Solid-state battery detection device and system for light in-situ characterization of micro-area heat-force-magnetism

Abstract

The embodiment of the utility model relates to a solid-state battery detection device and a solid-state battery detection system for representing micro-area heat-force-magnetism in situ by using light, and a cover body comprises a working electrode cover body and a test window arranged in the middle of the working electrode cover body; the tested electrode accommodating part comprises a through hole insulating sleeve and a lower die with a cylinder; the lower die with the cylinder comprises a central cylinder and a base; the through hole insulation sleeve is of a hollow cylindrical structure, the top end of the through hole insulation sleeve is connected with the lower surface of the working electrode cover body, and the test window corresponds to the hollow part of the through hole insulation sleeve; the bottom end is in clearance fit with the central cylinder of the lower die with the cylinder; a cavity is formed in the through hole insulating sleeve between the working electrode cover body and the lower die with the cylinder; the tested solid-state battery is arranged in the cavity and comprises a to-be-tested working electrode, a solid-state electrolyte and a counter electrode; the heating sheet is arranged in the base of the lower die with the cylinder; the pressure sensing and adjusting device comprises a stress sensor, and the stress sensor is arranged below the lower die with the cylinder.

Description

Technical Field

[0001] The utility model relates to the field of battery in-situ characterization, in particular to a solid-state battery detection device and system for in-situ characterization of micro-area heat, force and magnetism by light. Background Art

[0002] Lithium-ion batteries are becoming the main energy storage technology in the transportation, grid storage, and residential demand markets due to their high energy density, high energy efficiency, long cycle life, and transportation convenience. However, the rapid expansion of market demand places increasingly higher demands on the energy density and safety factor of lithium-ion batteries. Currently, the electrolytes of commercially used lithium-ion batteries are mostly composed of flammable organic solvents with low melting points, such as lithium salts and carbonates. When the battery is subjected to mechanical shock or excessive charge and discharge, it is easy to generate heat rapidly due to internal short circuits or lithium precipitation, causing thermal runaway, resulting in cascade reaction-like spontaneous combustion or explosion of the battery from the monomer to the module. Solid-state batteries that replace flammable organic electrolytes with non-flammable solid electrolytes have attracted widespread attention because they are expected to achieve high safety, high energy density, and long cycle stability at the same time.

[0003] However, the actual electrochemical performance of solid-state batteries is still far from the ideal target, mainly because the side reactions at the interfaces of solid electrolyte and positive electrode active particles, solid electrolyte and negative electrode active particles during the charge and discharge process will affect the stability of the interface, causing changes in temperature and stress in the local area of ​​the interface. Unlike the temperature difference and stress on the solid-liquid conformal interface in liquid batteries, which can be quickly dissipated with the infiltration flow of the liquid, the interface in solid-state batteries is mostly solid-solid rigid contact, and the particles squeeze each other. The stress generated by the volume strain of the active material due to lithiation / delithiation and the stress generated by the interface side reactions will accumulate at the interface because they cannot be dissipated, resulting in particle breakage and contact failure over a long period of time.

[0004] Therefore, the development of high-performance solid-state batteries requires an in-depth understanding of the evolution and attenuation mechanism of the microscopic morphology, structure, temperature, stress and other parameters of the internal interface of the battery during the charging and discharging process. However, most traditional characterization techniques usually disassemble the battery after charging and discharging to a specified state, and then extract some samples for analysis and characterization. The experimental data obtained have certain uncertainties and lags; on the other hand, the current in-situ scanning electron microscope, in-situ nuclear magnetic resonance imaging, atomic force microscope and other in-situ characterization methods for solid-state batteries are limited by instrument space and characterization accuracy, and the battery devices used are quite different from the real battery environment. Therefore, at this stage, there is still a lack of efficient and reliable characterization devices and test methods that can non-destructively monitor the evolution of internal microscopic interfaces in real solid-state batteries in situ. Utility Model Content

[0005] The purpose of the utility model is to provide a solid-state battery detection device and system for in-situ characterization of micro-area thermal-mechanical-magnetic properties using light. The detection device is used to test microscopic temperature, mechanics, magnetism and other parameters. Through the overall design of the device, it is possible to achieve in-situ non-destructive characterization of the interior of the solid-state battery through monitoring and analysis of optical signals under the working conditions of a real solid-state battery. At the same time, the device temperature and external stacking pressure can be adjusted to test changes in microscopic parameters inside the solid-state battery at different operating temperatures and pressures.

[0006] To achieve the above-mentioned purpose, in a first aspect, the utility model provides a solid-state battery detection device for in-situ characterization of micro-area thermal-mechanical-magnetic properties by light, the solid-state battery detection device comprising: a cover, a receiving portion for the electrode to be tested, a heating plate, a pressure sensing and regulating device;

[0007] The cover body comprises: a working electrode cover body and a test window opened in the middle of the working electrode cover body;

[0008] The tested electrode accommodating portion comprises: a through-hole insulating sleeve and a lower mold with a cylinder; the lower mold with a cylinder comprises a central cylinder and a base; the through-hole insulating sleeve is a hollow cylindrical structure, the top end of which is connected to the lower surface of the working electrode cover, and the test window corresponds to the hollow part of the through-hole insulating sleeve; the bottom end is gap-matched with the central cylinder of the lower mold with a cylinder; a cavity is formed inside the through-hole insulating sleeve between the working electrode cover and the central cylinder of the lower mold with a cylinder; the solid-state battery to be tested is placed in the cavity, and the solid-state battery to be tested comprises: a working electrode to be tested, a solid electrolyte and a counter electrode; wherein the working electrode to be tested is exposed below the test window;

[0009] The heating plate is arranged in the base with the cylindrical lower mold;

[0010] The pressure sensing and regulating device is arranged below the lower mold with a cylinder; the pressure sensing and regulating device includes a stress sensor.

