CN113972413A - Solid-state battery capable of monitoring electrolyte temperature in real time and temperature monitoring method - Google Patents

Solid-state battery capable of monitoring electrolyte temperature in real time and temperature monitoring method Download PDF

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Publication number
CN113972413A
CN113972413A CN202111039166.0A CN202111039166A CN113972413A CN 113972413 A CN113972413 A CN 113972413A CN 202111039166 A CN202111039166 A CN 202111039166A CN 113972413 A CN113972413 A CN 113972413A
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solid
state battery
temperature
electrolyte
embedded
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CN113972413B (en
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孙浩
马天鸿
席佳伟
黄曦
张建奇
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Xidian University
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Xidian University
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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
    • H01M10/486—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte for measuring temperature
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Materials Engineering (AREA)

Abstract

The invention discloses a solid-state battery capable of monitoring the temperature of an electrolyte in real time and a temperature monitoring method; the solid-state battery includes: a positive electrode, a negative electrode, a solid electrolyte and a temperature monitoring device; wherein, the temperature monitoring device includes: a single mode fiber and at least one FBG sensor; each FBG sensor is connected in the single-mode optical fiber at intervals in series; the single-mode optical fiber is partially embedded in the solid electrolyte between the positive electrode and the negative electrode, and at least one FBG sensor is connected in series with the embedded part. The invention can realize the rapid and in-situ measurement of multiple parameters of the internal temperature, the pressure and the strain of the solid-state battery.

