CN113889676A - Repairing and regenerating method for lithium-containing battery - Google Patents
Repairing and regenerating method for lithium-containing battery Download PDFInfo
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- CN113889676A CN113889676A CN202010636865.2A CN202010636865A CN113889676A CN 113889676 A CN113889676 A CN 113889676A CN 202010636865 A CN202010636865 A CN 202010636865A CN 113889676 A CN113889676 A CN 113889676A
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- 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
- H01M10/4242—Regeneration of electrolyte or reactants
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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
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- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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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
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/446—Initial charging measures
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Abstract
The invention provides a method for repairing and regenerating a lithium-containing battery, which is characterized in that when the battery capacity is reduced to a preset value of the nominal capacity, the lithium-containing battery is repaired and regenerated, and the potential of a negative electrode of the lithium-containing battery relative to a third electrode of the lithium-containing battery is positioned at 2.5 volts or more and V or less and 4 volts or less, so that the electrochemical decomposition of an SEI (solid electrolyte interphase) film of the negative electrode is excited. After the battery is cleaned and the liquid is changed, the positive electrode of the lithium-containing battery and the third electrode of the lithium-containing battery are connected for low-current density discharge, the concentration balance is realized by using the solvated lithium ions in the electrolyte, and the uniform lithium supplement of all positive plates is realized. And forming to re-form a stable SEI film on the surface of the negative electrode. The repair regeneration technology can simultaneously realize in-situ reduction of organic components of the negative electrode SEI film, replacement of failure electrolyte and uniform supplement of lost active lithium in each pole piece on the premise of not disassembling the battery and not damaging the battery core, thereby achieving the effect of reactivating the battery performance.
Description
Technical Field
The invention relates to the field of batteries, in particular to a lithium-containing battery repairing and regenerating method.
Background
Lithium ion batteries have gained wide use in the fields of portable electronic devices, wireless communications, and the like, and are gradually trying to be used in the fields of new energy vehicles and large-scale energy storage. However, the calendar service life requirement of the new energy automobile and the power energy storage system for the battery is far higher than the service life requirement of the small consumer battery. In particular, the power energy storage system basically requires that the battery has a calendar service life of ten years or even more than twenty years, and the existing lithium ion battery cannot meet the requirement in one life cycle. The current battery generally adopts a treatment mode of disassembling, crushing and recycling after the battery is in failure, so that the environment is polluted, a large amount of energy is consumed, and only limited metal ions can be recycled, therefore, a new technical approach is found to repair and regenerate the battery reaching the end of the service life, and the calendar service life of the energy storage battery is further prolonged.
The main reasons for the gradual failure of lithium ion batteries in practical use include the following: 1. the electrolyte is invalid; 2. the interfacial failure of the material (mainly caused by the thickening of an SEI film on the surface of the negative electrode material and the growth of lithium dendrites); 3. loss of active lithium; 4. the active material lattice is disordered. Among them, the interfacial failure of materials and the failure of electrolytes and the resulting loss of active lithium are the core factors causing the practical use failure of lithium ion batteries. How to repair and regenerate the lithium-containing battery is a problem which needs to be solved urgently at present.
Disclosure of Invention
In order to solve the problems, the invention provides a method for repairing and regenerating a lithium-containing battery, which is used for repairing and regenerating the lithium-containing battery when the battery capacity is reduced to a preset value of a nominal capacity, and the potential of a negative electrode of the lithium-containing battery relative to a third electrode of the lithium-containing battery is enabled to be more than or equal to 2.5 volts and less than or equal to 4 volts, so that the electrochemical decomposition of an SEI (solid electrolyte interphase) film of the negative electrode is excited. After the battery is cleaned and the liquid is changed, the positive electrode of the lithium-containing battery and the third electrode of the lithium-containing battery are connected for low-current density discharge, the concentration balance is realized by using the solvated lithium ions in the electrolyte, and the uniform lithium supplement of all positive plates is realized. And forming to re-form a stable SEI film on the surface of the negative electrode. After the formation of the battery, the positive electrode of the lithium-containing battery and the third electrode of the lithium-containing battery are connected again, and the positive electrode sheet is fully embedded with lithium by means of low-current-density discharge. By the repairing and regenerating method, repairing and regenerating are carried out before scrapping treatment is carried out on the battery, and the repairing and regenerating method comprises the steps of carrying out in-situ removal on part or all of the components of the negative electrode SEI film by an overdischarge or reverse charging method on the premise of not disassembling the battery and not damaging a battery cell; replacing the invalid electrolyte in the battery by replacing the electrolyte; and the lithium is supplemented by the third electrode to the battery cell in the discharging state, so that the active lithium lost in the battery cycling process is supplemented, and the aim of reactivating the battery performance is further fulfilled.