[0011] Preferably, the pressure sensing and regulating device comprises: a stress sensor fixing assembly;

[0012] The stress sensor fixing assembly also includes: an upper clamping plate and a lower clamping plate;

[0013] The stress sensor is arranged between the upper clamping plate and the lower clamping plate.

[0014] Further preferably, the pressure sensing and regulating device comprises: a pressure regulating component;

[0015] The pressure adjustment component includes an adjustable bolt set symmetrically arranged on four sides of the solid-state battery detection device and passing through the working electrode cover, the base, the upper clamping plate and the lower clamping plate;

[0016] The adjustable bolt set and the working electrode cover are isolated by an insulating sleeve.

[0017] Preferably, the working electrode cover and the cylindrical lower mold are respectively connected with conductive leads;

[0018] A microwave antenna penetrating the solid-state battery detection device is provided on the working electrode below the test window, and the microwave antenna is externally connected to a microwave source.

[0019] The heating plate is connected to a temperature control processor arranged outside the solid-state battery detection device.

[0020] Preferably, the stress sensor is connected to a stacking stress signal receiving and processing device disposed outside the solid-state battery detection device.

[0021] Preferably, both side ends of the through hole insulating sleeve are provided with grooves, and sealing rings are arranged in the grooves;

[0022] The working electrode cover and the through-hole insulating sleeve, as well as the through-hole insulating sleeve and the cylindrical lower mold are sealed by the sealing ring.

[0023] Preferably, the working electrode cover and the cylindrical lower mold are made of pressure-resistant conductive metal materials, including one or more of stainless steel, zinc, titanium, aluminum, copper and alloys thereof;

[0024] The material of the test window is transparent acrylic plastic or optical quartz glass used for diamond nitrogen-vacancy (NV) color center quantum detection, or optical quartz glass used for Raman testing or optical microscope testing, wherein the diameter of the optical quartz glass is larger than the diameter of the light spot emitted by the test instrument;

[0025] The through-hole insulating sleeve is made of a hard heat-resistant insulating material, including one or more of insulating ceramics, polyvinyl chloride, polyethylene, polypropylene, polycarbonate fiber, polyoxymethylene, polyphenylene sulfide, polyetheretherketone, polyimide, and polysulfone;

[0026] The heating plate is made of a high temperature and high pressure resistant material, including: a polyimide heating plate, a mica heating plate, a high temperature ceramic heating plate or a silicone rubber heating plate.

[0027] Preferably, the working electrode is a working electrode containing diamond NV color centers;

[0028] The light emitted by the excitation light source for exciting the diamond NV color center is incident on the working electrode to be tested near the microwave antenna from the outside of the test window;

[0029] The fluorescence signal receiver receives the fluorescence emitted by the diamond NV color center and passing through the test window.

[0030] In a second aspect, an embodiment of the utility model provides a solid-state battery detection system for in-situ characterization of micro-area thermal-mechanical-magnetic properties using light, the system comprising: the solid-state battery detection device described in the first aspect, an excitation light source, a microwave source, a fluorescence signal receiver, a stack stress signal receiving and processing device, and a temperature control processor;

[0031] The solid-state battery detection device is used for quantum detection of diamond NV color centers, Raman testing or optical microscope testing.

[0032] The solid-state battery detection device provided by the utility model can realize in-situ non-destructive characterization of micro-area thermal-mechanical-magnetic parameters such as micro-morphology, temperature, stress, and magnetic signals inside the solid-state battery under real solid-state battery test conditions. The device can adjust the external stacking pressure and operating temperature according to the test needs, and monitor the changes of signals such as micro-area temperature and stress distribution inside the solid-state battery in situ. The device has a simple and compact structure, a small volume, and a small test accuracy error.

[0033] The solid-state battery detection device for in-situ characterization of micro-area thermal, mechanical and magnetic properties using light provided by the utility model can replace the test window according to the test needs to adapt to a variety of solid-state battery in-situ characterization methods involving optical signals, and is particularly suitable for quantum detection of diamond NV color centers, Raman testing, optical microscopy and other technologies. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 An exploded diagram of a solid-state battery device that uses light to characterize micro-area thermal-mechanical-magnetic in situ provided by the utility model;

[0035] Figure 2 A cross-sectional schematic diagram of a solid-state battery device for in-situ characterization of micro-region thermal-mechanical-magnetic properties using light provided by the utility model;

[0036] Figure 3 A schematic diagram of a cover of a solid-state battery detection device for in-situ characterization of micro-area thermal-mechanical-magnetic properties using light provided by the utility model;

