CN112909321A - Liquid zinc ion battery charge state on-line monitoring device and method - Google Patents
Liquid zinc ion battery charge state on-line monitoring device and method Download PDFInfo
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- CN112909321A CN112909321A CN202110290740.3A CN202110290740A CN112909321A CN 112909321 A CN112909321 A CN 112909321A CN 202110290740 A CN202110290740 A CN 202110290740A CN 112909321 A CN112909321 A CN 112909321A
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- ion battery
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
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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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Abstract
The invention relates to the technical field of battery monitoring management, and particularly discloses a liquid zinc-ion battery charge state on-line monitoring device, which comprises: a light source capable of emitting an optical signal; the optical fiber sensor is connected with the light source, is positioned in the electrolyte of the liquid zinc ion battery and can monitor a response signal to the optical signal in the charge and discharge process of the liquid zinc ion battery, and the detector is connected with the optical fiber sensor and can record the output wavelength of the optical fiber sensor in the charge and discharge process of the liquid zinc ion battery; and the charge and discharge tester is connected with the liquid zinc ion battery and is used for realizing charge and discharge of the liquid zinc ion battery. The invention also discloses an online monitoring method for the state of charge of the liquid zinc-ion battery. The online monitoring device for the charge state of the liquid zinc ion battery provided by the invention can accurately reflect the actual charge state of the battery.
Description
Technical Field
The invention relates to the technical field of battery monitoring management, in particular to a liquid zinc-ion battery charge state online monitoring device and a liquid zinc-ion battery charge state online monitoring method.
Background
Clean energy such as solar energy and wind energy has the characteristics of irregular intensity change along with time and uneven spatial distribution, so that the clean energy cannot be directly merged into a power grid, and a local energy storage system is required to collect generated electric energy and then uniformly merge into the power grid. The liquid zinc ion battery as a secondary zinc-based battery has the advantages of low cost, environmental friendliness, high energy density and good rate capability, and is considered to be a battery technology which can be applied to the field of energy storage in a large scale.
However, in the energy storage system, the state of charge of the battery needs to be monitored to know the condition of the battery in real time so as to better manage the battery. Currently, the methods for monitoring the state of charge of the battery mainly include an open-circuit voltage method and an ampere-hour integration method. The open-circuit voltage method determines the charge state under the current state according to the one-to-one correspondence relationship between the charge state and the voltage in the charge-discharge curve under the ideal state, and the battery needs to stand for a long time when reaching the open-circuit voltage, so that the battery is not suitable for real-time monitoring of the charge state; the ampere-hour integration method calculates the current state of charge of the battery by calculating the ratio of the electric quantity discharged in the current cycle to the electric quantity completely discharged in the previous cycle, and a large error is generated because the battery is aged during each charging and discharging and the working conditions of the battery in each cycle are not necessarily the same. Both methods estimate that the state of charge inside the battery cannot meet the requirement of online monitoring of the state of charge of the battery based on external measured voltage and current information.
Disclosure of Invention
The invention provides a liquid zinc-ion battery charge state online monitoring device and a liquid zinc-ion battery charge state online monitoring method, which solve the problem that the charge state in a battery cannot be accurately reflected in the related technology.
As a first aspect of the present invention, an online state of charge monitoring device for a liquid zinc-ion battery is provided, wherein the online state of charge monitoring device comprises:
a light source capable of emitting an optical signal;
the optical fiber sensor is connected with the light source, is positioned in the electrolyte of the liquid zinc ion battery and can monitor the response signal of the liquid zinc ion battery to the optical signal in the charging and discharging process,
the detector is connected with the optical fiber sensor and can record the output wavelength of the optical fiber sensor in the charge and discharge process of the liquid zinc ion battery;
and the charge and discharge tester is connected with the liquid zinc ion battery and is used for realizing charge and discharge of the liquid zinc ion battery.
Further, the optical fiber sensor includes any one of a long period grating, a fiber fabry-perot sensor, and a tapered fiber interferometer.
Further, the light source comprises a wide-spectrum light source, and the wavelength of a light signal emitted by the light source is 1510 nm-1590 nm.
