JP3218920U - Apparatus for regenerating a battery containing a fluid electrolyte - Google Patents

Abstract

An object of the present invention is to provide a battery regenerator including a fluid electrolyte that can be regenerated without finely disassembling a degraded battery. SOLUTION: A container 10 in which a core structure C of a battery is accommodated, a sensor unit 20 including a plurality of sensors 21, and a plurality of functional electrolyte storage tanks 30A to 30C in which different functional electrolytes are stored. The pump 40 is connected to the container 10 and the functional electrolyte storage tanks 30A to 30C through the conduit P, and the controller 50 controls the pump 40 to store a functional electrolyte suitable for removing the solid electrolyte interface film. 10, the sensor 21 measures the characteristic parameters of the functional electrolyte in the vessel 10 in which the core structure C is immersed, and the controller 50 controls the pump 40 on the basis of the measured characteristic parameters. When the characteristic parameters of the functional electrolyte match the characteristic parameters of the normal battery, the injection of the functional electrolyte is stopped. [Selected figure] Figure 1

Description

  The present invention relates to a regeneration device for an electrochemical storage member, and more particularly to a regeneration device for a battery containing a fluid electrolyte such as a lithium, aluminum or sulfur battery.

Lithium batteries, lithium ion batteries, and high-performance lithium ion capacitors are the mainstream of electrochemical storage, and the manufacturing cost of lithium batteries is reduced year by year, promoting the rapid development of the battery industry, which is economical in various application fields Has an advantage.
A storage system having a lithium ion battery as a core is an important power system of an electric vehicle. With the widespread use of electric vehicles worldwide, the recovery of storage systems has become an urgent issue that needs to be solved.

Unfortunately, there are very few methods to recover these old waste lithium batteries, and there are few common methods such as mechanical processes, pyrometallurgical processes (abbr. PP), hydrometallurgy processes , Or abbreviated HP).
The mechanical processing basically uses a physical method to recover the material of the old waste lithium battery in the procedure of crushing, collection and classification, and includes magnetic separation, air ballistic separation and sieving.
Dry smelting processes use high temperatures to recover materials, including thermal melting, smelting, distillation, and refining. However, lithium and organic compounds can not be recovered using such methods.
The hydrosmelting process is usually machined and the ground material is leached in solution using acid or alkali, purified and extracted. The known old waste lithium battery recovery techniques are briefly described below.

Patent Document 1 already disclosed discloses a method for treating a battery member capable of separating a positive electrode active material and a sulfide solid electrolyte material and recovering lithium contained in the positive electrode active material and the sulfide solid electrolyte material. There is.
In this treatment method, hydrogen sulfide is generated by bringing the battery member and the treatment liquid into contact with each other, and a contact step in which lithium contained in the sulfide solid electrolyte material is dissolved in the treatment liquid, and lithium is dissolved. It has a positive electrode active material recovery step of recovering the positive electrode active material which is an insoluble component from the treatment liquid, and a lithium compound recovery step which recovers a lithium compound from the treatment liquid which is the positive electrode active material which is the insoluble component. It is characterized by

Further, Patent Document 2 is for extracting cathode materials from waste lithium ion batteries from useful elements such as Co (cobalt), Ni (nickel), Mn (manganese), Li (lithium) and Fe (iron). It provides methods and equipment used for recovery of lithium ion batteries which are dissolved in solution and produce active cathode materials for use in new batteries.
Patent Document 3 provides an alkaline battery recovery processing technology for recovering manganese dioxide, zinc hydroxide / oxide and steel from a wet-ground metal-cased alkaline dry battery.
There are also methods of recovering steel and high purity manganese dioxide that can be used directly for electrodes of alkaline batteries.
Further, Patent Document 4 provides an example of a method of recovering a positive electrode material of a lithium ion battery. In one example, the positive electrode material is heated in concentrated lithium hydroxide solution under pressure. After heating, the positive electrode material is separated from the concentrated lithium hydroxide solution. After separation, the positive electrode material is washed in an alkaline solution. After washing, the positive electrode material is dried and sintered.