[0037] Figure 4 An exploded diagram of a solid-state battery device with a microwave antenna for in-situ characterization of micro-region temperature and stress signals using diamond NV color center quantum detection provided by an embodiment of the utility model;

[0038] Figure 5 A cross-sectional schematic diagram of a solid-state battery device provided by an embodiment of the utility model that uses diamond NV color center quantum detection to in-situ characterize micro-area temperature and stress signals after being installed in a solid-state battery to be tested and in a test state;

[0039] Figure 6 This is an optically detected magnetic resonance (ODMR) spectrum obtained when the temperature of the micro-region inside the working electrode of the solid-state battery is tested by using diamond NV color center quantum detection in the embodiment of the utility model;

[0040] Figure 7 This is a curve showing the change of the temperature of the micro-region inside the working electrode of the solid-state battery with the heating time obtained by using the diamond NV color center quantum detection test in the embodiment of the present utility model;

[0041] Figure 8 This is the ODMR spectrum obtained when the diamond NV color center quantum detection is used to test the internal micro-area stress of the working electrode of the solid-state battery in the embodiment of the utility model;

[0042] Fig. 9 Li is obtained by testing the device in the embodiment of the utility model x S iL i6PS5C lL i4Ti5O 12 (0≤x≤4.4) All-solid-state battery capacity-voltage curve;

[0043] Fig.10 This is the evolution curve of the internal micro-area stress of the solid-state battery working electrode as a function of the charge and discharge time obtained by using the diamond NV color center quantum detection test in the embodiment of the utility model. DETAILED DESCRIPTION

[0044] The technical solution of the utility model is further described in detail below through the accompanying drawings and embodiments.

[0045] The solid-state battery detection device provided by the embodiment of the utility model uses light to characterize micro-area thermal-mechanical-magnetic in situ, Figure 1 An exploded diagram of a solid-state battery device for in-situ characterization of micro-area thermal-mechanical-magnetic properties using light provided by the utility model. Figure 2 This is a cross-sectional schematic diagram of a solid-state battery device for in-situ characterization of micro-area heat, force and magnetism using light provided by the utility model. The structure of the device is as follows Figure 1 , Figure 2 As shown, it includes: a cover body 1, a measured electrode accommodating portion 2, a heating plate 3, and a pressure sensing and regulating device 4.

[0046] The cover 1 is as follows Figure 3 As shown, Figure 3 For a stereogram, Figure 3 b is a top view, the cover body includes: a working electrode cover body 1-1 and a test window 1-2 opened in the middle of the working electrode cover body 1-1.

[0047] The electrode receiving portion 2 includes: a through-hole insulating sleeve 2-1 and a cylindrical lower mold 2-3; the cylindrical lower mold 2-3 includes a central cylinder and a base; the through-hole insulating sleeve 2-1 is a hollow cylindrical structure, the top of the through-hole insulating sleeve 2-1 is connected to the lower surface of the working electrode cover 1-1, and the test window 1-2 corresponds to the hollow part of the through-hole insulating sleeve 2-1; the bottom end of the through-hole insulating sleeve 2-1 is gap-matched with the central cylinder of the cylindrical lower mold 2-3;

[0048] Grooves are provided at both ends of the through-hole insulating sleeve 2-1, and sealing rings 2-2 are provided in the grooves. The working electrode cover 1-1 and the through-hole insulating sleeve 2-1, as well as the through-hole insulating sleeve 2-1 and the cylindrical lower mold 2-3 are sealed by the sealing rings 2-2 to ensure close contact between the through-hole insulating sleeve 2-1, the working electrode cover 1-1 and the cylindrical lower mold 2-3.

[0049] A cavity is formed inside the through-hole insulating sleeve 2-1 between the working electrode cover 1-1 and the central cylinder with the cylindrical lower mold 2-3, and the solid-state battery to be tested is placed inside. The height of the cavity is consistent with the height of the solid-state battery. Preferably, the working electrode cover 1-1 has a groove, and the through-hole insulating sleeve 2-1 is assembled corresponding to the groove on the working electrode cover 1-1.

[0050] When the solid-state battery to be tested is placed in the cavity, the working electrode to be tested is exposed below the test window 1-2. The working electrode cover 1-1, the sealing ring 2-2, the through-hole insulating sleeve 2-1 and the cylindrical lower mold 2-3 can seal, protect, constrain and pressurize the solid-state battery after being fixed together.

[0051] The heating plate 3 is arranged in the base of the cylindrical lower mold 2-3; preferably, there are grooves and grooves on the lower side of the cylindrical lower mold 2-3 for placing the heating plate 3, so that the heating plate 3 is not subjected to force inside the cylindrical lower mold 2-3.

[0052] The pressure sensing and regulating device 4 is arranged below the cylindrical lower mold 2-3; the pressure sensing and regulating device 4 comprises: a stress sensor 4-1, a stress sensor fixing assembly and a pressure regulating component.

[0053] The stress sensor fixing assembly in this example may specifically include: an upper clamping plate 4-2 and a lower clamping plate 4-3; the stress sensor 4-1 is arranged between the upper clamping plate 4-2 and the lower clamping plate 4-3, and further, a shallow groove is provided on the upper clamping plate 4-2 and the lower clamping plate 4-3 for fixing the position of the stress sensor 4-1.