The technical scheme provided by the invention is as follows:
according to the present invention, there is provided a method of repairing and regenerating a lithium-containing battery, the method comprising the steps of: (a) a judging step: when the capacity of the lithium-containing battery is reduced to a preset value of the nominal capacity, judging that the lithium-containing battery needs to be repaired and regenerated; (b) removing the SEI film: under the preset current density, the potential of the negative electrode relative to the third electrode is more than or equal to 2.5V and less than or equal to 4V, so that the components of the SEI film of the negative electrode are decomposed and fall off under the oxidation action, and are dissolved or dispersed in the electrolyte, and the preset current density is 0.005-10C; (c) liquid changing step: discharging the original electrolyte in the lithium-containing battery, and injecting new electrolyte into the battery; (d) and (3) regeneration and lithium supplement: connecting the positive electrode and the third electrode to perform low-current density discharge, and realizing concentration balance by using solvated lithium ions in the electrolyte, so that lithium in the third electrode is fully and uniformly embedded into the positive active material of each positive plate, and after the fully embedded lithium positive plates are formed, the positive electrode and the third electrode are disconnected, wherein the low-current density is 0.005-0.1C; (e) formation: and (3) carrying out formation on the lithium-containing battery, and reforming a stable SEI film on the surface of the negative electrode.
In the step (a), the predetermined value may be 60% to 90% of the nominal capacity. That is, during use of the battery, when a drop in the capacity of the lithium-containing battery to, for example, 80% of the nominal capacity is detected, a repair regeneration procedure may be initiated. The predetermined value for the drop in battery capacity may be set according to actual needs.
In the step (b), the predetermined current density is 0.005C to 10C. That is, the predetermined current density may be 0.005 times to 10 times the current density at 1C (1 magnification). At a predetermined current density, by passingThe potential of the negative electrode relative to the third electrode is 2.5V-4V to remove the SEI film. This step may be implemented using a discharge system or may be implemented using a charging power supply. When the discharging system is used, the anode and the cathode of the lithium-containing battery are connected, the lithium-containing battery is discharged until V is less than or equal to 0V, namely the lithium-containing battery is overdischarged, so that the potential of the cathode of the lithium-containing battery relative to the third electrode of the lithium-containing battery is less than or equal to 2.5V and less than or equal to 4V. When a charging power supply is utilized, the positive electrode of the lithium-containing battery can be electrically connected with the negative electrode of the charging power supply, the negative electrode of the lithium-containing battery is electrically connected with the positive electrode of the charging power supply, and when the positive electrode and the negative electrode of the lithium-containing battery are reversely connected with the positive electrode and the negative electrode of the power supply, the potential of the negative electrode of the lithium-containing battery relative to the third electrode of the lithium-containing battery can be enabled to be more than or equal to 2.5V and less than or equal to 4V; alternatively, when a charging power supply is used, the negative electrode of the lithium-containing battery may be electrically connected to the positive electrode of the charging power supply and the third electrode of the lithium-containing battery may be electrically connected to the negative electrode of the charging power supply, or the potential of the negative electrode of the lithium-containing battery with respect to the third electrode of the lithium-containing battery may be 2.5V 4V. When a discharging system or a charging power supply is utilized to enable the potential of the negative electrode of the lithium-containing battery relative to the third electrode of the lithium-containing battery to be more than or equal to 2.5V and less than or equal to 4V, organic components with higher thickness, larger impedance and instability at the outside of the SEI film can be effectively removed, and inorganic components with denser inside and higher stability are reserved. Since the SEI film mainly comprises an internal inorganic layer and an external organic layer, the organic layer can be electrochemically oxidized and decomposed generally at 4 volts or less, and the decomposition potential of the inorganic component is higher (generally at 4 volts or more), in a conventional lithium ion battery, the copper foil is used as a negative current collector in a negative electrode, the copper foil is oxidized and dissolved at about 3.3 volts and is precipitated on a contraposition positive electrode, and the phenomenon that the battery performance is seriously affected by short circuit and the like is caused, so that the potential on the negative electrode side cannot be too high. If the negative electrode current collector with higher oxidation potential stability is adopted, the further increase of the electrode potential on the negative electrode side can be realized, and the oxidative decomposition of organic components in an SEI film can be realized, such as a stainless steel current collector and the like. Since the organic component in the SEI film is more easily oxidized and decomposed than the inorganic component, the site where the first reaction of oxidative decomposition occurs is the closest part of the organic component to the negative electrode in the SEI filmThe organic component being, for example, (CH)2OCO2Li)2、ROCO2Li, ROLi, RCOOLi, etc., oxidation causes the fusing of the organic component with the negative contact point, causing the organic component to be detached from the negative SEI film. In the current density selection when the SEI film is removed, high-current density charging and discharging are preferably adopted, so that the fusing of the organic components and the contact point of the negative electrode is realized, but the low-current density gradually raises the voltage of the negative electrode of the lithium-containing battery, and the gradual raising of the voltage of the low-current density can cause collapse of a graphite structure, so that the later performance of the battery is influenced. Therefore, the large current density of 2C to 10C, and more preferably 4C to 7C is preferably selected in the SEI film removal step.
