative electrode sheet and a positive electrode sheet after lithium supplementation, and a diaphragm and electrolyte between the negative electrode sheet and the positive electrode sheet after lithium supplementation.
The lithium battery assembled by the lithium-ion-supplementing negative electrode plate has the advantages that the lithium ions are uniformly embedded into the negative electrode plate after lithium supplementation, so that the irreversible consumption of active lithium separated from the positive electrode by the negative electrode can be greatly reduced in the first charging process, the first coulomb efficiency, the battery capacity and the cycle performance of the battery are improved, and the energy density of the battery is further improved.
Drawings
Fig. 1 is a schematic structural diagram of a conventional electrochemical lithium-supplementing device.
Fig. 2a is a schematic structural diagram of an electrochemical lithium-supplementing device according to an embodiment of the present application.
Fig. 2b is a schematic structural diagram of an electrochemical lithium-supplementing device according to an embodiment of the present application.
Fig. 2c is a schematic structural diagram of an electrochemical lithium-supplementing device according to an embodiment of the present application.
Detailed Description
The following describes the technical scheme of the embodiment of the present application in detail with reference to the accompanying drawings.
Referring to fig. 2a, the electrochemical lithium supplementing device provided by the present application includes: the electrolytic tank 10 filled with the electrolyte 10a is provided with a lithium source C2, a diaphragm S2 and a negative electrode plate A2 to be filled with lithium, wherein the lithium source C2, the diaphragm S2 and the negative electrode plate A2 to be filled with lithium are respectively and electrically connected with the positive electrode and the negative electrode of a power source Au, and the negative electrode plate A2 is immersed in the electrolyte when the lithium filling is started and is separated from the lithium source C2 by the diaphragm S2. Of course, in other embodiments of the present application, the separator A2 may be omitted, and the negative electrode sheet A2 to be compensated with lithium may be controlled to be placed at a certain distance from the lithium source C2, so as to avoid direct contact between the two.
The electrochemical lithium supplementing device further comprises a gas purging component, wherein the gas purging component is used for introducing purging gas (shown by arrow directions) into the electrolyte 10a to purge the surface of the negative electrode sheet A2 in the process of supplementing lithium to the negative electrode sheet A2 by switching on the power supply Au.
Compared with the existing electrochemical lithium supplementing device shown in fig. 1, the purge gas output from the gas purge component can generate gas turbulence for the electrolyte, so that the convection capability of the electrolyte and the negative electrode plate A2 is enhanced, the concentration uniformity of the electrolyte near the negative electrode plate is improved, lithium ions for lithium intercalation are avoided from being absent in the electrolyte near the negative electrode plate, bubbles adsorbed on the negative electrode plate A2 in the electrochemical lithium supplementing process can be removed due to the presence of the purge gas, the negative electrode plate is fully contacted with the electrolyte, and the uniformity and lithium supplementing efficiency of the negative electrode lithium supplementing are improved. In addition, the concentration of flammable and explosive gases (such as hydrogen and the like) generated in the electrochemical lithium supplementing process can be diluted by introducing the purge gas, so that the safety of the electrochemical lithium supplementing process is higher.
In fig. 2a, a vent line is shown with a gas purge assembly, the vent line 20 being immersed in a tube section of electrolyte, and a plurality of holes are provided at intervals in the tube wall facing the negative electrode sheet A2. The purge gas in the vent line 20 can flow out from each hole, and can purge the surface of the negative electrode sheet in the forward direction, thereby improving the purge efficiency. Thereby better improving the uniformity of lithium supplement of the negative plate. Alternatively, the shape of the holes formed in the wall of the ventilation tube 20 is not limited, and may be circular, elliptical, rectangular, trapezoidal, regular polygonal, or other irregular shape. It will be appreciated that the vent line 20 may be inserted into the electrolyte within the cell 10 through an opening formed in the top cover of the cell 10.
The ventilation pipeline of the gas purging assembly is not limited to the arrangement mode shown in fig. 2a, and can be specifically adjusted according to the placement state of the negative electrode plate in the electrolytic tank. For example, when the negative electrode sheet A2 is placed parallel to the bottom of the electrolytic cell 10, the gas outlet of the vent line of the gas purge assembly may be directed toward the negative electrode sheet A2.