[0054] In this example, the pressure adjustment component includes an adjustable bolt set 4-4 symmetrically arranged on the four sides or four corners of the solid-state battery detection device and passing through the working electrode cover 1-1, the base, the upper clamping plate 4-2 and the lower clamping plate 4-3. In this example, the four groups of adjustable bolt sets 4-4 are distributed axially symmetrically, and they apply pressure to the entire device. The external stacking pressure of the device is the torque force applied to the solid-state battery detection device by the adjustable bolt set 4-4, ranging from 0-500MPa, which can be adjusted according to test needs. In order to ensure the isolation of the adjustable bolt set 4-4, an insulating sleeve is set between the adjustable bolt set 4-4 and the working electrode cover 1-1 for isolation.

[0055] In solid-state batteries, electrode stress is generated by the battery's own charge and discharge process and external pressure. This embodiment simulates the external stress environment of the battery through the adjustable bolt set 4-4, so that the changes in internal microscopic stress under different external stress conditions can be observed.

[0056] The working electrode cover 1-1 and the cylindrical lower mold 2-3 are respectively connected with conductive leads.

[0057] The heating plate 3 is connected to a temperature control processor disposed outside the solid-state battery detection device. The setting of the heating plate 3 can change the operating temperature of the solid-state battery and isolate the influence of the external ambient temperature on the one hand, and can reduce or eliminate the local temperature influence caused by the laser source irradiation during the test on the other hand.

[0058] The stress sensor 4 - 1 is connected to a stack stress signal receiving and processing device disposed outside the solid-state battery detection device.

[0059] The light emitted by the excitation light source for exciting the diamond NV color center is incident from the outside of the test window 1-2 onto the working electrode to be tested near the microwave antenna.

[0060] The fluorescence signal receiver receives the fluorescence emitted by the diamond NV color center that passes through the test window 1-2.

[0061] When the device is used for different tests, the conductive leads can be connected or the microwave source and / or light source and different external devices can be connected or used in different ways. At the same time, the electrodes of the battery to be tested can be selected accordingly for different tests. For example, when the diamond NV color center quantum detection is used to test the stress change of the solid-state battery micro-area, the working electrode used is a working electrode containing a diamond NV color center. The device is provided with a microwave antenna 6 that penetrates the solid-state battery detection device below the test window 1-2 on the working electrode. Figure 4 , Figure 5 As shown in . The microwave antenna 6 is externally connected to a microwave source. The microwave antenna is preferably an enameled wire, more preferably an enameled copper wire, and the diameter is preferably 20 microns to 200 microns.

[0062] The specific usage of this device will be described in the subsequent embodiments.

[0063] In the embodiment of the utility model, the working electrode cover 1-1 and the cylindrical lower mold 2-3 are made of pressure-resistant conductive materials, such as stainless steel, zinc, titanium alloy, brass, aluminum alloy and other alloy materials, preferably lightweight and non-deformable titanium alloy.

[0064] The through-hole insulating sleeve 2-1 is made of pressure-resistant and high-temperature resistant material, preferably insulating ceramics or insulating rubber that are resistant to high temperatures and not easily deformed, including one or more of polyvinyl chloride, polyethylene, polypropylene, polycarbonate fiber, polyformaldehyde, polyphenylene sulfide, polyetheretherketone, polyimide, and polysulfone, and more preferably insulating ceramics and polyetheretherketone (PEEK) rubber.

[0065] The sealing ring 2-2 is made of an O-ring material that is resistant to pressure and high temperature, preferably one or more of a SIL silicone rubber sealing ring, a VI TON fluororubber sealing ring, a FLS fluorosilicone rubber sealing ring, and a metal rubber sealing ring, and more preferably a metal rubber sealing ring.

[0066] The heating plate 3 is made of a pressure-resistant and high-temperature-resistant heating plate material, preferably one or more of a polyimide (PI) heating plate, a mica heating plate, a high-temperature ceramic heating plate, and a silicone rubber heating plate, and more preferably a high-temperature ceramic heating plate.

[0067] The material used for the test window on the working electrode cover 1-1 can be adjusted according to the test requirements. In this embodiment, the test window material used for diamond NV quantum detection is highly transparent acrylic plastic or quartz glass, and the test window material used for Raman testing and optical microscope testing is quartz glass.

[0068] The structure of the solid-state battery to be tested installed in the solid-state battery detection device provided in this embodiment is shown as follows: Figure 4 , Figure 5 shown. Figure 4 An exploded diagram of a solid-state battery device with a microwave antenna for in-situ characterization of micro-region temperature and stress signals using diamond NV color center quantum detection provided by an embodiment of the utility model; Figure 5 A cross-sectional schematic diagram of a solid-state battery device provided in the embodiment of the utility model that uses diamond NV color center quantum detection to in-situ characterize micro-area temperature and stress signals after being loaded into a solid-state battery to be tested in a test state. It can be seen that the solid-state battery 5 includes: a working electrode 5-1 containing a diamond NV color center to be tested, a solid electrolyte 5-2, and a counter electrode 5-3. The solid-state battery working electrode 5-1 near the test window 1-2 contains a diamond NV color center.