In addition, in the step (b), a pyrolysis step may be further included, in which the interior of the lithium-containing battery is heated to a temperature of 40 ℃ to 100 ℃ so as to promote the decomposition of the SEI film and increase the solubility of the SEI film and its decomposed components in the electrolyte or the dissolving solution. The SEI film may be decomposed at a high temperature, and increasing the internal temperature of the battery may also increase the solubility of the easily soluble portions of the SEI. In addition, in the high-temperature pyrolysis step, a dissolving solution can be injected into the lithium-containing battery, the dissolving solution is kept for a preset time at a high temperature and then discharged, and the circulation is carried out for 1-3 times, so that the dissolved part of the decomposed SEI film and the fallen matters dispersed in the dissolving solution are discharged out of the battery. The temperature of the solution in a high temperature state may be 40 to 100 ℃, and the solution may be heated inside the lithium-containing battery, or the solution may be heated outside and then injected into the lithium-containing battery. The dissolving solution can be a solvent which has dissolving performance on organic components in the SEI film and has no damage effect on electrode materials, and the dissolving solution can be one or a mixture of carbonates, carboxylic esters, alcohols, ethers, ketones and water. For example, the carbonate-based solvent may include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, vinyl chlorocarbonate, vinyl fluorocarbonate, propylene difluorocarbonate, propylene trifluorocarbonate, and the like; the carboxylic ester-based solvent may include methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, etc.; the alcohol solvent may include methanol, ethanol, propanol, butanol, pentanol, hexanol, etc.; the ether solvent may include dimethoxymethane, 1, 2-dimethoxyethane, tetrahydrofuran, dimethyltetrahydrofuran, diethylene glycol dimethyl ether, tetramethyl-1, 3-dioxolane, etc.; the ketone solvent may include acetone, butanone, pentanone, etc. In order to facilitate later operation, the dissolving solution is preferably a solvent component with higher dissolving capacity contained in the electrolyte, such as a solvent with higher dielectric constant in carbonates and carboxylates. After step (b), a cooling step may also be included, for example, cooling the lithium-containing cell to 20 ℃ to 80 ℃. Since the battery is not easily in a high temperature state when a new electrolyte is injected, the battery can be cooled in advance.
In the step (c), the original electrolyte in the lithium-containing battery is discharged, and a leaching step can be carried out after the original electrolyte in the lithium-containing battery is discharged, wherein a leaching agent is added into the battery to leach the residual electrolyte in the battery, and then the leaching agent is discharged out of the battery, wherein the leaching agent can be one or a mixture of carbonic acid esters, carboxylic acid esters, alcohols, ethers, ketones and water. The leaching agent is preferably a solvent with low viscosity and good fluidity. For example, the carbonate-based solvent may include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, vinyl chlorocarbonate, vinyl fluorocarbonate, propylene difluorocarbonate, propylene trifluorocarbonate, and the like; the carboxylic ester-based solvent may include methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, etc.; the alcohol solvent may include methanol, ethanol, propanol, butanol, pentanol, hexanol, etc.; the ether solvent may include dimethoxymethane, 1, 2-dimethoxyethane, tetrahydrofuran, dimethyltetrahydrofuran, diethylene glycol dimethyl ether, tetramethyl-1, 3-dioxolane, etc.; the ketone solvent may include acetone, butanone, pentanone, etc. For easier later operation, the leaching agent is preferably a solvent component with lower viscosity and better fluidity contained in the electrolyte, such as a solvent with lower carbon number in carbonates and carboxylates. And then, cleaning the interior of the battery for m times, wherein m is more than or equal to 1, and injecting new electrolyte into the interior of the battery after cleaning. The cleaning agent for cleaning can be one or a mixture of carboxylic acid esters, carbonic acid esters, ethers and ketones. An SEI film stabilizer and a repair agent may be added to the newly added electrolyte.