Referring to fig. 2b, another embodiment of the present application provides a ventilation circuit. The part of the ventilation pipeline 20 immersed in the electrolyte comprises a first pipe section 201, a second pipe section 202 and a third pipe section 203 which are sequentially connected, wherein an accommodating space is defined by the three pipe sections, a negative electrode plate A2 to be filled with lithium, a diaphragm S2 and a lithium source C2 are all positioned in the accommodating space, and the opening direction of the accommodating space faces to the top cover of the electrolytic tank 10. Wherein, the first pipe section 201 and the third pipe section 203 are perpendicular to the bottom of the electrolytic cell 10 (i.e. parallel to the side wall of the electrolytic cell 10) and respectively face to the opposite side surfaces of the negative electrode sheet A2, the second pipe section 202 is parallel to the bottom of the electrolytic cell 10 and faces to the side surface of the negative electrode sheet A2, and holes are arranged on the pipe walls of the three pipe sections facing to the negative electrode sheet A2 at intervals. At this time, the ventilation line 20 can remove the adsorption bubbles generated on the negative electrode sheet A2 well, and can increase the fluidity of the electrolyte in the entire electrolytic cell 10, thereby greatly improving the overall uniformity of the electrolyte concentration. In some embodiments, the portion of the vent line 20 shown in fig. 2b immersed in the electrolyte may be arranged along the bottom and side walls of the electrolytic cell 10, and the wall of the tube facing the negative electrode sheet A2 is provided with a plurality of holes. The first 201 and third 203 tube sections are arranged against the side walls of the cell 10 and the second 202 tube section is arranged against the bottom of the cell 10. The vent line 20 may be arranged as described above by means of brackets provided in the cell 10.
It will be appreciated that the gas purge assembly described above includes a gas supply 30 (see fig. 2a, 2 b) in communication with the vent line 20. Optionally, a pump (not shown) for conveying purge gas is arranged on a pipeline, communicated with the gas supply source 30, of the vent pipeline 20, and a flow regulating valve (not shown) is arranged on a pipeline, connected with the pump, of the vent pipeline 20, so that the flow rate, the flow velocity and the like of the purge gas introduced into the electrolyte are regulated, the convection capability of the electrolyte and the negative electrode plate is controllably improved, and the uniformity and the reaction rate of lithium intercalation on the surface of the negative electrode plate are promoted.
Wherein the number of gas supplies 30 may be one or more, wherein when the purge gas is 1, the number of gas supplies may be 1; when the purge gas includes two or more kinds, the number of the gas supply sources 30 may be plural, corresponding to the kind of the purge gas, or one mixed gas source of plural kinds of gases. The number of the vent lines is not limited to one, and when two or more purge gases are provided, the electrolyte may be introduced through two vent lines, or two or more purge gases may be mixed outside the electrolytic cell 10 and introduced into the electrolyte through one vent line. In fig. 2b, only one air supply 30, one ventilation line 20 is illustrated. The purge gas may be introduced into the electrolyte 10a continuously, intermittently, or by pulse.
With continued reference to fig. 2a and 2b, the electrochemical lithium-compensating device provided by the present application further includes a gas treatment device 40 in communication with the electrolytic cell 10, where the gas treatment device 40 can collect the gas escaping from the electrolytic cell 10, treat and separate the gas, and obtain an exhaust gas and a recycle gas that can be reused as a purge gas, respectively. Taking fig. 2b as an example, the gas treated by the gas treatment device 40 may be divided into two paths, one path being the exhaust gas, and flowing into the exhaust gas collector 50 communicating with an outlet of the gas treatment device 40; the other is a recycle gas, which flows into the supply 30 of purge gas through a recycle gas line. The gas treatment device 40 can treat inflammable and explosive gas, electrolyte volatile matters and the like generated in the electrochemical lithium supplementing process, reduce the pollution of direct discharge to the environment, and the treated circulating gas can be used as purge gas for recycling, so that the cost is saved. Wherein the communication line between the gas treatment device 40 and the electrolytic cell 10 is not inserted into the electrolyte, for example, as in fig. 2c, the end of the communication line extends above the level of the electrolyte in the electrolytic cell, or the communication line is not located in the electrolytic cell and is only connected to an opening in the top cover of the electrolytic cell 10.