[0069] The light used to excite the diamond NV color center is incident from the outside of the test window and irradiates the working electrode near the microwave antenna. The fluorescence emitted by the diamond NV color center passes through the test window, is collected outside the battery to obtain the ODMR spectrum and analyzed to obtain the micro-area temperature, stress or magnetic signal. The diamond NV color center can be selected with different particle sizes according to the test needs, preferably with a particle size similar to that of the active material particles in the working electrode.

[0070] The solid-state battery detection device provided in this embodiment, the excitation light source, the microwave source, the fluorescence signal receiver, the stack stress signal receiving and processing device, and the temperature control processor together constitute a solid-state battery detection system. In this system, the solid-state battery detection device can be used to perform quantum detection of diamond NV color centers, Raman testing or optical microscope testing.

[0071] The test method for in-situ characterization of temperature and stress changes in micro-regions inside a solid-state battery working electrode by using the solid-state battery device of this embodiment to perform diamond NV color center quantum detection includes the following steps:

[0072] 1) Assemble the through-hole insulating sleeve 2-1 with the upper and lower sealing rings 2-2, and then assemble them with the cylindrical lower mold 2-3;

[0073] 2) placing the solid-state battery 5 to be tested in the cavity formed by assembling the through-hole insulating sleeve 2-1 and the cylindrical lower mold 2-3, with the working electrode 5-1 of the solid-state battery to be tested facing upward and the counter electrode 5-3 facing downward and contacting the cylindrical lower mold 2-3;

[0074] 3) Cover the working electrode cover 1-1 with the test window 1-2 installed on the through-hole insulating sleeve 2-1, and assemble the through-hole insulating sleeve 2-1 correspondingly with the groove on the working electrode cover 1-1;

[0075] 4) Place the heating plate 3 in the groove on the lower side of the cylindrical lower mold 2-3, and place the lead wire of the heating plate 3 for connecting the external temperature control processor in the groove; assemble the stress sensor 4-1 and the upper clamping plate 4-2 and the lower clamping plate 4-3 together under the heating plate 3 and fix them;

[0076] 5) Insert four sets of bolts 4-4 with insulating sleeves through the reserved holes at the four axially symmetrical corners through the entire detection device, and adjust the four bolts to the required external stacking pressure using a torque wrench according to the test requirements;

[0077] 6) Connect the conductive lead on the working electrode cover 1-1 and the conductive lead on the cylindrical lower mold 2-3 to the positive electrode / negative electrode of the electrochemical testing workstation respectively for charging and discharging of the solid-state battery;

[0078] 7) Perform in-situ optical monitoring of the solid-state battery working electrode, receive the electromagnetic waves emitted by the microwave source to the diamond NV color center through the microwave antenna to modulate the electronic spin state of the diamond NV color center, and emit light for exciting the diamond NV color center through the excitation light source, which is incident from the outside of the test window 1-2 on the working electrode to be tested near the microwave antenna, and the fluorescence signal receiver receives the fluorescence emitted by the diamond NV color center that passes through the test window 1-2. Collect the ODMR spectrum corresponding to the fluorescence signal emitted by the diamond NV color center, analyze and process the ODMR spectrum to further obtain the temperature, stress, magnetic signal and other data of the micro-area of ​​the solid-state battery working electrode.

[0079] The detection device of the utility model can control the temperature of the solid-state battery detection device and record it in real time through the heating plate 3 and its external temperature control processor, or can maintain the temperature of the device during the solid-state battery test according to the test needs to avoid the influence of the ambient temperature on the stress test; according to the test needs, the torque force of the bolt 4-4 can be changed to adjust the external stacking pressure of the solid-state battery, and the adjustment range is 0-500MPa; the external stacking pressure changes of the solid-state battery detection device can be recorded in real time through the stress sensor and its external stacking stress signal receiving and processing device.

[0080] Example 1

[0081] This embodiment provides a testing method based on a solid-state battery detection device to in-situ characterize the temperature changes of micro-regions inside the working electrode of a solid-state battery using diamond NV color center quantum detection.

[0082] This example uses Figure 5 Solid-state battery device with the structure shown, monitoring Li x S iL i6PS5C iL i4T i5O 12 (0≤x≤4.4) Li in all-solid-state batteries x Changes of the temperature of the micro-area inside the Si working electrode with heating time. x The Si negative electrode is the working electrode for observation. The following is the specific preparation method of the solid-state battery used in this test:

[0083] Negative electrode (working electrode) preparation: The negative electrode active material uses pre-lithiated micron silicon negative electrode Li x The Si powder material was mixed with 4 wt.‰ of diamond NV color center powder, and then manually ground and mixed in a mortar for 20 minutes to uniformly disperse the diamond NV color center in the electrode.

[0084] Positive electrode (counter electrode) preparation: The positive electrode active material uses commercial lithium titanate Li4Ti5O 12 Materials: weigh the positive electrode active material Li4Ti5O according to the mass ratio of 50:40:10 12, solid electrolyte Li6PS5C l, and conductive additive acetylene black were manually ground in a mortar for 30 minutes to fully mix the three materials.