In step (d), the lithium-containing cell is first fully discharged, and then the positive electrode is connected to the third electrode for small current density discharge, that is, the positive electrode of the lithium-containing cell is connected to the third electrode of the lithium-containing cell via a discharge system or a load. Wherein, the third electrode of the lithium-containing battery is electrically connected with the lithium-containing metal body arranged in the lithium-containing battery. The material of the lithium-containing metal body may be metallic lithium or a lithium-rich alloy. The lithium-containing metal body may be one or more, and when a plurality of lithium-containing metal bodies are provided, at least one positive electrode tab may be spaced between the two lithium-containing metal bodies. In particular, in the case where the battery is in a fully discharged state, i.e., discharged to the cut-off voltage, for example, the capacity of the battery itself has dropped to 80% of the nominal capacity, theoretically there are still 20% of the vacancies in the positive electrode available for lithium intercalation. If the lithium-containing battery is not completely discharged before lithium is supplemented, and lithium ions are completely inserted into the positive plate in the lithium supplementing process and the positive plate is fully inserted with lithium, the lithium is supplemented too much in the battery due to the fact that the negative electrode still contains the inserted lithium ions, and lithium precipitation occurs in the using process of the battery. In addition, if the lithium-containing battery is not completely discharged before lithium supplement and the positive electrode plate is not fully inserted with lithium during the lithium supplement process, lithium ions are preferentially inserted into the positive electrode plate adjacent to the third electrode rather than the positive electrode plate far away from the third electrode, which causes uneven lithium supplement of each positive electrode plate. The positive electrode and the third electrode are connected for small current density discharge, so that a lithium-containing metal body electrically connected with the third electrode enters the electrolyte in the form of lithium ions, the speed of the lithium ions entering the electrolyte is controlled through the small current density, the solvated lithium ions in the electrolyte can reach concentration balance, and the lithium in the third electrode is fully and uniformly embedded into the positive active material of each positive plate. And after the fully lithium-embedded positive plate is formed, the positive electrode and the third electrode are disconnected. The low current density may be 0.005C to 0.1C. By utilizing the method, even and proper lithium supplement of each positive plate can be realized under the condition of less lithium-containing metal bodies, and over-lithium supplement or uneven lithium supplement can not occur, so that a complex third electrode structure does not need to be designed and excessive lithium-containing metal body material cost is not wasted.
In the step (e), the lithium-containing battery is formed, and a stable SEI film is formed on the surface of the negative electrode again. Part of the active lithium is consumed in the process of reforming a stable SEI film on the surface of the negative electrode. Therefore, after the step (e), the method can further comprise (f) a first lithium supplement step: and connecting the positive electrode with the third electrode to perform low-current density discharge so that the positive active material of each positive plate is fully embedded with lithium, and the low-current density is 0.005-0.1C. When the battery is in a fully discharged state, the positive electrode of the lithium-containing battery is connected to the third electrode of the lithium-containing battery via a discharge system or a load, and is discharged at a low current density to supplement active lithium consumed in the process of forming the SEI film.
The invention has the advantages that:
1) the repair regeneration technology can simultaneously realize in-situ reduction of organic components of a negative electrode SEI film, replacement of failure electrolyte and uniform supplement of lost active lithium in each pole piece on the premise of not disassembling a battery and not damaging a battery cell, thereby achieving the effect of reactivating the performance of the battery;
2) the method for increasing the potential of the negative electrode of the lithium-containing battery by increasing the potential of the negative electrode relative to the third electrode can excite partial or complete decomposition of high-impedance organic components in the SEI film of the negative electrode and retain high-ion-conductivity inorganic components in the SEI film. In addition, a complete SEI film can be continuously formed on the surface of the negative electrode in the subsequent formation step, so that the reduction of the internal resistance of the battery is realized;
3) by replacing the new electrolyte, the defects of shortage and failure of the electrolyte after the battery is used for a long time are overcome, and an SEI film with a more compact structure and more stable performance is regenerated by combining an SEI film stabilizer and a repairing agent which are newly added into the electrolyte, so that the service life of the battery is further prolonged;
4) according to the invention, in the process of regenerating and lithium supplementing, the battery core is in a discharging state, at the moment, the porous anodes are in a non-full lithium-embedding state due to the loss of active lithium in the battery circulation process, and when the third electrode is used for lithium supplementing, the low-current density discharging is adopted, so that the lithium ions in the electrolyte can reach slow concentration balance, the uniform diffusion of the lithium ions among the porous electrodes is realized, and the uniform lithium supplementing of all the positive plates is finally realized.
Drawings
Fig. 1 is a schematic cross-sectional view of a lithium-containing battery according to the present invention;
fig. 2 is a flow chart of a method for repairing and regenerating a lithium-containing battery according to the present invention;
fig. 3 is an operational view illustrating a step of removing an SEI film of a lithium-containing battery repairing regeneration method according to a first embodiment of the present invention;
fig. 4 is an operational view illustrating a step of removing an SEI film of a lithium-containing battery repairing regeneration method according to a second embodiment of the present invention;
fig. 5 is an operational view illustrating a step of removing an SEI film of a lithium-containing battery repairing regeneration method according to a third embodiment of the present invention;
fig. 6 is an operational view illustrating a liquid replacement step of a repair regeneration method for a lithium-containing battery according to the present invention;
fig. 7 is an operation diagram of a lithium replenishing regeneration or first-effect lithium replenishing step of the lithium-containing battery repairing regeneration method according to the present invention.