Description

Solid-state battery capable of monitoring electrolyte temperature in real time and temperature monitoring method
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a solid-state battery capable of monitoring the temperature of an electrolyte in real time and a temperature monitoring method.
Background
Rechargeable batteries are currently a common reusable energy storage device. The size of the battery can be freely made, so that the battery can be applied to various devices, for example, electric vehicles, smart phones, notebook computers, mobile tablets, watches, hybrid electric vehicles and other devices use rechargeable batteries. The increasing demand for use of rechargeable batteries has challenged the life and reliability of batteries.
Solid-state batteries are suitable choices for providing electrical energy to various devices because of their advantages of high energy density, long cycle life, low self-discharge capability, and the like. However, accidents caused by the quality of the battery, such as the self-explosion of the mobile phone battery, the spontaneous combustion of the battery and the like, occur frequently, and serious influence is caused on the life and property safety of the public. These accidents occur because, in the current application scenario of the solid-state battery, only the electrical performance of the output of the solid-state battery is concerned, and the thermal performance inside the solid-state battery is not concerned. However, the thermal performance inside the battery is the index that can reflect the performance and safety state of the solid-state battery most; therefore, only real-time monitoring of the internal thermal performance of the solid-state battery is the best solution for evaluating the battery performance and thus preventing battery safety accidents.
Currently, only in precision electronic devices, temperature sensors are arranged around the solid-state battery to monitor the thermal performance of the solid-state battery by monitoring the ambient temperature of the solid-state battery. However, since a certain time is required for the heat energy to be conducted from the inside of the solid-state battery to the external environment and further affect the ambient temperature, the method for monitoring the ambient temperature around the battery cannot acquire the changes of parameters such as the temperature, the pressure, the strain and the like in the battery in real time; therefore, how to realize the rapid and in-situ measurement of multiple parameters of the internal temperature, pressure and strain of the solid-state battery has not been a feasible solution in the prior art.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a solid-state battery capable of monitoring the temperature of an electrolyte in real time and a temperature monitoring method.
The technical problem to be solved by the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a solid-state battery capable of monitoring the temperature of an electrolyte in real time, comprising: a positive electrode, a negative electrode, and a solid state electrolyte, further comprising: a temperature monitoring device; wherein,
the temperature monitoring device includes: a single mode Fiber and at least one FBG (Fiber Bragg Grating) sensor; each FBG sensor is connected in the single-mode optical fiber at intervals in series;
the single-mode optical fiber is partially embedded in the solid electrolyte between the positive electrode and the negative electrode, and at least one FBG sensor is connected in series with the embedded part.
Preferably, the FBG sensors include at least 2;
wherein at least one of the FBG sensors is located in the solid electrolyte and at least one of the FBG sensors is located outside the solid electrolyte.
Preferably, a distance between adjacent two of the FBG sensors is not less than a length of the FBG sensors.
Preferably, the positive electrode and the negative electrode are both lithium sheets.
Preferably, the portion of the single mode optical fibre embedded in the solid state electrolyte is single strand embedded.
Preferably, the single-mode optical fiber is embedded in the solid electrolyte in a roll.
In a second aspect, the present invention provides a temperature monitoring method, applied to any one of the above solid-state batteries capable of monitoring the temperature of an electrolyte in real time;
the method comprises the following steps:
emitting light waves to a single-mode optical fiber embedded in a solid electrolyte of the solid-state battery through one port of an optical splitter;
at the other port of the optical splitter, detecting the wavelength and the wavelength drift amount of the light wave reflected by each FBG sensor connected in series on the single-mode fiber by using a fiber bragg grating demodulation module;
and calculating the temperature of the position of each FBG sensor based on the detected wavelength and the wavelength drift amount.
In the solid-state battery capable of monitoring the electrolyte temperature in real time, the single-mode optical fiber and the FBG sensor are embedded in the solid-state electrolyte; temperature and pressure changes at different positions inside the battery and temperature changes of the external environment of the battery can be obtained by monitoring Bragg wavelength drift of an FBG sensor inscribed in the single-mode fiber, detected data have high response speed, and detection precision is high. Based on the solid-state battery provided by the invention, high-precision measurement of parameters such as temperature, pressure and the like in the operation process of the battery can be realized, so that the thermal performance of the solid-state battery in electronic equipment is monitored in real time, disastrous accidents are prevented, and the rapid and in-situ measurement of multiple parameters such as the internal temperature, the pressure and the strain of the solid-state battery is realized.
Moreover, the solid-state battery provided by the invention can help to analyze the SEI (solid electrolyte interface) forming process and evaluate the service life of the battery, so that hidden faults can be found in advance in the battery design stage, and the effect of avoiding catastrophic accidents is also achieved.
The present invention will be described in further detail with reference to the accompanying drawings.
Drawings
Fig. 1 is a schematic structural diagram of a solid-state battery capable of monitoring electrolyte temperature in real time according to an embodiment of the present invention;
FIG. 2 is a schematic illustration of a single mode optical fiber embedded in a solid electrolyte;
FIG. 3 is a pictorial representation corresponding to FIG. 2;
FIG. 4 is another schematic illustration of a single mode optical fiber embedded in a solid electrolyte;
FIG. 5 is a pictorial representation corresponding to FIG. 4;
FIG. 6 is a flow chart of a pool monitoring method provided by an embodiment of the present invention;
fig. 7 is a diagram of device connection in the method shown in fig. 6.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