[0085] Battery preparation: The same as the conventional solid-state battery preparation method. Take 80mg of solid electrolyte Li6PS5C l powder and place it in a metallographic cold pressing mold, then place it under a cold press, and cold press it for 3 minutes at a uniaxial pressure of 360MPa to form a solid electrolyte sheet; then place the negative electrode powder and the positive electrode powder on both sides of the solid electrolyte sheet, respectively, place it under a cold press, and cold press it for 3 minutes at a pressure of 200MPa; carefully remove the mold and eject the complete solid-state battery.

[0086] Solid-state battery device assembly: assemble the through-hole insulating sleeve 2-1 and the upper and lower sealing rings 2-2 and then assemble them with the cylindrical lower mold 2-3; place the solid-state battery obtained by ejecting the mold into the cavity formed by the through-hole insulating sleeve 2-1 and the cylindrical lower mold 2-3, and the working electrode Li containing the diamond NV color center x Si faces upward, the counter electrode faces downward and contacts the cylindrical lower mold 2-3; x A microwave antenna penetrating the device is fixed on the Si surface and an external microwave source is connected; the working electrode cover 1-1 with an optical quartz glass test window 1-2 is covered on the through-hole insulating sleeve 2-1, and the through-hole insulating sleeve 2-1 is assembled corresponding to the grooves on the working electrode cover 1-1; the heating plate 3 is placed in the groove on the lower side of the cylindrical lower mold 2-3, and the lead wire of the external temperature control processor of the heating plate is placed in the groove; the stress sensor 4-1 and the upper clamping plate 4-2 and the lower clamping plate 4-3 are assembled together under the heating plate 3 and fixed; four sets of bolts 4-4 with insulating sleeves are passed through the entire device at the four axially symmetrical corners through the reserved holes, and the four bolts are tightened to the required external stacking stress with a torque wrench according to the test requirements.

[0087] The temperature of the heating plate is set to 100°C by the temperature control processor, and the electromagnetic wave emitted by the microwave source to the diamond NV color center is received by the microwave antenna to modulate the electron spin state of the diamond NV color center, and the light used to excite the diamond NV color center is emitted by the excitation light source and incident on the working electrode to be tested near the microwave antenna from the outside of the test window 1-2, and then the fluorescence signal receiver is used to collect the fluorescence information of the diamond NV color center on the working electrode that changes with time, and the following is obtained: Figure 6 The ODMR spectrum shown in Figure 2 can be analyzed by analyzing the changes of the ODMR spectrum over time to obtain the following Figure 7 The temperature variation curve with time is shown, which shows the Li x The temperature of the micro-area inside the Si electrode changes with the heating time, and the test error is small. It can reflect the change of the micro-area environmental temperature with high accuracy and meet the in-situ test requirements.

[0088] Example 2

[0089] This embodiment provides a test method for in-situ non-destructive characterization of micro-area stress changes inside a solid-state battery working electrode using diamond NV color center detection based on a solid-state battery detection device.

[0090] This example uses Figure 5 Solid-state battery device with the structure shown, in situ monitoring of Li x Si-Li6PS5C l-Li4T i5O 12 (0≤x≤4.4) Li in all-solid-state batteries x The evolution of the internal micro-area stress of the Si working electrode during the charge and discharge process. The following is the specific preparation method, Li x The Si negative electrode is the working electrode for observation. The following is the specific preparation method of the solid-state battery used in this test:

[0091] Negative electrode (working electrode) preparation: The negative electrode active material uses pre-lithiated micron silicon negative electrode Li x The Si powder material was mixed with 4 wt.‰ of diamond NV color center powder, and then manually ground and mixed in a mortar for 20 minutes to uniformly disperse the diamond NV color center in the electrode.

[0092] Positive electrode (counter electrode) preparation: The positive electrode active material uses commercial lithium titanate Li4Ti5O 12 Materials: weigh the positive electrode active material Li4Ti5O according to the mass ratio of 50:40:10 12 , solid electrolyte Li6PS5C l, and conductive additive acetylene black were manually ground in a mortar for 30 minutes to fully mix the three materials.

[0093] Battery preparation: The same as the conventional solid-state battery preparation method. Take 80mg of solid electrolyte Li6PS5C l powder and place it in a metallographic cold pressing mold, then place it under a cold press, and cold press it for 3 minutes at a uniaxial pressure of 360MPa to form a solid electrolyte sheet; then place the negative electrode powder and the positive electrode powder on both sides of the solid electrolyte sheet, respectively, place it under a cold press, and cold press it for 3 minutes at a pressure of 200MPa; carefully remove the mold and eject the complete solid-state battery.