Further, the liquid zinc ion battery comprises a container and electrolyte positioned in the container, and the optical fiber sensor is fixed in the electrolyte.
Further, the electrolyte comprises an aqueous phase solution and an organic phase solution, the aqueous phase solution and the organic phase solution can be arranged in a layered mode, the organic phase solution is arranged on the upper layer of the aqueous phase solution, and the optical fiber sensor is fixed in the aqueous phase solution.
Further, liquid zinc ion battery is still including setting up the anodal mass flow body and the setting of organic phase solution top are in the negative pole metal conductive electrode of aqueous phase solution below, anodal mass flow body with the positive pole of charge-discharge tester is connected, negative pole metal conductive electrode with the negative pole of charge-discharge tester is connected.
As another aspect of the present invention, there is provided an online state of charge monitoring method for a liquid zinc-ion battery, which is implemented by the online state of charge monitoring device for a liquid zinc-ion battery described above, and the method includes:
placing an optical fiber sensor in the electrolyte of the liquid zinc ion battery;
the device is sequentially connected with a light source, an optical fiber sensor and a detector, and a charge and discharge tester is connected with the liquid zinc ion battery;
and when the liquid zinc ion battery is charged and discharged, the detector records the output wavelength of the optical fiber sensor.
Further, the liquid zinc ion battery includes a container and an electrolyte in the container, the electrolyte includes an aqueous phase solution and an organic phase solution, the aqueous phase solution and the organic phase solution can be layered, the organic phase solution is on the upper layer of the aqueous phase solution, the placing of the optical fiber sensor in the electrolyte of the liquid zinc ion battery includes:
fixing the optical fiber sensor in the aqueous phase solution.
Further, the liquid zinc ion battery further includes a positive current collector disposed above the organic phase solution and a negative metal conductive electrode disposed below the aqueous phase solution, and the charging and discharging tester is connected to the liquid zinc ion battery, including:
and connecting the positive current collector with the positive electrode of the charge and discharge tester, and connecting the negative metal conductive electrode with the negative electrode of the charge and discharge tester.
According to the on-line monitoring device for the charge state of the liquid zinc ion battery, the response of the electrolyte to the optical signal is monitored through the optical fiber sensor, the diffusion of substances in the electrolyte is fast, long-time standing is not needed, meanwhile, the optical signal collected by the optical fiber sensor is only related to the chemical state in the electrolyte and is not related to the load size of the battery, and the actual charge state of the battery can be accurately reflected. Therefore, the online monitoring device for the state of charge of the liquid zinc ion battery realizes the measurement of the state of charge of the battery by monitoring the ion concentration change in the electrochemical reaction process in real time, and has more accurate and effective electric quantity estimation compared with an open-circuit voltage method and an ampere-hour integration method for monitoring voltage and current information.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
Fig. 1 is a schematic structural diagram of an on-line monitoring device for the state of charge of a liquid zinc ion battery provided by the invention.
Fig. 2 is a top view of the online state of charge monitoring device for a liquid zinc ion battery provided by the invention.
Fig. 3 is a graph showing the voltage variation with time and the current variation with time during a charge-discharge cycle of the present invention.
Fig. 4 is a data point diagram of the change of the center wavelength of the sensor with time during one charge-discharge cycle provided by the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged under appropriate circumstances in order to facilitate the description of the embodiments of the invention herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
In this embodiment, an on-line monitoring device for a state of charge of a liquid zinc-ion battery is provided, and fig. 1 is a schematic structural diagram of the on-line monitoring device for a state of charge of a liquid zinc-ion battery provided according to an embodiment of the present invention, as shown in fig. 1 and fig. 2, including:
a light source 8 capable of emitting a light signal;
the optical fiber sensor 7 is connected with the light source 8, is positioned in the electrolyte of the liquid zinc ion battery and can monitor the response signal of the liquid zinc ion battery to the optical signal in the charging and discharging process,
the detector 9 is connected with the optical fiber sensor 7 and can record the output wavelength of the optical fiber sensor 7 in the charge and discharge process of the liquid zinc ion battery;
and the charge and discharge tester 4 is connected with the liquid zinc ion battery and is used for realizing charge and discharge of the liquid zinc ion battery.