In order to enable fast, in-situ measurement of multiple parameters of temperature, pressure and strain within a solid-state battery, the inventors of the present invention have attempted to employ thermal resistance devices. The heat-resistant device includes a thermistor, a resistance temperature detector, and the like.
Wherein the thermistor may be placed on a surface, terminal, or near the battery. A Resistance Temperature Detector (RTD) is a device containing a metal conductor whose resistance increases with changes in temperature. Resistance temperature detectors RTD monitor temperature on a principle similar to thermistors, and after applying a small current, the voltage can then be converted to temperature by measuring the voltage drop. However, thermistors, resistance temperature detectors, are only available for local surface or local internal temperature measurement of the battery; for internal measurements, the preferred measurement scheme should not affect the service life and performance of the battery, should be resistant to the chemical environment of the battery material, and is compatible with the battery assembly process. Neither the thermistor nor the resistance temperature detector can detect temperature gradients and possible hot spots elsewhere on or within the battery, with the monitored temperature deviating from the maximum temperature.
In view of the above factors and the current state of the deposition and preparation technology, the inventor tries to perform in-situ real-time monitoring on the temperature and the pressure of the all-solid-state battery by using the FBG optical fiber sensor, and proposes a solid-state battery capable of monitoring the electrolyte temperature in real time so as to realize rapid and in-situ measurement on multiple parameters of the internal temperature, the pressure and the strain of the solid-state battery. Referring to fig. 1, the solid-state battery includes: a positive electrode, a negative electrode, a solid electrolyte, and a temperature monitoring device.
This temperature monitoring device includes: a single mode fiber and at least one FBG sensor; each FBG sensor is connected in series in a single mode fiber at intervals; the single-mode optical fiber part is embedded in the solid electrolyte between the positive electrode and the negative electrode, and at least one FBG sensor is connected in series with the embedded part.
Wherein, the distance between two adjacent FBG sensors is not less than the length of the FBG sensors.
It is understood that FBGs have gratings disposed along the length of the fiber for controlling the behavior of light. Bragg gratings are permanently changed by the application of ultraviolet light and then embedded into the core of an optical fiber. These bragg gratings act as wavelength selective mirrors, reflecting back specific wavelengths as the spectrum propagates through the core, while the rest of the spectrum is hardly affected.
In an embodiment of the invention, the sensor in the single mode fiber acts as a wavelength specific reflector, the wavelength of the light wave reflected by it being denoted λB＝2neffΛ; wherein λ isBIs the Bragg wavelength, neffIs the effective index of the grating and Λ is the bragg grating period.
In practical applications, the reflection peak Δ λ can be monitoredBIs shifted by neffAnd Λ, both of which depend on the environment around the local temperature, pressure and strain (epsilon) variations in the FBG sensor. The bragg reflection wavelength is shifted due to the influence of temperature. The measurement of this wavelength shift is the basis for fiber grating sensors; for temperature variations, changes in bragg wavelength can be observed, mainly due to temperature dependent changes in refractive index, while the effects of thermal expansion are very small and the grating spacing is negligible.
Another advantage of embodiments of the present invention is that FBG sensors can be multiplexed, which means that multiple fiber gratings can be inscribed into one fiber, making measurements possible at different locations along the length of the fiber. Furthermore, the bragg wavelength varies linearly with temperature.
By comparing the capacity retention rates of 100 cycles of the all-solid-state battery without the optical fiber sensor implantation, it can be determined that the responses under both conditions are almost the same, which indicates that the FBG sensor implantation of the solid-state battery does not affect the electrochemical performance of the battery.
In summary, in the embodiment of the present invention, the temperature and pressure changes at different positions inside the battery and the temperature change of the external environment of the battery can be obtained by monitoring the bragg wavelength drift of the FBG sensor inscribed in the single-mode fiber, and the data has a higher response speed and a higher detection accuracy. Based on the solid-state battery provided by the embodiment of the invention, high-precision measurement of parameters such as temperature, pressure and the like in the operation process of the battery can be realized, so that the thermal performance of the solid-state battery in electronic equipment is monitored in real time, catastrophic accidents are prevented, and the rapid and in-situ measurement of multiple parameters such as the internal temperature, the pressure and the strain of the solid-state battery is realized.
Moreover, the solid-state battery provided by the embodiment of the invention can help to analyze the SEI (solid electrolyte interface) forming process and evaluate the service life of the battery, so that hidden faults can be found in advance in the battery design stage, and the effect of avoiding catastrophic accidents is also achieved.
Preferably, in the embodiment of the present invention, both the positive electrode and the negative electrode are lithium sheets. The solid electrolyte can be common polymers, such as polyvinylidene fluoride (PVDF-HFP) and lithium salt lithium bistrifluoromethanesulfonylimide (C)2F6LiNO4S2). The lithium sheets are used as the positive electrode and the negative electrode, so that the function of collecting a large number of lithium positive ions can be realized; under the action of chemical potential, the positive ions lose electrons, and the electrons flow to the negative electrode from an external circuit; the lithium ions losing electrons are dissociated to the negative electrode through the solid electrolyte; the lithium sheet as a solid negative electrode functions to largely intercalate electron-lost lithium ions, and these electron-lost negative ions are dissociated toward the positive electrode from positive ions after the negative electrode is combined with electrons; the solid electrolyte functions to allow lithium ions to be smoothly conducted between the positive and negative electrodes. In short, the solid-state lithium battery also relies on the movement of lithium ions between the positive and negative electrodes to realize the charging and discharging process.