In addition, in order to facilitate batch lithium supplementation of the negative electrode sheet, a battery excellent in electrochemical performance is assembled again. In industry, a negative electrode sheet to be subjected to lithium supplementation is generally wound into a roll, and is immersed in an electrolyte solution in regions for lithium supplementation. Referring to fig. 2c, fig. 2c is a schematic structural diagram of an electrochemical lithium-compensating device according to an embodiment of the application. The electrochemical lithium supplementing device further comprises a mechanism for conveying the negative electrode sheet A2 to be supplemented with lithium, and particularly comprises a pole piece unreeling mechanism 60 and a pole piece reeling mechanism 70, which are arranged outside the electrolytic tank 10. One end of the negative electrode sheet A2 to be subjected to lithium supplementation is wound on the pole piece unreeling mechanism 60, the other end is wound on the pole piece reeling structure 70, and the pole piece reeling structure 70 is configured to pull the negative electrode sheet A2 to be subjected to lithium supplementation to move so that the negative electrode sheet A2 to be subjected to lithium supplementation can be soaked in the electrolyte 10a for electrochemical lithium supplementation, and the negative electrode sheet after lithium supplementation is reeled. The electrochemical lithium supplementing device shown in fig. 2c is more convenient for realizing batch lithium supplementing of the negative plate and is convenient for industrialized application. In fig. 2c, a first intermediate roller 61 is fixed in the electrolytic cell 10 near the pole piece unreeling mechanism 60, a second intermediate roller 71 is arranged between the first intermediate roller 61 and the pole piece reeling structure 70, and the second intermediate roller 71 is positioned above the outside of the electrolytic cell 10 and can be fixed on an external member. The negative electrode sheet A2 to be supplied with lithium may bypass the first and second intermediate rolls 61 and 71 so that the negative electrode sheet A2 to be supplied with lithium may be in a state parallel to the separator S2 between the first and second intermediate rolls 61 and 71. This can facilitate shortening of the ion conduction path between the negative electrode sheet A2 to be lithium-supplemented and the lithium source C2. In other embodiments of the present application, the mechanism for winding and unwinding the negative electrode sheet A2 to be compensated may be other configurations, for example, a mechanism having more than 3 transfer rollers, etc., to increase the travelling distance of the electrode sheet in the electrolyte, so as to increase the lithium compensation efficiency.
It can be understood that when the device shown in fig. 2c is used for lithium supplementing, the rolled negative electrode sheet A2 is flattened by sections, the sections are immersed in electrolyte to realize sequential lithium supplementing, and each section of the negative electrode sheet is rolled up in sequence after lithium supplementing is finished and stored for later use. When the battery is assembled, the rolled lithium-supplementing negative plate can be unfolded and cut into the required size to be assembled into the battery.
In the present application, the purge gas for purging the surface of the anode sheet A2 may include an inert gas. The inert gas includes at least one of argon and helium. Obviously, inert gas does not participate in the electrochemical lithium supplementing process, and the quality influence on the pole piece after lithium supplementing is small.
In some embodiments of the present application, the purge gas may contain a gas that may participate in forming the SEI film, in addition to the inert gas, and the gas that may participate in forming the negative electrode SEI film may include at least one of a sulfur-containing gas, a nitrogen-containing gas, an oxygen-containing gas, a fluorine-containing gas, and a reducing hydrocarbon gas. Specifically, the gases that can participate in forming the negative electrode SEI film may be one of these five gases (e.g., fluorine-containing gas), any two (e.g., a mixture of sulfur-containing gas and nitrogen-containing gas, a mixture of nitrogen-containing gas and oxygen-containing gas), any three (e.g., a mixture of sulfur-containing gas, nitrogen-containing gas and reducing hydrocarbon gas), any four (e.g., a mixture of sulfur-containing gas, nitrogen-containing gas, oxygen-containing gas, reducing hydrocarbon gas), or all five. The method can participate in the introduction of the gas for forming the negative electrode SEI film, can improve the quality and film forming efficiency of the SEI film formed on the surface of the negative electrode plate in the lithium supplementing process, further better improve the first cycle efficiency and the cycle performance of the full battery assembled by the negative electrode plate after lithium supplementing, and further facilitate the improvement of the energy density of the full battery.
Specifically, the sulfur-containing gas may include at least one of hydrogen sulfide (H 2 S), sulfur dioxide (SO 2), and sulfur trioxide (SO 3). In the electrochemical lithium supplementing process, the introduced sulfur-containing gas can react with electrolyte and active lithium on the surface of the negative electrode plate to generate lithium sulfate, and the lithium sulfate can be used as one of constituent components of an SEI film to enhance the strength and stability of the SEI film, so that the first cycle efficiency and cycle performance of a full battery prepared by the negative electrode plate after lithium supplementation are better improved.
The nitrogen-containing gas may include at least one of nitrogen (N 2), nitric Oxide (NO), and nitrogen dioxide (NO 2). The nitrogen-containing gas can participate in the electrochemical lithium supplementing process, and inorganic lithium salts such as lithium nitrate, lithium nitrite and lithium nitride are generated on the surface of the negative electrode plate by reaction to become constituent components of the SEI film, so that the stability and strength of the SEI film are improved, the electron conductivity of the SEI film is improved, and the first cycle efficiency, the cycle performance and the multiplying power performance of a full battery prepared by the negative electrode plate after lithium supplementing are improved better.