It should be understood that the embodiment of the present invention monitors the response of the electrolyte to the light signal through the optical fiber sensor, while the diffusion of the substance in the electrolyte is fast, and does not need to be left for a long time, and the light signal collected by the optical fiber sensor is only related to the chemical state inside the electrolyte, and is not related to the load of the battery, so that the actual charge state of the battery can be reflected more accurately. Therefore, the online monitoring device for the state of charge of the liquid zinc ion battery realizes the measurement of the state of charge of the battery by monitoring the ion concentration change in the electrochemical reaction process in real time, and has more accurate and effective electric quantity estimation compared with an open-circuit voltage method and an ampere-hour integration method for monitoring voltage and current information.
In some embodiments, the fiber optic sensor 7 comprises any one of a long period grating, a fiber optic fabry-perot sensor, and a tapered fiber optic interferometer.
It should be understood that the optical fiber sensor 7 can also be implemented by other sensors capable of implementing the above functions, and is not limited herein.
Specifically, the light source 8 comprises a wide-spectrum light source, and the wavelength of a light signal emitted by the light source 8 is 1510 nm-1590 nm.
In the embodiment of the invention, the liquid zinc-ion battery comprises a container 3 and electrolyte in the container 3, and the optical fiber sensor 7 is fixed in the electrolyte.
Specifically, the electrolyte comprises an aqueous phase solution 6 and an organic phase solution 5, the aqueous phase solution 6 and the organic phase solution 5 can be arranged in layers, the organic phase solution 5 is arranged on the upper layer of the aqueous phase solution 6, and the optical fiber sensor 7 is fixed in the aqueous phase solution 6.
In the present example, the aqueous solution 6 includes magnesium sulfate, zinc sulfate, and the like.
Specifically, liquid zinc ion battery is still including setting up the anodal mass flow body 1 and the setting of organic phase solution 5 top are in negative pole metal conductive electrode 2 of aqueous phase solution 6 below, anodal mass flow body 1 with charge and discharge tester 4's positive pole is connected, negative pole metal conductive electrode 2 with charge and discharge tester 4's negative pole is connected.
In the embodiment of the present invention, the optical fiber sensor 7 is exemplified by a long-period optical fiber grating, the long-period optical fiber grating is prepared by using an ultraviolet writing method, the length of the long-period optical fiber grating is about 5mm, and the grid period is about 500 nm. The long-period fiber grating sensor is placed in a container 3 containing positive and negative electrodes, and an aqueous solution 6 of magnesium sulfate and zinc sulfate, and an organic phase solution 5 of a positive active material are poured. In this example, the positive electrode active material is 2,2,6, 6-tetramethylpiperidine oxide TEMPO, which is convertible between an oxidized state and a reduced state. The organic phase solvent is tetraethylene glycol dimethyl ether. The negative pole in the container 3 is a zinc pole piece, and is fixed at the bottom of the container by using ultraviolet glue, and the positive pole adopts a current collector which is a carbon fiber felt. A certain space is reserved between the zinc cathode and the long-period fiber grating in space.
In this embodiment, the anode and the cathode of the zinc battery are connected to the charge and discharge tester 4, and the concentration of the components in the aqueous electrolyte changes during the charge and discharge of the zinc battery, which causes the refractive index of the liquid environment in which the long-period fiber grating sensor is placed to change, so that the output wavelength of the optical fiber sensor 7 detected by the detector 9 changes.
In the embodiment of the invention, the liquid zinc ion battery is charged and discharged at a constant current of 60mA, the voltage and the current change along with time are shown in figure 3, and the wavelength change information of the optical fiber sensor tracked by using the detector is shown in figure 4. The state of charge information of the battery is obtained through calculation according to the voltage and current change curve and is compared with the change information of the center wavelength of the sensor, and the state of charge information of the battery can be obtained according to the position of the center wavelength of the optical fiber sensor in the battery.