The prior art described above basically involves the recycling and recovery process of physical processes or chemical reactions. The physical process is, for example, the destruction of the hardware part of old waste lithium batteries. Chemical processes, for example, use alkaline and acidic agents to dissolve the inner materials (such as powder material) of old waste lithium batteries. Both physical and chemical processes are destruction of the original battery module, and too much energy is required, resulting in environmental burden of waste collection. Besides these, these processes have to go through a number of steps to finally complete the recovery of the material.
Technology for disassembling old waste lithium batteries causes pollution of waste gas, waste liquid, wastes, etc. in the decomposition process, causing hidden hazards to the ecological environment, and may even be harmful to health, but recovery It is understandable that it will be a waste of resources if it does not process. In practice, the cost of lithium battery recovery is very high, for example, the energy costs and time costs consumed in the recovery process can cause the recovery cost to outweigh the value of the recovered material.

U.S. Pat. No. 5,857,412 B2 US Patent US20130302226A1 U.S. Pat. No. 8,728,419 B1 US Patent US20160043450A1 Specification

  The problem to be solved by the present invention is to provide a battery regenerator including a fluid electrolyte that can be regenerated without finely disassembling a degraded battery.

  An apparatus for regenerating a battery containing a fluid electrolyte according to the present invention comprises a container, a sensor unit, a plurality of functional electrolyte storage tanks, at least one pump and a controller, wherein the container is a core of a battery whose package housing has been removed. The functional electrolyte storage tank stores different functional electrolytes, the pump is connected to the container and the functional electrolyte storage tank through a pipeline, and the controller is used to store the structure. Is electrically connected to the sensor unit and the pump, and the controller controls the pump to inject a functional electrolyte suitable for removing the solid electrolyte interface film out of different functional electrolytes into the container, A core structure is immersed in the functional electrolyte, the sensor unit includes a plurality of sensors, and the core structure is immersed in the functional electrolyte. When the sensor measures a characteristic parameter of the functional electrolyte in the container, and the controller controls the pump based on the characteristic parameter obtained by the measurement by the sensor, the functional electrolyte storage tank The functional electrolyte is injected into the container, and the characteristic parameters of the functional electrolyte in the container match the characteristic parameters of the electrolyte used in the normal battery. Stop the injection.

Preferably, the functional electrolyte contains several types of functional electrolytes having different ion concentrations, and a solvent suitable for the functional electrolyte.
Preferably, the container comprises an inlet and an outlet, and the pump is connected to the inlet of the container and the functional electrolyte storage tank via a pipeline, and the controller controls the pump to inlet the functional electrolyte And the sensor unit is connected to the outlet of the container through a conduit and used to measure the characteristic parameter of the functional electrolyte flowing out of the outlet of the container, and the controller is used to measure the characteristic parameter of the functional electrolyte. The pump is controlled based on the characteristic parameter obtained by the measurement by the sensor to inject any suitable functional electrolyte in the functional electrolyte storage tank into the container from the inlet.

Alternatively, the container comprises an inlet and an outlet, and the pump is connected to the inlet of the container and the functional electrolyte storage tank through a multi-pass control valve and a pipeline, and the controller is provided with the pump and the multi-pass The control valve is controlled to inject functional electrolyte into the container from the inlet, and the sensor unit is connected to the outlet of the container through a conduit, and the characteristic parameter of the functional electrolyte flowing out of the outlet of the container And the controller controls the pump and the multi-pass control valve based on the characteristic parameters obtained by the measurement by the sensor to use any suitable function in the functional electrolyte storage tank. Electrolyte is injected into the vessel from the inlet.
In this case, the outlet of the container is connected to the multi-channel control valve through a pipeline, and the characteristic parameters of the functional electrolyte in the container match the characteristic parameters of the electrolyte used in the normal battery. At the same time, the controller may control the multi-channel control valve to return the functional electrolyte discharged from the outlet of the container to one of the functional electrolyte storage tanks for storage.

Preferably, the power output circuit includes a power output circuit electrically connected to the core structure of the package housing removed battery, and the power output circuit applies a voltage to the core structure of the package housing removed battery; Is between 0V and 5V.
Preferably, the package measurement circuit includes a capacitance measurement circuit electrically connected to the core structure of the battery whose package housing has been removed, and the capacitance measurement circuit is used to measure the capacitance of the core structure of the battery whose package housing has been removed. When the capacity reaches the normal range of capacity, the injection of the functional electrolyte is stopped.

  The effect of the present invention is that even with a damaged battery, a solid electrolyte interface (SEI) film is removed using a different functional electrolyte without finely disassembling, and the battery is activated by replacing it with a useful electrolyte. It is about being able to recover.