The oxygen-containing gas may include at least one of oxygen (O 2), carbon monoxide (CO), carbon dioxide (CO 2). The oxygen-containing gas can react with the electrolyte and active lithium on the surface of the negative electrode plate to generate lithium oxide, lithium carbonate and the like, and can be used as one of the constituent components of the SEI film to enhance the strength and stability of the SEI film.
The fluorine-containing gas may include at least one of fluorine gas (F 2), carbon tetrafluoride (CF 4), perfluorobutadiene (C 4F6), nitrogen trifluoride (NF 3), hexafluoroethane (C 2F6), perfluoropropane (CF 3CHFCF3), trifluoromethane (CHF 3), sulfur hexafluoride (SF 6). The introduced fluorine-containing gas can participate in the electrochemical lithium supplementing process, lithium fluoride and the like are generated on the surface of the negative electrode plate by means of reaction, the content of LiF and other components in the SEI film is increased, and therefore the strength and stability of the SEI film are improved.
The reducing hydrocarbon gas may include at least one of ethylene (C 2H4), propylene (C 3H6), butene (C 4H8), acetylene (C 2H2), propyne (C 3H4), butyne (C 4H6). The reductive hydrocarbon gas can participate in the electrochemical lithium supplementing process, is favorable for generating an SEI film containing a polymer with certain toughness on the surface of the negative electrode plate, improves the compactness and the elasticity of the SEI film, improves the structural stability of the SEI film, can better improve the volume expansion problem of a full battery prepared by the negative electrode plate after lithium supplementing in the charge and discharge cycle process, and further improves the cycle performance of the battery.
Further, when the purge gas contains both an inert gas and a gas that can participate in forming the negative electrode SEI film, the volume ratio of the gas that can participate in forming the negative electrode SEI film in the purge gas may be 0.1 to 50%. Specifically, the volume ratio may be 0.5%, 1%, 2%, 5%, 10%, 20%, 30%, 40%, 45%, or the like. Inert gas and gas which can participate in forming a negative electrode SEI film are mixed according to a proper proportion, so that the efficiency, uniformity and safety of electrochemical lithium supplementing can be well considered, and the electrochemical performance of the battery can be better improved. In some embodiments, the volume fraction may be 0.1-20%. At this time, the safety of the electrochemical lithium supplementing process is higher. Illustratively, in some embodiments, the purge gas is a mixture of argon and carbon tetrafluoride, wherein the carbon tetrafluoride comprises 1.5% by volume of the overall purge gas. In another embodiment, the purge gas is a mixed gas of argon, carbon tetrafluoride and perfluorobutadiene, wherein the volume ratio of the carbon tetrafluoride and the perfluorobutadiene in the whole purge gas is 0.4% and 0.7% in sequence.
In the present application, the lithium source C2 for electrochemically supplementing lithium to the negative electrode sheet A2 may be a self-supporting lithium plate, a lithium sheet, a lithium-plated metal sheet, or the like, or may be a lithium foil attached to another film base material. The lithium-plated metal sheet can be obtained by using electrode materials of waste lithium batteries or lithium-containing electrolyte as an electroplating lithium source and adopting an electroplating method. Alternatively, the thickness of the lithium plating layer on the lithium-plated metal sheet is 5 μm to 1000 μm.
Wherein, the lithium plate can be manufactured by a die casting method. For example, a lithium ingot is die-cast in a die with a certain size through a cold rolling process, and after the die casting is finished, a lithium plate which can be used for electrochemical lithium supplement is obtained through demoulding operation. The length and the width of the lithium plate are not particularly required, and can be adjusted according to the lithium supplementing device and the size of the negative electrode plate to be supplemented with lithium. The thickness of the lithium plate is typically 1mm to 5cm, preferably 3mm to 4cm. Similarly, lithium sheets may also be made by die casting. The thickness of the lithium sheet is generally 100 μm to 1000 μm. The fabrication of lithium foil attached to other film substrates can be achieved in a variety of ways. For example, the metallic lithium heated to a molten state may be directly coated on the film substrate, or the metallic lithium powder may be dispersed in an inert organic solvent such as hexane and then coated on the film substrate; evaporating lithium on the film substrate by adopting an evaporation method; the metallic lithium may also be attached to the film substrate by roll-pressing. The film substrate for attaching the lithium foil may be a metal film material such as copper foil, aluminum foil, nickel foil, iron foil, tin foil, or an alloy or composite thereof; but may also be a plastic or polymeric film material such as polyethylene film, polypropylene film, polyvinylidene fluoride film, polyethylene terephthalate (PET) film, polyimide (PI) film, or modifications or composites thereof. The thickness of the lithium foil is generally 1 μm to 1mm, preferably 3 μm to 200. Mu.m.