[0094] Solid-state battery device assembly: assemble the through-hole insulating sleeve 2-1 and the upper and lower sealing rings 2-2 and then assemble them with the cylindrical lower mold 2-3; place the solid-state battery obtained by ejecting the mold into the cavity formed by the through-hole insulating sleeve 2-1 and the cylindrical lower mold 2-3, and the working electrode Li containing the diamond NV color center x Si faces upward, the counter electrode faces downward and contacts the cylindrical lower mold 2-3; xA microwave antenna penetrating the device is fixed on the Si surface and an external microwave source is connected; the working electrode cover 1-1 with an optical quartz glass test window 1-2 is covered on the through-hole insulating sleeve 2-1, and the through-hole insulating sleeve 2-1 is assembled corresponding to the grooves on the working electrode cover 1-1; the heating plate 3 is placed in the groove on the lower side of the cylindrical lower mold 2-3, and the lead wire of the external temperature control processor of the heating plate is placed in the groove; the stress sensor 4-1 and the upper clamping plate 4-2 and the lower clamping plate 4-3 are assembled together under the heating plate 3 and fixed; four sets of bolts 4-4 with insulating sleeves are passed through the entire device at the four axially symmetrical corners through the reserved holes, and the four bolts are tightened to the required external stacking stress with a torque wrench according to the test requirements.

[0095] The working electrode lead on the working electrode cover 1-1 and the working electrode lead on the cylindrical lower mold 2-3 are connected to the positive electrode / negative electrode of the charging and discharging equipment respectively, and the charging and discharging are performed. The capacity-voltage curve of the solid-state battery is as follows: Figure 8 As shown. It can be seen that the battery charge and discharge cycle of this embodiment is normal. Figure 8 Solid-state battery device test Li x Si-L i6PS5Cl-Li4T i5O 12 The first week charge and discharge curve of the all-solid-state battery shows a battery capacity of up to 4.7mAh, which meets normal charge and discharge requirements.

[0096] Then, the microwave antenna receives the reference electromagnetic wave emitted by the microwave source to the diamond NV color center to modulate the electron spin state of the diamond NV color center, and the light emitted by the excitation light source to excite the diamond NV color center is incident on the working electrode to be tested near the microwave antenna from the outside of the test window 1-2, and the fluorescence signal receiver is used to collect the fluorescence information of the diamond NV color center on the working electrode that changes with time, and the following is obtained: Fig. 9 The ODMR spectrum shown in Figure 2 can be analyzed by analyzing the changes of the ODMR spectrum over time to obtain the following Fig.10 The in-situ micro-area stress variation curve with charge and discharge time is shown. Fig.10 Shows Li x The stress of the micro-area inside the Si electrode changes with the charge and discharge time, and the test error is small. It can reflect the stress evolution of the micro-area with high precision and meet the requirements of in-situ testing.

[0097] Example 3

[0098] This embodiment provides a testing method based on a solid-state battery detection device that uses Raman spectroscopy to non-destructively characterize the phase change evolution of a solid-state battery working electrode material during electrochemical charging and discharging.

[0099] This example uses Figure 5 Solid-state battery device with the structure shown, in-situ monitoring of Si-Li6PS5C lL iNi0.8 Co 0.1 Mn 0.1 Phase evolution of Si in the working electrode of O2 all-solid-state battery with charge and discharge state. Si negative electrode is the observed working electrode. The following is the specific preparation method of the solid-state battery used in this test:

[0100] Negative electrode (working electrode) preparation: The negative electrode active material uses micron Si powder material without adding additional substances.

[0101] Positive electrode (counter electrode) preparation: The positive electrode active material uses commercial lithium titanate Li Ni 0.8 Co 0.1 Mn 0.1 O2 material, weigh the positive electrode active material LiniNi according to the mass ratio of 70:28:2 0.8 Co 0.1 Mn 0.1 O2, solid electrolyte Li6PS5Cl, and conductive additive acetylene black were manually ground in a mortar for 30 min to fully mix the three materials.

[0102] Battery preparation: The same as the conventional solid-state battery preparation method. Take 80mg of solid electrolyte Li6PS5C l powder and place it in a metallographic cold pressing mold, then place it under a cold press, and cold press it for 3 minutes at a uniaxial pressure of 360MPa to form a solid electrolyte sheet; then place the negative electrode powder and the positive electrode powder on both sides of the solid electrolyte sheet, respectively, place it under a cold press, and cold press it for 3 minutes at a pressure of 200MPa; carefully remove the mold and eject the complete solid-state battery.

[0103] Solid-state battery device assembly: assemble the through-hole insulating sleeve 2-1 and the upper and lower sealing rings 2-2 and then assemble them with the cylindrical lower mold 2-3; place the solid-state battery obtained by ejecting the mold into the cavity formed by the through-hole insulating sleeve 2-1 and the cylindrical lower mold 2-3, and the working electrode Li containing the diamond NV color center x Si faces upward, the counter electrode faces downward and contacts the cylindrical lower mold 2-3; x A microwave antenna penetrating the device is fixed on the Si surface and an external microwave source is connected; the working electrode cover 1-1 with an optical quartz glass test window 1-2 is covered on the through-hole insulating sleeve 2-1, and the through-hole insulating sleeve 2-1 is assembled corresponding to the grooves on the working electrode cover 1-1; the heating plate 3 is placed in the groove on the lower side of the cylindrical lower mold 2-3, and the lead wire of the external temperature control processor of the heating plate is placed in the groove; the stress sensor 4-1 and the upper clamping plate 4-2 and the lower clamping plate 4-3 are assembled together under the heating plate and fixed; four sets of bolts 4-4 with insulating sleeves are passed through the entire device at the four axially symmetrical corners through the reserved holes, and the four bolts are tightened to the required external stacking stress with a torque wrench according to the test requirements.