FIG. 1 is a block diagram illustrating an embodiment of a battery regeneration device including a fluid electrolyte according to the present invention. FIG. 6 is a block diagram showing another embodiment of a battery regeneration device including a fluid electrolyte according to the present invention. FIG. 6 is a block diagram showing still another embodiment of a battery regeneration device including a fluid electrolyte according to the present invention.

Hereinafter, an embodiment of the present invention will be described in detail based on the drawings. In the following description, the positional relationship including upper, lower, left, and right will conform to the direction of the drawings unless otherwise specified.
A lithium ion battery will be described as an example.
In a lithium ion battery, lithium ions are released from the active material of the positive electrode at the first charge and discharge, pass through the separator and further enter the electrolytic solution, and are finally taken into the layered voids of the negative electrode carbon material to The behavior of one release and uptake is completed. At this time, electrons are emitted from the positive electrode along the circuit and enter the negative electrode carbon material.
After obtaining some electrons, the electrolytic solution generates a reduction reaction and bonds with lithium ions to form an interfacial film having a thickness of about 100 to 120 nm. This interface film is a solid electrolyte interphase (SEI) film and is hereinafter abbreviated as a SEI film. The SEI film is usually a solid-liquid phase interface film formed between the electrode material and the electrolyte. An oxidation-reduction reaction occurs between the electron, the solvent in the electrolytic solution and the lithium ion, and after the solvent molecule receives the electron, it combines with the lithium ion to form a SEI film, and H2, CO, CH2 = CH2, etc. To produce a gas. As the thickness of the SEI film increases, electrons can not pass through, a blunting layer is formed, and the continuation of the redox reaction is suppressed.

Most of the decaying cause of old waste lithium batteries is caused by the irregularity of the SEI film formed on the negative electrode, the loss of lithium ions in the electrolyte reduces the capacity, and the positive and negative electrodes have Be in balance. Besides, an excessively thick SEI film prevents lithium ions from being inserted into the SEI layer and performing charge exchange. As a result, the capacity of the battery may be extremely reduced, or the resistance (low voltage) may be too high.
The method of regenerating a battery containing a fluid electrolyte according to the present invention can appropriately remove the SEI film which has an adverse effect on the battery. It can also be explained that there is a need to test concentration and conductivity in the regeneration process.

FIG. 1 shows an embodiment of a battery regeneration device including a fluid electrolyte of the present invention.
An apparatus for regenerating a battery including a fluid electrolyte includes a container 10, a sensor unit 20, a plurality of functional electrolyte storage tanks 30A to 30C, at least one pump 40, and a controller 50.

The container 10 is used to accommodate the core structure C of the battery from which the package housing has been removed, and it is preferable to secure the core structure C in the container 10 using a frame or fixing means.
Since different functional electrolytes are applied to different batteries, it is necessary to store different functional electrolytes of different types used in the battery regeneration process in different functional electrolyte storage tanks 30A to 30C, and thus different functions. The functional electrolyte is stored in the functional electrolyte storage tanks 30A to 30C.
The pump 40 is connected to the container 10 and the functional electrolyte storage tanks 30A to 30C through a conduit P.
The controller 50 is electrically connected to the sensor unit 20 and the pump 40, and the controller 50 controls the pump 40 so that a functional electrolyte suitable for removing the SEI film among the different functional electrolytes (for example, functional electrolyte) The functional electrolytic solution (stored in the storage tank 30A) is injected into the container 10, and the core structure C is immersed in the functional electrolytic solution.

  A functional electrolyte suitable for removing a solid electrolyte interface (SEI) film is a typical functional electrolyte having carbonate and / or alcohol and / or ketone groups, and the functional electrolyte has functional groups. Containing chemicals such as carbonic acid ester, represented by R1 O-CO-O R2 (of which R1, R2 = H (hydrogen group), methyl group, ethyl group, cyclic ring), and the aqueous solution is alcohol and ketone including. The typical chemical formula is as follows.

The sensor unit 20 includes a plurality of sensors 21. The sensor 21 measures characteristic parameters of the functional electrolyte in the container 10 while the core structure C is immersed in the functional electrolyte.
The controller 50 controls the pump 40 based on the characteristic parameter obtained by the measurement by the sensor 21 to inject any suitable functional electrolytic solution in the functional electrolytic solution storage tanks 30A to 30C into the container 10. This is intended to adjust the components of the functional electrolyte, and when the characteristic parameters of the functional electrolyte in the container 10 match the characteristic parameters of the electrolyte used in the normal battery, the injection of the functional electrolyte is It is stopped. The functional electrolyte contains several types of functional electrolytes having different ion concentrations, and a solvent suitable for the functional electrolyte.