In the present application, the negative electrode tab A2 to be lithium-supplemented generally includes a negative current collector and a negative electrode material layer disposed on the negative current collector, and the negative electrode material layer generally includes a negative electrode active material, a binder, and an optional conductive agent. Among them, the negative electrode active material is a general choice in the battery field, including, but not limited to, one or more of a carbon-based material, a silicon-based material, a tin-based material, a germanium-based material, a phosphorus-based material, lithium titanate, lithium titanium phosphate, titanium dioxide, iron oxide, and the like. Specifically, the carbon-based material may include graphite (e.g., natural graphite, artificial graphite), non-graphitized carbon (soft carbon, hard carbon), and the like; the silicon-based material may include one or more of elemental silicon, silicon-based alloys, silicon oxides, silicon-carbon composites, and the like; the tin-based material may include one or more of elemental tin, tin alloys, tin oxides, tin carbon composites, and the like; the germanium-based material may include elemental germanium, germanium carbon composites, germanium oxides, sulfides; the phosphorus-based material may include red phosphorus, black phosphorus, phosphorus-carbon composite materials, and the like. Among them, the negative electrode binder may be selected from one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyacrylamide (PAM), polyacrylic acid (PAA), polyacrylate, polyvinyl alcohol (PVA), sodium carboxymethyl cellulose (CMC), styrene Butadiene Rubber (SBR), and the like, but is not limited thereto. Alternatively, the mass of the binder is 0.1 to 15wt%, preferably 1 to 7wt%, of the mass of the anode active material. The conductive agent may be one or more of acetylene black, ketjen black, feeder P conductive carbon black, furnace black, graphite, carbon fiber, carbon nanotube, etc., which are conventional in the art. Alternatively, the mass of the conductive agent is 0.1 to 20wt%, preferably 1 to 10wt% of the mass of the anode active material.
The negative electrode sheet A2 can be obtained by coating a negative electrode slurry containing a negative electrode active material, a bonding agent, a conductive agent and a solvent on a negative electrode current collector, drying to form a negative electrode material layer, rolling and cutting. The solvent in the negative electrode slurry can be one or more of N-methyl pyrrolidone (NMP), dimethylformamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), alcohol solvents, water and the like. Generally, the mass of the solvent is 20 to 90wt%, preferably 40 to 85wt%, of the mass of the anode active material. The temperature during drying can be 60-150deg.C, preferably 80-120deg.C; the drying time may be 0.5 to 5 hours. The specific drying process can be adjusted according to the anode slurry.
In addition, a negative electrode tab may be further disposed on the negative electrode tab A2, and the negative electrode tab may be electrically connected with the negative electrode material layer, so as to facilitate fixing of the negative electrode tab A2 and realizing electrical connection between the negative electrode tab A2 and the power supply during lithium supplementing (wherein, the negative electrode tab is not shown in fig. 2a, 2b, and 2 c). Similarly, the lithium source C2 may also be provided with lithium supplementing tabs, so as to fix the lithium source C2 and electrically connect the lithium source C2 with a power supply. Typically, the lithium source C2 is connected to the negative electrode of the power supply, i.e. as the anode of the electrolytic cell; the negative plate A2 is connected with the positive electrode of the power supply and serves as the cathode of electrolysis. When the power supply is switched on to supplement lithium, lithium ions extracted from the lithium source C2 move to the negative electrode plate A2 through the diaphragm S2, can be embedded into the surface of the negative electrode plate A2, and form an SEI film on the surface of the negative electrode plate A2.
In addition, the application also provides an electrochemical lithium supplementing method. The electrochemical lithium supplementing method can be combined with the above fig. 2a, 2b and 2c, and comprises the following steps:
immersing a negative plate A2 to be subjected to lithium supplementation, a diaphragm S2 and a lithium source C2 in electrolyte, separating the negative plate A2 from the lithium source C2 by the diaphragm S2, respectively electrically connecting the negative plate A2 and the lithium source C2 with the positive electrode and the negative electrode of a power source Au, switching on the power source Au to supplement lithium to the negative plate A2, and obtaining the negative plate after lithium supplementation after the lithium supplementation is finished;
In the process of supplementing lithium to the negative electrode sheet A2, a purge gas is introduced into the electrolyte to purge the surface of the negative electrode sheet A2.