List of reference numerals
1-outer casing
1 a-Positive electrode
1 b-negative electrode
1 c-third electrode
1 d-first injection and exhaust port
1 e-second notes Row Port
2-electric core
3-lithium-containing metal body
4-discharge system
4 a-positive electrode of discharge system
4 b-negative electrode of discharge System
5-charging Power supply
5 a-positive electrode of charging source
5 b-negative electrode of charging Source
Detailed Description
The invention will be further explained by embodiments in conjunction with the drawings.
Fig. 1 is a schematic cross-sectional view of a lithium-containing battery according to the present invention. A lithium-containing battery includes: the device comprises an outer shell 1, wherein a positive electrode 1a (positive pole), a negative electrode 1b (negative pole), a third electrode 1c (third pole), a first injection and discharge port 1d and a second injection and discharge port 1e are arranged on the outer shell 1; the battery cell 2 comprises a positive plate, a negative plate and an isolating layer, wherein the positive plate and the negative plate are stacked in a crossed manner, the isolating layer is arranged between the positive plate and the negative plate, a porous positive material layer and a porous positive current collector are arranged in the positive plate, and a porous negative material layer and a porous negative current collector are arranged in the negative plate; and a lithium-containing metal body 3, wherein the lithium-containing metal body 3 is arranged inside the outer casing of the lithium-containing battery. In the lithium-containing battery, all positive electrode sheets are electrically connected to the positive electrode 1a, all negative electrode sheets are electrically connected to the negative electrode 1b, and the lithium-containing metal body 3 is electrically connected to the third electrode 1 c. In the lithium-containing battery, corresponding lithium-containing metal bodies 3 do not need to be arranged close to each positive plate (or negative plate), but at least one positive plate can be spaced among the lithium-containing metal bodies 3, and uniform lithium supplement of each positive plate in the whole lithium-containing battery is realized through complete pre-discharge in the lithium regenerating and supplementing process, low-current density discharge in the lithium supplementing of the third electrode and a porous structure of the porous electrode. The first injection and discharge port 1d and the second injection and discharge port 1e can be used for injecting and discharging electrolyte, solution, leaching agent, cleaning agent, and the like, respectively.
Fig. 2 is a flowchart of a method for repairing and regenerating a lithium-containing battery according to the present invention. In the flowchart of the repair regeneration method, the main steps of the repair regeneration method are indicated in solid line boxes, and the optional steps of the repair regeneration method are indicated in dashed line boxes. In the determination step, it is determined whether the battery needs repair regeneration by a capacity detection of the lithium-containing battery. When the capacity of the battery drops to 60% to 90% of the nominal capacity, the next steps of the repair regeneration method may be performed. In the SEI film removing step, the potential of the negative electrode relative to the third electrode is more than or equal to 2.5V and less than or equal to 4V, so that the organic components in the SEI film are fused with a negative electrode contact point under the oxidation action, the unstable organic components with higher thickness and higher impedance outside the SEI film are effectively removed, and the internal inorganic components with higher density and higher stability are reserved. The lithium-containing battery can be discharged to a voltage V' of 0 by utilizing a discharge system or a load to connect the positive electrode and the negative electrode of the lithium-containing battery, wherein the current density of the discharge can be controlled by the discharge system; the lithium-containing battery can be discharged to a voltage V ' <0 by using a discharging system, or the voltage V ' <0 of the lithium-containing battery can be caused by reversely connecting the positive and negative electrodes of the charging power supply with the positive and negative electrodes of the lithium-containing battery, or the voltage of the negative electrode of the lithium-containing battery relative to the third electrode is 2.5 volts or more and V '. or more and 4 volts or less by electrically connecting the positive and negative electrodes of the charging power supply with the negative electrode of the lithium-containing battery and the third electrode. Therefore, the potential of the negative electrode relative to the third electrode is more than or equal to 2.5V and less than or equal to 4V. Since the SEI film is removed by increasing the potential of the negative electrode in the present invention, the negative electrode preferably uses a porous stainless steel current collector having a higher oxidation potential instead of a conventional copper current collector, thereby being more advantageous to oxidative decomposition of organic components in the SEI film under high pressure. In addition, in the process of removing the SEI film, the conventional methods for removing the SEI film, such as ultrasonic heating, repeated high-temperature charge and discharge, large-current charge and discharge and the like, can be combined, so that the SEI film can be more effectively removed. In the SEI film removal step, decomposition of a part of organic components in the negative electrode SEI film and solubility in the electrolyte may also be increased by means of heating or by means of heating and injecting a dissolving solution. After the battery heats up, the battery may also be returned to normal