  The purpose of measuring the characteristic parameters of the functional electrolyte is to determine the applicability of the functional electrolyte through the concentration in the characteristic parameters obtained by the measurement (for example, the lithium ion concentration of the lithium ion battery electrolyte) and the conductivity. It is to do. That is, when the measured concentration is too low or too high, functional electrolytes of different concentrations can be injected and adjusted to restore the functional electrolyte to a concentration that allows normal use. . The conductivity is also one of the important measurement indexes of the functional electrolyte, and when the conductivity of the functional electrolyte is too low, the battery can not be charged and discharged with high performance, so the concentration of the functional electrolyte is By measuring the conductivity and measuring the conductivity, the battery can be restored to its normal state by injecting another suitable functional electrolyte.

Preferably, the core structure C is placed in the container 10, and after being immersed in the functional electrolyte, the flow of the functional electrolyte can be maintained to enhance the effect of washing and removing the SEI film.
To realize the flow, for example, as in the alternative embodiment shown in FIG. 2, the vessel 10 comprises an inlet 11 and an outlet 12 and the pump 40 via the line P the inlet 11 of the vessel 10 and several functions. The controller 50 controls the pump 40 to inject functional electrolyte from the inlet 11 into the vessel 10, which is connected to the alkaline electrolyte storage tanks 30A to 30C.
The sensor unit 20 is connected to the outlet 12 of the container 10 through the conduit P, and the characteristic parameter of the functional electrolyte flowing out of the outlet 12 of the container 10 is measured, and the controller 50 is obtained by measurement by the sensor 21 The pump 40 is controlled based on the characteristic parameter, and any one of the functional electrolyte storage tanks 30A to 30C is injected into the container 10 through the inlet 11. Thereby, the flow of the functional electrolyte in which the core structure C is immersed can be maintained.

FIG. 3 shows still another embodiment of a battery regeneration device containing a fluid electrolyte according to the present invention.
In this embodiment, the container 10 has an inlet 11 and an outlet 12, and a pump 40 is connected to the inlet 11 of the container 10 and the functional electrolyte storage tanks 30A to 30D through the multi-channel control valve 60 and the pipe line P. The controller 50 controls the pump 40 and the multi-channel control valve 60 to inject functional electrolyte from the inlet 11 into the vessel 10.
Also, a sensor unit 20 is connected to the outlet 12 of the container 10 through the pipe line P, and is used to measure characteristic parameters of the functional electrolyte flowing out of the outlet 12 of the container 10.
The controller 50 controls the pump 40 and the multi-channel control valve 60 based on the characteristic parameters obtained by the measurement by the sensor 21 to enter any suitable functional electrolyte in the functional electrolyte storage tanks 30A to 30D. 11 to inject into container 10

In one embodiment of the device for regenerating a battery containing a fluid electrolyte according to the present invention, the outlet 12 of the container 10 is connected to the multi-pass control valve 60 through the conduit P, and the characteristic parameters of the functional electrolyte in the container 10 The controller 50 controls the multi-pass control valve 60 to match the functional electrolyte discharged from the outlet 12 of the container 10 with the functional electrolyte when the characteristic parameter of the normal battery is matched with the characteristic parameter of the electrolyte used in the battery. It is returned to one of the storage tanks 30A to 30D and stored.
For example, the functional electrolyte suitable for removing the solid electrolyte interface (SEI) film is returned to the same functional electrolyte storage tank 30A, or is returned to the functional electrolyte storage tank 30D dedicated to recovery of other functional electrolytes. May be That is, the functional electrolyte recovered in the functional electrolyte storage tank 30A in this way is a rebalanced electrolyte, for example, a lithium-containing electrolyte used in a lithium ion battery has a suitable lithium ion concentration and the like. The functional electrolyte which has conductivity and is recovered in such a functional electrolyte storage tank 30A can be directly injected into a new package housing of the restored core structure C to make a regenerated battery.

  The embodiment shown in FIG. 1 includes a power output circuit 70 electrically connected to the core structure C, wherein the power output circuit 70 applies a voltage to the core structure C, and the core structure C is immersed in the functional electrolyte. Used to support SEI membrane removal during operation. The voltage range is between 0V and 5V.