As described in the foregoing, for the lithium supplementing using the apparatus shown in fig. 2c, the negative electrode sheet A2 to be supplemented with lithium is not immersed in the electrolyte at once, but is immersed in the electrolyte in sections one after another. The negative electrode sheet region immersed in the electrolyte in fig. 2c can be understood as the lithium-to-be-replenished region of the entire negative electrode sheet A2. In the actual operation process, the diaphragm S2 and the lithium source C2 can be immersed in electrolyte, the negative electrode sheet A2 to be supplemented with lithium is arranged on the sheet unreeling mechanism 60, and the other end of the negative electrode sheet A2 is connected with the sheet reeling mechanism 70; the negative electrode plate A2 and the lithium source C2 are respectively and electrically connected with the positive electrode and the negative electrode of the power Au, and the power Au is connected to supplement lithium to the negative electrode plate A2; the pole piece winding structure 70 may pull the negative pole piece A2 to be compensated for tape, so that the negative pole piece A2 can be soaked in the electrolyte when lithium compensation begins, and the negative pole piece A2 and the lithium source C2 are separated by the separator S2.
The vent line for introducing the purge gas into the electrolyte may be described in any of the implementations of the application described above, and the specific type of purge gas and the gas treatment device in communication with the electrolytic cell containing the electrolyte may be described in the application described above, and will not be described again.
According to the electrochemical lithium supplementing method provided by the application, the surface of the negative electrode plate to be supplemented with lithium is purged by adopting the purge gas in the lithium supplementing process, so that the convection capability between the negative electrode plate and the electrolyte can be increased, the concentration of the electrolyte near the negative electrode plate is ensured to be uniform, bubbles adsorbed on the negative electrode plate in the electrochemical lithium supplementing process can be removed, the negative electrode plate is fully contacted with the electrolyte, and the uniformity and the lithium supplementing efficiency of the negative electrode lithium are improved.
Correspondingly, the application also provides a lithium ion battery, which comprises the lithium-supplemented negative plate prepared by the electrochemical lithium supplementing method. Specifically, the lithium ion battery comprises a positive plate, a negative plate after lithium supplementation, a diaphragm positioned between the positive plate and the negative plate after lithium supplementation, and electrolyte.
And taking out the anode piece after lithium supplement after the electrochemical lithium supplement, and washing and drying the anode piece to assemble the battery. Specifically, the negative plate, the diaphragm and the positive plate after lithium supplementation are sequentially stacked to prepare a battery core, the battery core is contained in a battery shell, electrolyte is injected into the battery shell, and then the battery shell is sealed, so that the lithium ion battery can be prepared.
Because proper lithium ions are uniformly embedded in the negative electrode plate after lithium supplementation, the irreversible consumption of active lithium separated from the positive electrode by the negative electrode can be greatly reduced in the first charging process of the lithium battery assembled by adopting the lithium ion battery, the first coulomb efficiency, the battery capacity and the cycle performance of the battery are improved, and the energy density of the battery is further improved.
In addition, the electrolyte contained in the above-described electrolytic tank and the electrolyte contained in the produced lithium ion battery may independently include an electrolyte lithium salt and a nonaqueous solvent. Wherein the electrolyte lithium salt may be selected from one or more of lithium hexafluorophosphate (LiPF 6), lithium perchlorate (LiClO 4), lithium tetrafluoroborate (LiBF 4), lithium hexafluoroarsenate (LiAsF 6), lithium hexafluorosilicate (LiSiF 6), lithium tetraphenylborate (LiB (C 6H5)4), lithium chloride (LiCl), lithium bromide (LiBr), lithium chloroaluminate (LiAlCl 4) and lithium fluorocarbon sulfonate (LiC(SO2CF3)3)、LiCH3SO3、LiN(SO2CF3)2、LiN(SO2C2F5)2 the nonaqueous solvent may be selected from one or more of a chain acid ester, a cyclic acid ester, a chain ether and a cyclic ether, the cyclic acid esters may be one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC), dipropyl carbonate (DPC) and other fluorine-, sulfur-or unsaturated bond-containing chain organic esters, the cyclic acid esters may be one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), vinylene Carbonate (VC), gamma-butyrolactone (gamma-BL), sultone and other fluorine-, sulfur-or unsaturated bond-containing cyclic organic esters, the cyclic ethers may be Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), 1, 3-Dioxolane (DOL) and 4-methyl-1, 3-dioxolane (4-MeDOL), and other fluorine-, gamma-butyrolactone (gamma-BL) compounds, one or more of cyclic organic ethers containing sulfur or unsaturated bonds. The chain ethers include one or more of Dimethoxymethane (DMM), 1, 2-Dimethoxyethane (DME), 1, 2-Dimethoxypropane (DMP) and Diglyme (DG), and other fluorine-, sulfur-or unsaturated bond-containing chain organic ethers. Alternatively, the concentration of the electrolyte lithium salt in the electrolyte is generally 0.1 to 15mol/L, preferably 1 to 10mol/L.
The effects of the embodiments of the present application will be further described below in terms of a plurality of examples.