It can be understood that the all-solid-state battery has the following advantages compared to the liquid lithium ion battery: first, solid electrolytes are poor in flammability; secondly, no liquid electrolyte is provided, the voltage platform can be made high, and the specific energy of the battery can be further improved; thirdly, the solid electrolyte can adopt metal lithium as a negative electrode, and because the solid electrolyte has higher hardness and lithium dendrites are relatively more difficult to penetrate through the electrolyte, the growth of the dendrites can be inhibited to a certain degree; fourthly, the specific energy of the metal lithium battery is obviously higher than that of the lithium ion battery.
In one embodiment, the single mode fiber may have at least two FBG sensors connected in series, one inside the solid electrolyte and one outside the solid electrolyte. It can be understood that the FBG sensors inside the solid electrolyte are used to monitor the temperature and pressure inside the solid electrolyte, and the FBG sensors outside the solid electrolyte are mainly used to monitor the ambient temperature of the solid battery, so as to facilitate the comparison of the temperature inside and outside the solid battery.
In practical applications, the portion of the single mode optical fibre embedded in the solid state electrolyte may be single strand embedded, as shown in figure 2. Fig. 3 is a schematic diagram of the solid-state battery embedded in this manner.
It can be understood that the solid-state battery shown in fig. 2 and 3 is suitable for a small-sized solid-state battery that requires only a few FBG sensors to comprehensively detect the temperature inside the electrolyte.
In another implementation, referring to fig. 4, the single-mode optical fiber may be embedded in a roll of solid electrolyte. Fig. 5 is a schematic diagram of the solid-state battery embedded in this manner.
It is understood that the solid-state battery shown in fig. 4 and 5 is suitable for a large-volume solid-state battery; this is because a large number of FBG sensors can be connected in series to the coiled single-mode fiber embedded in the solid electrolyte, and when the coiled single-mode fiber and the FBG sensors connected in series therewith are coiled inside the solid electrolyte from top to bottom, thereby performing all-around monitoring inside the solid electrolyte.
Based on the solid-state battery capable of monitoring the temperature of the electrolyte in real time provided in the above embodiment of the present invention, the embodiment of the present invention further provides a monitoring method for the battery, as shown in fig. 6 and 7, the method includes the following steps:
s10: the light waves are launched through one port of the optical splitter into a single mode fiber in the solid state battery.
Here, a broadband light wave can be emitted into a single-mode optical fiber.
S20: and at the other port of the optical splitter, a fiber bragg grating demodulation module is used for detecting the wavelength and the wavelength drift amount of the light wave reflected by each FBG sensor connected in series on the single-mode fiber.
It can be understood that for a precise device which needs to monitor the temperature of the electrolyte inside the solid-state battery, a fiber grating demodulation module can be integrated inside the device, and the working principle of the fiber grating demodulation module can be referred to the existing fiber grating demodulator.
For common equipment, a temperature monitoring device is only required to be additionally arranged in the solid-state battery in the research and development stage, and the existing fiber bragg grating demodulator is used for monitoring the electrolyte temperature in real time, so that the design of the solid-state battery is assisted; after the solid-state battery is designed and shaped, the solid-state battery in the common equipment does not need to be provided with the temperature monitoring device, and further does not need to be integrated with the fiber bragg grating demodulation module.
In practical application, a solid-state battery needs to be prepared in advance to realize temperature monitoring; illustratively, acetone and DMF (N, N-dimethylformamide) may be used as a solvent, dissolved with PVDF-HFP under stirring; then, adding lithium salt and stirring to fully dissolve the lithium salt to obtain an electrolyte solution; then, organic glass or silicone grease is used for encapsulating the electrolyte solution, and an electrode is placed; then, a single-mode optical fiber connected with the FBG sensor in series is placed between the electrolyte solution between the positive electrode and the negative electrode, and solid electrolyte is formed after the electrolyte solution is solidified, so that the solid-state battery capable of monitoring the electrolyte temperature in real time is obtained.
S30: based on the detected wavelength and the amount of wavelength drift, the temperature at the location of each FBG sensor is calculated.
It is understood that since the light waves with different wavelengths can be regarded as independent from each other, the multiplexing transmission of multiple optical signals can be realized in one optical fiber. Signals in two directions are respectively arranged at different wavelengths for transmission, so that bidirectional transmission can be realized. The number of wavelengths that can be multiplexed varies from 2 to several tens of wavelengths depending on the wavelength division multiplexer, and 8-wavelength and 16-wavelength systems are generally commercialized depending on the size of the interval of the allowed optical carrier wavelengths.
Specifically, in the embodiment of the present invention, a plurality of FBG sensors are connected in series to one optical fiber, a broadband light wave emitted from a broadband light source passes through all gratings via a splitter, each grating reflects light with different central wavelengths, and the reflected light wave is coupled into a fiber grating demodulation module via another port of the splitter; the fiber bragg grating demodulation module is utilized to detect the wavelength of the light wave reflected by the FBG sensors arranged at various positions and the wavelength drift amount of the light wave relative to the initial state center wavelength, so that data are demodulated; and calculating to obtain the actual temperature of the environment where each grating is located through corresponding data processing.
It should be noted that the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more features. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description of the specification, reference to the description of the term "one embodiment", "some embodiments", "an example", "a specific example", or "some examples", etc., means that a particular feature or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples described in this specification can be combined and combined by those skilled in the art.
While the present application has been described in connection with various embodiments, other variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed application, from a review of the drawings, the disclosure, and the appended claims.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (7)