operating temperature via a cooling step. In the liquid changing step, the fluid inside the lithium-containing battery case may be discharged and then a new electrolyte may be injected. Before injecting new electrolyte, the electrolyte which is not easy to discharge and permeates into the gap of the battery core can be leached and discharged by the leaching agent, thereby achieving the purpose of thoroughly removing the old electrolyte. In addition, before injecting new electrolyte, the interior of the battery can be cleaned for a plurality of times by using the cleaning agent so as to remove impurities remained in the interior of the battery. In the step of regenerating and replenishing lithium, the lithium-containing battery is preferably completely discharged so that lithium in the negative electrode material is completely inserted into the positive electrode material, and since the capacity of the battery itself has decreased to, for example, 80% of the nominal capacity, 20% of the voids in the positive electrode still remain for lithium insertion, and then the positive electrode of the lithium-containing battery is connected to the third electrode of the lithium-containing battery for small current density discharge. Compared with the lithium supplement under the condition that a large number of vacant positions exist in the positive electrode, the lithium supplement of the positive electrode plate under the condition can realize that each positive electrode plate is quickly and uniformly embedded, and the lithium supplement of the positive electrode plate which is close to the lithium-containing metal body cannot be quickly met due to the large number of lithium supplements of the positive electrode plate which is far away from the lithium-containing metal body, so that the lithium supplement effect of each positive electrode plate is unbalanced. In the process of lithium supplement of the third electrode, the anode of the lithium-containing battery can be connected with the anode of the discharge system, the cathode of the lithium-containing battery is connected with the cathode of the discharge system, and the discharge system can control the current density in the discharge process, so that the concentration balance of lithium ions in the electrolyte and the uniform lithium supplement of each anode plate can be realized under low current density; in addition, the positive electrode of the lithium-containing cell may be connected to the third electrode of the lithium-containing cell via a load, thereby achieving a discharge reaction between the positive electrode and the third electrode. After the step of regenerating and replenishing lithium, the battery is formed by methods common in the art. And (3) because a stable SEI film is formed on the surface of the negative electrode again in the formation process, and part of active lithium is consumed in the process, a first-effect lithium supplementing step can be carried out again, and preferably, the positive electrode and the third electrode are connected to carry out low-current density discharge in the state that the lithium-containing battery is completely discharged, so that the positive electrode material of the positive plate is fully embedded with lithium.
Fig. 3 is an operational view illustrating a step of removing an SEI film in a lithium-containing battery repairing regeneration method according to a first embodiment of the present invention. In the SEI film removing step, the anode 1a of the lithium-containing battery is connected with the anode 4a of the discharge system 4, the cathode 1b of the lithium-containing battery is connected with the cathode 4b of the discharge system 4, so that the potential of the cathode relative to the third electrode is 2.5V-4V, and the oxidative decomposition of the organic components of the SEI film is realized.
Fig. 4 is an operational view illustrating a step of removing an SEI film in a lithium-containing battery repairing regeneration method according to a second embodiment of the present invention. In the SEI film removing step, the anode 1a of the lithium-containing battery is connected with the charging power supply cathode 5b of the charging power supply 5, and the cathode 1b of the lithium-containing battery is connected with the charging power supply anode 5a of the charging power supply 5, so that the potential of the cathode relative to the third electrode is more than or equal to 2.5V and less than or equal to 4V, and the oxidative decomposition of the organic components of the SEI film is realized.
Fig. 5 is an operational view illustrating a step of removing an SEI film in a lithium-containing battery repairing regeneration method according to a third embodiment of the present invention. In the SEI film removing step, the negative electrode 1b of the lithium-containing battery is connected with the positive electrode 5a of the charging power supply 5, and the third electrode 1c of the lithium-containing battery is connected with the negative electrode 5b of the charging power supply 5, so that the potential of the negative electrode relative to the third electrode is more than or equal to 2.5V and less than or equal to 4V, and the oxidative decomposition of the organic components of the SEI film is realized.
Fig. 6 is an operation view illustrating a liquid replacement step of a repair regeneration method of a lithium-containing battery according to the present invention. In the liquid changing step, old electrolyte in the battery can be discharged through the second injection and discharge port 1e, then cleaning agent can be injected into the battery through the first injection and discharge port 1d and the cleaning agent in the battery can be discharged through the second injection and discharge port 1e, and new electrolyte can be injected into the battery through the first injection and discharge port 1d when the cleaning agent in the battery is exhausted.