Example 1
An electrochemical lithium supplementing method of a negative electrode sheet, comprising:
(1) Preparing a negative electrode sheet A2 to be supplemented with lithium: the negative electrode slurry obtained by mixing a negative electrode active material (specifically a mixture of carbon-coated silicon oxide and graphite), a conductive agent (specifically Super P and carbon nano tubes) and a binder (specifically a mixture of PAA, SBR and CMC) according to a mass ratio of 90:5:5 is coated on a copper foil, and the negative electrode slurry is dried and rolled to obtain a negative electrode sheet A2 to be supplemented with lithium.
(2) And (3) lithium is supplemented to the negative plate A2 by adopting the electrochemical lithium supplementing device shown in the figure 2C, wherein the lithium source C2 is a self-supporting lithium plate, the power supply voltage between the negative plate A2 and the lithium source C2 is 0.5V, and purge gas is continuously introduced into the electrolyte to purge the surface of the negative plate A2, wherein the purge gas is a mixed gas of argon and carbon tetrafluoride, and the volume ratio of the carbon tetrafluoride in the purge gas is 1.5%. And after the lithium is supplemented, washing the negative plate with an organic solvent, and drying to obtain the negative plate after the lithium is supplemented.
Preparation of a full cell: positive electrode active material (specifically lithium cobaltate), conductive agent (specifically carbon nanotube and conductive carbon) and binder (specifically PVDF) are mixed according to a ratio of 96:2:2, coating the positive electrode slurry prepared by the mass ratio on the two side surfaces of the aluminum foil, drying and tabletting to prepare a positive electrode plate; and sequentially stacking the positive plate, the diaphragm and the negative plate after lithium supplementation to prepare a battery core, accommodating the battery core in a battery shell, injecting electrolyte (specifically, EC+DEC mixed solution of 1mol/L LiPF 6 (the volume ratio of EC to DEC is 1:1)), and sealing the battery shell to prepare the full battery. The full cell was charged to 4.45V at 0.7C and then charged to 0.05C at a constant voltage of 4.45V; during discharging, the full battery is discharged to 3.0V at 0.5C, and the charging and discharging processes are repeated, so that the cycle life and the energy density of the full battery are measured.
Preparation of a half cell: and assembling the negative plate after lithium supplementation and the metal lithium plate into a button cell, and testing the first-week coulomb efficiency of the half cell. Wherein, the half cell is firstly discharged, and the constant current is 0.1 to 10mV, then 0.05 to 10mV, then 0.02 to 10mV, and then 0.01 to 10mV; thereafter, the half cell was charged to 1.5V at 0.1C. Wherein, first week coulombic efficiency = battery first charge capacity/battery first discharge capacity 100%.
Example 2
An electrochemical lithium supplementing method for a negative electrode sheet is different from example 1 in that: argon was used as the purge gas.
Example 3
An electrochemical lithium supplementing method for a negative electrode sheet is different from example 1 in that: a mixture of argon and SO 2 was used as the purge gas, wherein the volume ratio of SO 2 in the purge gas was 1%.
Example 4
An electrochemical lithium supplementing method for a negative electrode sheet is different from example 1 in that: argon, O 2 and CO 2 are mixed as a purge gas, wherein the volume ratio of the sum of the volumes of O 2 and CO 2 in the purge gas is 20%, and the volume ratio of O 2 and CO 2 is 2:8.
Example 5
An electrochemical lithium supplementing method for a negative electrode sheet is different from example 1 in that: a mixture of argon and NO 2 was used as the purge gas, wherein NO 2 was present in the purge gas at a volume ratio of 10%.
Example 6
An electrochemical lithium supplementing method for a negative electrode sheet is different from example 1 in that: as purge gas, a mixture of argon and ethylene was used, wherein the volume ratio of ethylene in the purge gas was 5%.
Comparative example 1
An electrochemical lithium supplementing method for a negative electrode sheet is different from example 1 in that: purge gas is not introduced into the electrolyte during the lithium supplementing process.
The negative electrode sheets obtained by the electrochemical lithium-replenishing methods of examples 2 to 6 and comparative example 1 were assembled into half cells and full cells, respectively, according to the method described in example 1, and the first-week coulombic efficiency of the half cells, the cycle life of the full cells, the energy density, and the like were measured, and the results are summarized in table 1 below.
TABLE 1
As can be seen from table 1, in examples 1 to 6 of the present application, the purge gas was introduced during lithium supplementation of the negative electrode, the lithium supplementation effect of the negative electrode sheet was improved, and accordingly, the electrochemical performance of the battery fabricated from the negative electrode sheet after lithium supplementation was superior, as compared to comparative example 1 in which the purge gas was not introduced during lithium supplementation of the negative electrode sheet. In addition, as can be seen from comparison of the results of examples 1,3 to 6 with example 2, the use of the inert gas together with the gas that can participate in the formation of the SEI film as the purge gas can better enhance the negative electrode lithium supplementing effect and improve the electrochemical performance of the battery, as compared with the use of the inert gas alone as the purge gas.