1. A solid-state battery that can monitor electrolyte temperature in real time, comprising: a positive electrode, a negative electrode, and a solid electrolyte, further comprising: a temperature monitoring device; wherein,
the temperature monitoring device includes: a single mode fiber and at least one FBG sensor; each FBG sensor is connected in the single-mode optical fiber at intervals in series;
the single-mode optical fiber is partially embedded in the solid electrolyte between the positive electrode and the negative electrode, and at least one FBG sensor is connected in series with the embedded part.
2. The solid-state battery according to claim 1, wherein the FBG sensors include at least 2;
wherein at least one of the FBG sensors is located in the solid electrolyte and at least one of the FBG sensors is located outside the solid electrolyte.
3. The solid-state battery according to claim 1, wherein a distance between adjacent two of the FBG sensors is not less than a length of the FBG sensors.
4. The solid-state battery according to claim 1, wherein the positive electrode and the negative electrode are both lithium sheets.
5. The solid-state battery according to claim 1, wherein the portion of the single-mode optical fiber embedded in the solid-state electrolyte is single-strand embedded.
6. The solid-state battery according to claim 1, wherein the portion of the single-mode optical fiber embedded in the solid-state electrolyte is embedded in a roll.
7. A temperature monitoring method applied to the solid-state battery according to any one of claims 1 to 6;
the method comprises the following steps:
emitting light waves to a single-mode optical fiber embedded in a solid electrolyte of the solid-state battery through one port of an optical splitter;
at the other port of the optical splitter, detecting the wavelength and the wavelength drift amount of the light wave reflected by each FBG sensor connected in series on the single-mode fiber by using a fiber bragg grating demodulation module;
and calculating the temperature of the position of each FBG sensor based on the detected wavelength and the wavelength drift amount.
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Application publication date: 20220125

Assignee: Xi'an xilinzi Energy Technology Co.,Ltd.

Assignor: XIDIAN University

Contract record no.: X2022610000004

Denomination of invention: Solid state battery capable of real-time monitoring electrolyte temperature and its temperature monitoring method

License type: Common License

Record date: 20220531

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