Fig. 7 is an operation diagram of a lithium replenishing regeneration or first-effect lithium replenishing step of the lithium-containing battery repairing regeneration method according to the present invention. The operation of the lithium regeneration and supplement step is substantially the same as that of the first-effect lithium supplement step, the lithium-containing battery is completely discharged, for example, to 2 v, then the positive electrode 1a of the lithium-containing battery is connected with the positive electrode 4a of the discharge system 4, the third electrode 1c of the lithium-containing battery is connected with the negative electrode 4b of the discharge system 4, and the connection is disconnected after the lithium supplement is finished.
Example 1
And monitoring the capacity of the lithium-containing battery in real time, and judging that the lithium-containing battery needs to be repaired and regenerated when the capacity of the lithium-containing battery is reduced to a preset value (70%) of the nominal capacity.
The interior of the lithium-containing battery was heated to 80 ℃, and then the lithium-containing battery was discharged at a current density of 0.1C so that the potential V of the negative electrode of the lithium-containing battery with respect to the third electrode became 3 volts.
And discharging the old electrolyte in the battery through a second discharging port of the lithium-containing battery. And a leaching agent, namely dimethyl carbonate with low viscosity and good fluidity is injected into the battery through the first injection and discharge port of the lithium-containing battery, so that electrolyte which is adsorbed in gaps between the anode and cathode of the battery core and the diaphragm and is difficult to discharge is leached and sucked out. The leaching agent is drained via a secondary drain port of the lithium-containing cell. New electrolyte is injected through a first injection and discharge port of the lithium-containing cell.
The lithium-containing cell was fully discharged. And connecting the positive electrode of the lithium-containing battery and the third electrode, and continuing to perform 0.02C low-current discharge so that lithium in the third electrode is fully inserted into the positive electrode material layer to form a fully inserted lithium positive electrode material layer.
And connecting the lithium-containing batteries into a formation cabinet, and forming the batteries according to a formation program.
And (3) completely discharging the lithium-containing battery, connecting the positive electrode of the lithium-containing battery with a third electrode to perform 0.05C low-current density discharge, and supplementing active lithium consumed in the formation process, thereby completing the repair and regeneration of the lithium-containing battery.
Example 2
And monitoring the capacity of the lithium-containing battery in real time, and judging that the lithium-containing battery needs to be repaired and regenerated when the capacity of the lithium-containing battery is reduced to a preset value (75%) of the nominal capacity.
And connecting the positive electrode and the negative electrode of the lithium-containing battery to the positive electrode and the negative electrode of the rechargeable battery in a reverse direction, and reversely charging the battery at a large current density of 7C, so that the battery is stopped when the potential V of the negative electrode of the lithium-containing battery relative to the third electrode is 3.5V.
Heating the interior of the lithium-containing battery to 70 ℃, then injecting the high-temperature pyrolysis liquid at 70 ℃ into the interior of the battery, keeping the temperature for a certain time, discharging the pyrolysis liquid, and circulating for 3 times. The lithium-containing cell was sealed and left to cool to 40 ℃.
New electrolyte is injected through a first injection and discharge port of the lithium-containing cell.
The lithium-containing cell was fully discharged. And connecting the positive electrode of the lithium-containing battery and the third electrode, and continuing to perform 0.05C low-current discharge so that lithium in the third electrode is fully inserted into the positive electrode material layer to form a fully inserted lithium positive electrode material layer.
And connecting the lithium-containing batteries into a formation cabinet, and forming the batteries according to a formation program.
And (3) completely discharging the lithium-containing battery, connecting the positive electrode of the lithium-containing battery with a third electrode to perform 0.02C low-current density discharge, and supplementing active lithium consumed in the formation process, thereby completing the repair and regeneration of the lithium-containing battery.
Example 3
And monitoring the capacity of the lithium-containing battery in real time, and judging that the lithium-containing battery needs to be repaired and regenerated when the capacity of the lithium-containing battery is reduced to a preset value (80%) of the nominal capacity.
The interior of the lithium-containing battery is heated to 90 ℃, the negative electrode of the lithium-containing battery is electrically connected with the positive electrode of the charging power supply, the third electrode of the lithium-containing battery is electrically connected with the negative electrode of the charging power supply, and the lithium-containing battery is charged at a large current density of 5C, so that the potential V of the negative electrode of the lithium-containing battery relative to the third electrode is 4V.
And cleaning the interior of the lithium-containing battery for 2 times by using a cleaning agent, and injecting new electrolyte through a first injection and discharge port of the lithium-containing battery after cleaning.
The lithium-containing cell was fully discharged. And connecting the positive electrode of the lithium-containing battery and the third electrode to continue to carry out 0.1C low-current discharge, so that lithium in the third electrode is fully inserted into the positive electrode material layer, and forming a fully inserted lithium positive electrode material layer.
And connecting the lithium-containing batteries into a formation cabinet, and forming the batteries according to a formation program.