The specific working principle is as follows:
when the light wave is transmitted to the grating region in the optical fiber, part of the light can be diffracted to the cladding in the form of a radiation mode to form a cladding mode; the cladding mode, when reflected back into the core, will form mode interference with the core mode, and will be spectrally represented as a resonant envelope. When the ion concentration of the external environment changes, the refractive index around the fiber grating region also changes, so that the effective refractive index of the cladding mode changes, the resonance wavelength of the interference spectrum drifts, and the ion concentration information can be indirectly obtained by tracking the change relation between the wavelength drift and the ion concentration. From the ion concentration information, the ion migration process in the electrolyte solution can be inverted, thereby obtaining the state of charge of the battery.
It should be understood that when the monitoring is performed by other charge state monitoring methods, for example, when the monitoring is performed by an open-circuit voltage method, the open-circuit voltage method determines the charge state in the current state according to the one-to-one correspondence relationship between the charge state and the voltage in the charge-discharge curve in the ideal state, and the battery needs to be left for a long time when reaching the open-circuit voltage, and is not suitable for the real-time monitoring of the charge state; because the actual voltage during the charging process is higher than the open-circuit voltage and the voltage during the discharging process is lower than the open-circuit voltage due to the existence of the overpotential, the data recorded in fig. 2 reflects the actual voltage and cannot be used as the open-circuit voltage. The open circuit voltage requires the battery to pass through a long time (more than two hours) because it is required that the substances on the electrode surface are sufficiently diffused.
For another example, when the ampere-hour integration method is used, the ampere-hour integration method calculates the current state of charge of the battery by calculating the ratio of the discharged electric quantity in the current cycle to the fully discharged electric quantity in the previous cycle, and a large error is generated because the battery is aged during each charge and discharge and the working conditions of the battery in each cycle are not necessarily the same. The capacity of the battery under high power load is lower than the rated capacity, so the capacity of the previous period cannot be equal to the capacity of the current period.
The embodiment of the invention realizes monitoring of the response of the electrolyte to the optical signal through the optical fiber sensor, and the diffusion of substances in the electrolyte is fast without long-time standing. Meanwhile, the optical signal collected by the optical fiber is related to the chemical state in the solution and is unrelated to the load of the battery, so that the actual charge state of the battery can be more accurately reflected.
As another embodiment of the present invention, there is provided an online monitoring method for the state of charge of a liquid zinc-ion battery, implemented by the online monitoring device for the state of charge of a liquid zinc-ion battery, including:
placing an optical fiber sensor in the electrolyte of the liquid zinc ion battery;
the device is sequentially connected with a light source, an optical fiber sensor and a detector, and a charge and discharge tester is connected with the liquid zinc ion battery;
and when the liquid zinc ion battery is charged and discharged, the detector records the output wavelength of the optical fiber sensor.
Specifically, the liquid zinc ion battery includes a container and an electrolyte located in the container, where the electrolyte includes an aqueous phase solution and an organic phase solution, the aqueous phase solution and the organic phase solution can be layered, the organic phase solution is on an upper layer of the aqueous phase solution, and the placing of the optical fiber sensor in the electrolyte of the liquid zinc ion battery includes:
fixing the optical fiber sensor in the aqueous phase solution.
Specifically, the liquid zinc ion battery further includes a positive current collector disposed above the organic phase solution and a negative metal conductive electrode disposed below the aqueous phase solution, and the charging and discharging tester is connected to the liquid zinc ion battery, including:
and connecting the positive current collector with the positive electrode of the charge and discharge tester, and connecting the negative metal conductive electrode with the negative electrode of the charge and discharge tester.
For the specific working process of the online monitoring method for the state of charge of the liquid zinc ion battery provided by the embodiment of the present invention, reference may be made to the foregoing description, and details are not described herein again.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (9)
1. The utility model provides a liquid zinc ion battery state of charge on-line monitoring device which characterized in that includes:
a light source capable of emitting an optical signal;
the optical fiber sensor is connected with the light source, is positioned in the electrolyte of the liquid zinc ion battery and can monitor the response signal of the liquid zinc ion battery to the optical signal in the charging and discharging process,
the detector is connected with the optical fiber sensor and can record the output wavelength of the optical fiber sensor in the charge and discharge process of the liquid zinc ion battery;
and the charge and discharge tester is connected with the liquid zinc ion battery and is used for realizing charge and discharge of the liquid zinc ion battery.