In addition, it may include a capacitance measurement circuit 80 electrically connected to the core structure C.
The capacity measuring circuit 80 is used to measure the capacity of the core structure C while the core structure C is immersed in the functional electrolyte, and when the capacity reaches the capacity in the normal range, the functional electrolyte Injection is stopped.

  The above shows only preferred embodiments of the present invention, and the scope of rights of the present invention is not limited to these embodiments, and changes and modifications that do not deviate from the claims of the utility model registration Both are included in the scope of the present invention.

DESCRIPTION OF SYMBOLS 10 container 11 inlet 12 outlet 20 sensor unit 21 sensor 30A-30D functional electrolyte storage tank 40 pump 50 controller 60 multi-pass control valve 70 electric power output circuit 80 capacity measurement circuit C core structure P pipe line

Claims (7)

  An apparatus for regenerating a battery containing a fluid electrolyte, comprising: a container, a sensor unit, a plurality of functional electrolyte storage tanks, at least one pump and a controller, wherein the container has a package housing-removed battery core structure Are used to store different functional electrolytes in the functional electrolyte storage tank, the pump is connected to the container and the functional electrolyte storage tank via a pipeline, and the controller is used to store the functional electrolyte storage tank. The core is electrically connected to the sensor unit and the pump, and the controller controls the pump to inject a functional electrolyte suitable for removing a solid electrolyte interface film out of different functional electrolytes into the container, and the core The structure is immersed in the functional electrolyte, the sensor unit comprises a plurality of sensors, and the core structure is immersed in the functional electrolyte The sensor measures a characteristic parameter of the functional electrolyte in the container, and the controller controls the pump on the basis of the characteristic parameter obtained by the measurement by the sensor; Injection of a functional electrolyte when any suitable functional electrolyte is injected into the container and the characteristic parameters of the functional electrolyte in the container match the characteristic parameters of the electrolyte used in the normal battery An apparatus for regenerating a battery containing a fluid electrolyte, comprising:   The apparatus for regenerating a battery containing a fluid electrolyte according to claim 1, wherein the functional electrolyte comprises two or more kinds of functional electrolytes having different ion concentrations, and a solvent suitable for the functional electrolyte. .   The container comprises an inlet and an outlet, and the pump is connected to the inlet of the container and the functional electrolyte storage tank through a pipeline, and the controller controls the pump to supply the functional electrolyte from the inlet to the container , And the sensor unit is connected to the outlet of the container through a pipeline, and is used to measure the characteristic parameter of the functional electrolyte flowing out of the outlet of the container, and the controller measures the sensor 2. The method according to claim 1, further comprising controlling the pump to inject any suitable functional electrolyte in the functional electrolyte storage tank into the container from the inlet based on the characteristic parameter obtained in An apparatus for the regeneration of a battery comprising the described fluid electrolyte.   The container comprises an inlet and an outlet, and the pump is connected to the inlet of the container and the functional electrolyte storage tank through a multi-pass control valve and a pipeline, and the controller is the multi-pass control valve Control electrolyte is injected into the container through the inlet, and the sensor unit is connected to the outlet of the container through a conduit to measure characteristic parameters of the functional electrolyte flowing out of the outlet of the container And the controller controls the pump and the multi-pass control valve based on the characteristic parameters obtained by the measurement by the sensor to use the controller to control the pump and the multi-flow path control valve. The apparatus for regenerating a battery containing a fluid electrolyte according to claim 1, wherein the solution is injected into the vessel from an inlet.   The outlet of the container is connected to the multi-channel control valve through a conduit, and when the characteristic parameter of the functional electrolyte in the container matches the characteristic parameter of the electrolyte used in the normal battery, The controller is characterized in that the controller controls the multi-channel control valve to return the functional electrolyte discharged from the outlet of the container to one of the functional electrolyte storage tanks for storage. An apparatus for regenerating a battery comprising the fluid electrolyte according to 4.   The power output circuit includes a power output circuit electrically connected to the core structure of the package housing removed battery, and the power output circuit applies a voltage to the core structure of the package housing removed battery, and the voltage range is 0 V to An apparatus for regenerating a battery comprising a fluid electrolyte according to claim 1, characterized in that it is between 5V.   It includes a capacitance measurement circuit electrically connected to the core structure of the battery whose package housing has been removed, and the capacitance measurement circuit is used to measure the capacitance of the core structure of the battery whose package housing has been removed, and the capacitance is normal The apparatus for regenerating a battery containing a fluid electrolyte according to claim 1, wherein the injection of the functional electrolyte is stopped when the capacity of the range is reached.

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