And (3) completely discharging the lithium-containing battery, connecting the positive electrode of the lithium-containing battery with a third electrode to perform 0.01C low-current density discharge, and supplementing active lithium consumed in the formation process, thereby completing the repair and regeneration of the lithium-containing battery.
The specific embodiments of the present invention are not intended to be limiting of the invention. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments, using the methods and techniques disclosed above, without departing from the scope of the present invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (11)
1. A method for repairing and regenerating a lithium-containing battery, the method comprising the steps of: (a) a judging step: when the capacity of the lithium-containing battery is reduced to a preset value of the nominal capacity, judging that the repair regeneration is needed; (b) removing the SEI film: under a preset current density, the potential of the negative electrode of the lithium-containing battery relative to the third electrode is more than or equal to 2.5V and less than or equal to 4V, so that the organic components of the negative electrode SEI film are decomposed and fall off under the oxidation action, and are dissolved or dispersed in the electrolyte, wherein the preset current density is 0.005-10C; (c) liquid changing step: discharging the original electrolyte in the lithium-containing battery, and injecting new electrolyte into the battery; (d) and (3) regeneration and lithium supplement: fully discharging the lithium-containing battery, connecting the positive electrode of the lithium-containing battery with a third electrode of the lithium-containing battery to perform low current density discharge, and realizing concentration balance by using solvated lithium ions in electrolyte so that lithium in the third electrode is fully and uniformly embedded into a positive active material of each positive plate of the lithium-containing battery to form a fully embedded lithium positive plate, and then disconnecting the positive electrode of the lithium-containing battery and the third electrode of the lithium-containing battery, wherein the low current density is 0.005-0.1C; (e) formation: and (3) carrying out formation on the lithium-containing battery, and reforming a stable SEI film on the surface of the negative electrode.
2. The method for repairing and regenerating a lithium-containing battery according to claim 1, wherein, in the step (a), the predetermined value is 60% to 90% of a nominal capacity.
3. The method for repairing and regenerating a lithium-containing battery according to claim 1, wherein, in the step (b), the predetermined current density is a large current density, and the large current density is 2C to 10C.
4. The method for repairing and regenerating a lithium-containing battery according to claim 3, wherein, in the step (b), the voltage of the lithium-containing battery is reduced by using a discharge device so that the potential of the negative electrode of the lithium-containing battery with respect to the third electrode is 2.5V 4V.
5. The method for repairing and regenerating a lithium-containing battery according to claim 3, wherein in the step (b), the positive and negative electrodes of the lithium-containing battery are reversely connected with the positive and negative electrodes of the charging power supply, so that the potential of the negative electrode of the lithium-containing battery relative to the third electrode is 2.5V 4V.
6. The method for repairing and regenerating a lithium-containing battery according to claim 3, wherein in the step (b), the negative electrode of the lithium-containing battery is electrically connected to the positive electrode of the charging power source, and the third electrode of the lithium-containing battery is electrically connected to the negative electrode of the charging power source, so that the potential of the negative electrode of the lithium-containing battery with respect to the third electrode is 2.5V 4V.
7. The method for repairing and regenerating a lithium-containing battery according to claim 1, wherein the step (b) further comprises a high-temperature pyrolysis step of heating the interior of the lithium-containing battery so that the temperature of the interior of the battery is heated to 40 ℃ to 100 ℃.
8. The method for repairing and regenerating a lithium-containing battery according to claim 7, wherein in the high-temperature pyrolysis step, a dissolving solution is injected into the lithium-containing battery, the dissolving solution is maintained at a high temperature for a predetermined time and then discharged, and the cycle is performed for 1 to 3 times, wherein the temperature of the dissolving solution at the high temperature is 40 ℃ to 100 ℃, the dissolving solution is a solvent having a dissolving property for organic components in the SEI film and having no destructive effect on electrode materials, and the dissolving solution is one or a mixture of more of carbonates, carboxylates, alcohols, ethers, ketones and water.
9. The method for repairing and regenerating a lithium-containing battery according to claim 7, wherein a cooling step of cooling the lithium-containing battery to 20 ℃ to 80 ℃ is further included after the step (b).
10. The method for repairing and regenerating a lithium-containing battery according to claim 1, wherein in the step (c), the original electrolyte in the lithium-containing battery is discharged and then subjected to a leaching step, a leaching agent is added into the battery to leach the electrolyte remained in the battery, and then the leaching agent is discharged out of the battery, wherein the leaching agent is one or more of carbonates, carboxylates, alcohols, ethers, ketones and water.
11. The method for repairing and regenerating a lithium-containing battery according to claim 1, wherein after the step (e), further comprising (f) a first-effect lithium-replenishing step: and connecting the positive electrode of the lithium-containing battery with a third electrode to perform low-current density discharge so that the positive active material of each positive plate is fully embedded with lithium, wherein the low-current density is 0.005-0.1C.
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