2. The on-line monitoring device for the state of charge of the liquid zinc-ion battery according to claim 1, wherein the optical fiber sensor comprises any one of a long-period grating, a fiber Fabry-Perot sensor and a tapered fiber interferometer.
3. The liquid zinc-ion battery state of charge on-line monitoring device of claim 1, wherein the light source comprises a broad spectrum light source, and the wavelength of the light signal emitted by the light source is 1510 nm-1590 nm.
4. The on-line monitoring device for the state of charge of the liquid zinc-ion battery according to claim 1, wherein the liquid zinc-ion battery comprises a container and an electrolyte in the container, and the optical fiber sensor is fixed in the electrolyte.
5. The device for on-line monitoring of the state of charge of the liquid zinc-ion battery according to claim 4, wherein the electrolyte comprises an aqueous phase solution and an organic phase solution, the aqueous phase solution and the organic phase solution can be arranged in layers, the organic phase solution is arranged on the upper layer of the aqueous phase solution, and the optical fiber sensor is fixed in the aqueous phase solution.
6. The on-line monitoring device for the state of charge of the liquid zinc-ion battery according to claim 5, wherein the liquid zinc-ion battery further comprises a positive electrode current collector arranged above the organic phase solution and a negative electrode metal conductive electrode arranged below the aqueous phase solution, the positive electrode current collector is connected with a positive electrode of the charge and discharge tester, and the negative electrode metal conductive electrode is connected with a negative electrode of the charge and discharge tester.
7. The liquid zinc ion battery state of charge on-line monitoring method realized by the liquid zinc ion battery state of charge on-line monitoring device according to any one of claims 1 to 6, is characterized by comprising the following steps:
placing an optical fiber sensor in the electrolyte of the liquid zinc ion battery;
the device is sequentially connected with a light source, an optical fiber sensor and a detector, and a charge and discharge tester is connected with the liquid zinc ion battery;
and when the liquid zinc ion battery is charged and discharged, the detector records the output wavelength of the optical fiber sensor.
8. The on-line monitoring method for the state of charge of the liquid zinc-ion battery according to claim 7, wherein the liquid zinc-ion battery comprises a container and an electrolyte solution located in the container, the electrolyte solution comprises an aqueous phase solution and an organic phase solution, the aqueous phase solution and the organic phase solution can be arranged in layers, the organic phase solution is on the upper layer of the aqueous phase solution, and the placing of the optical fiber sensor in the electrolyte solution of the liquid zinc-ion battery comprises:
fixing the optical fiber sensor in the aqueous phase solution.
9. The on-line monitoring method for the state of charge of the liquid zinc-ion battery according to claim 8, wherein the liquid zinc-ion battery further comprises a positive electrode current collector disposed above the organic phase solution and a negative electrode metal conductive electrode disposed below the aqueous phase solution, and the connecting a charge and discharge tester with the liquid zinc-ion battery comprises:
and connecting the positive current collector with the positive electrode of the charge and discharge tester, and connecting the negative metal conductive electrode with the negative electrode of the charge and discharge tester.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110290740.3A CN112909321A (en) | 2021-03-18 | 2021-03-18 | Liquid zinc ion battery charge state on-line monitoring device and method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110290740.3A CN112909321A (en) | 2021-03-18 | 2021-03-18 | Liquid zinc ion battery charge state on-line monitoring device and method |
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| CN112909321A true CN112909321A (en) | 2021-06-04 |
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| CN202110290740.3A Pending CN112909321A (en) | 2021-03-18 | 2021-03-18 | Liquid zinc ion battery charge state on-line monitoring device and method |
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- 2021-03-18 CN CN202110290740.3A patent/CN112909321A/en active Pending
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