While the foregoing is directed to exemplary embodiments of the present application, it will be appreciated by those skilled in the art that various modifications and adaptations can be made thereto without departing from the principles of the present application, and such modifications and adaptations are intended to be comprehended within the scope of the present application.
Claims (9)
1. The electrochemical lithium supplementing device comprises an electrolytic tank filled with electrolyte, a lithium source arranged in the electrolyte and a negative plate to be supplemented with lithium, wherein the negative plate and the lithium source are arranged at intervals, and the negative plate and the lithium source are respectively electrically connected with the positive electrode and the negative electrode of a power supply;
The electrochemical lithium supplementing device further comprises a gas purging component, wherein the gas purging component is used for introducing purging gas into the electrolyte to purge the surface of the negative plate in the process of supplementing lithium to the negative plate by switching on the power supply.
2. The electrochemical lithium-compensating device of claim 1, wherein the gas purging component has a vent line inserted into the electrolyte, the vent line being immersed in the electrolyte, a plurality of holes being provided at intervals on a wall of the vent line facing the negative electrode sheet, the purge gas flowing out through the holes and purging a surface of the negative electrode sheet.
3. The electrochemical lithium-supplementing device according to claim 2, further comprising a separator disposed in the electrolyte, the negative electrode tab being separated from the lithium source by the separator;
the part of the ventilation pipeline immersed in the electrolyte comprises a first pipe section, a second pipe section and a third pipe section which are sequentially connected, the first pipe section, the second pipe section and the third pipe section enclose an accommodating space, the opening direction of the accommodating space faces to the top cover of the electrolytic tank, and the negative plate to be subjected to lithium supplementation, the diaphragm and the lithium source are all positioned in the accommodating space.
4. The electrochemical lithium-supplementing apparatus according to claim 1, further comprising a gas treatment device in communication with the electrolytic cell for treating the gas evolved from the electrolytic cell to obtain an exhaust gas and a recycle gas capable of being used as a purge gas, respectively.
5. The electrochemical lithium-supplementing device according to any one of claims 1-4, wherein the purge gas comprises an inert gas comprising at least one of argon and helium.
6. The electrochemical lithium-compensating device of claim 5, wherein the purge gas further comprises a gas that can participate in forming a negative electrode SEI film, the gas that can participate in forming a negative electrode SEI film comprising at least one of a sulfur-containing gas, a nitrogen-containing gas, an oxygen-containing gas, a fluorine-containing gas, and a reducing hydrocarbon gas;
wherein the sulfur-containing gas comprises at least one of hydrogen sulfide, sulfur dioxide, and sulfur trioxide; the nitrogen-containing gas comprises at least one of nitrogen, nitric oxide and nitrogen dioxide; the oxygen-containing gas comprises at least one of oxygen, carbon monoxide and carbon dioxide; the fluorine-containing gas comprises at least one of fluorine gas, carbon tetrafluoride, perfluorobutadiene, nitrogen trifluoride, hexafluoroethane, perfluoropropane, trifluoromethane and sulfur hexafluoride; the reducing hydrocarbon gas comprises at least one of ethylene, propylene, butylene, acetylene, propyne and butyne.
7. The electrochemical lithium-supplementing device according to claim 6, wherein the volume ratio of the gas that can participate in forming the negative electrode SEI film in the purge gas is 0.1 to 50%.
8. The electrochemical lithium-supplementing device according to claim 1, further comprising a pole piece unreeling mechanism and a pole piece reeling mechanism, wherein the negative pole piece to be supplemented with lithium is arranged on the pole piece unreeling mechanism, and the pole piece reeling mechanism is configured to pull the negative pole piece to be supplemented with lithium to be carried out in a tape so as to be soaked in electrolyte for supplementing lithium, and reel the negative pole piece after supplementing lithium.
9. The electrochemical lithium supplementing method for the battery negative plate is characterized by comprising the following steps of:
placing a negative plate to be subjected to lithium supplementation and a lithium source in electrolyte, placing the negative plate to be subjected to lithium supplementation and the lithium source at intervals, respectively electrically connecting the negative plate and the lithium source with the positive electrode and the negative electrode of a power supply, and switching on the power supply to supplement lithium to the negative plate, and obtaining the negative plate after lithium supplementation;
And in the process of supplementing lithium to the negative electrode plate, introducing a purge gas into the electrolyte to purge the surface of the negative electrode plate.
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