[0104] The working electrode lead on the working electrode cover 1-1 and the working electrode lead on the cylindrical lower mold 2-3 are respectively connected to the positive electrode / negative electrode of the charging and discharging equipment to perform charging and discharging, and at the same time, the working electrode is subjected to in-situ Raman testing.

[0105] Example 4

[0106] This embodiment provides a testing method based on a solid-state battery detection device and using an optical microscope to non-destructively characterize the morphological changes of a solid-state battery working electrode material during the charge and discharge process.

[0107] use Figure 5 Solid-state battery device with the structure shown, in-situ monitoring of SiL i6PS5C lL i Ni 0.8 Co 0.1 Mn 0.1 The morphological evolution of Si in the working electrode of O2 all-solid-state battery with charge and discharge state. The Si negative electrode is the observed working electrode. The following is the specific preparation method of the solid-state battery used in this test:

[0108] Negative electrode (working electrode) preparation: The negative electrode active material uses micron Si powder material without adding additional substances.

[0109] Positive electrode (counter electrode) preparation: The positive electrode active material uses commercial lithium titanate Li Ni 0.8 Co 0.1 Mn 0.1 O2 material, weigh the positive electrode active material LiniNi according to the mass ratio of 70:28:2 0.8 Co 0.1 Mn 0.1 O2, solid electrolyte Li6PS5C l, and conductive additive acetylene black were manually ground in a mortar for 30 min to fully mix the three materials.

[0110] Battery preparation: The same as the conventional solid-state battery preparation method. Take 80mg of solid electrolyte Li6PS5C l powder and place it in a metallographic cold pressing mold, then place it under a cold press, and cold press it for 3 minutes at a uniaxial pressure of 360MPa to form a solid electrolyte sheet; then place the negative electrode powder and the positive electrode powder on both sides of the solid electrolyte sheet, respectively, place it under a cold press, and cold press it for 3 minutes at a pressure of 200MPa; carefully remove the mold and eject the complete solid-state battery.

[0111] Solid-state battery device assembly: assemble the through-hole insulating sleeve 2-1 and the upper and lower sealing rings 2-2 and then assemble them with the cylindrical lower mold 2-3; place the solid-state battery obtained by ejecting the mold into the cavity formed by the through-hole insulating sleeve 2-1 and the cylindrical lower mold 2-3, and the working electrode Li containing the diamond NV color center xSi faces upward, the counter electrode faces downward and contacts the cylindrical lower mold 2-3; x A microwave antenna penetrating the device is fixed on the Si surface and an external microwave source is connected; the working electrode cover 1-1 with an optical quartz glass test window 1-2 is covered on the through-hole insulating sleeve 2-1, and the through-hole insulating sleeve 2-1 is assembled corresponding to the grooves on the working electrode cover 1-1; the heating plate 3 is placed in the groove on the lower side of the cylindrical lower mold 2-3, and the lead wire of the external temperature control processor of the heating plate is placed in the groove; the stress sensor 4-1 and the upper clamping plate 4-2 and the lower clamping plate 4-3 are assembled together under the heating plate and fixed; four sets of bolts 4-4 with insulating sleeves are passed through the entire device at the four axially symmetrical corners through the reserved holes, and the four bolts are tightened to the required external stacking stress with a torque wrench according to the test requirements.

[0112] The working electrode lead on the working electrode cover 1-1 and the working electrode lead on the cylindrical lower mold 2-3 are respectively connected to the positive / negative electrodes of the charging and discharging equipment to perform charging and discharging, and at the same time, the working electrode is observed by in-situ optical microscope morphology.

[0113] The solid-state battery detection device provided by the utility model realizes in-situ non-destructive monitoring of micro-area temperature, mechanics and other parameters inside the solid-state battery under real solid-state battery test conditions. The device can adjust the external stacking pressure and working temperature of the test according to the test needs, and monitor the changes of micro-area stress distribution and temperature inside the solid-state battery in situ. The device has a simple and compact structure, small size, and small test accuracy error.

[0114] The device can replace the test window according to the test needs to adapt to a variety of in-situ solid-state battery characterization methods involving optical detection, especially suitable for technologies including quantum detection of diamond NV color centers, Raman testing, optical microscope testing, etc.

[0115] The specific implementation methods described above further illustrate the purpose, technical solutions and beneficial effects of the utility model in detail. It should be understood that the above description is only the specific implementation method of the utility model and is not used to limit the protection scope of the utility model. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the utility model should be included in the protection scope of the utility model.

Claims

1. A solid-state battery detection device that uses light to characterize micro-area thermal, mechanical and magnetic in situ, characterized in that: The solid-state battery detection device comprises: a cover body, a detected electrode accommodating portion, a heating plate, and a pressure sensing and regulating device; The cover body comprises: a working electrode cover body and a test window opened in the middle of the working electrode cover body; The tested electrode accommodating portion comprises: a through-hole insulating sleeve and a lower mold with a cylinder; the lower mold with a cylinder comprises a central cylinder and a base; the through-hole insulating sleeve is a hollow cylindrical structure, the top end of which is connected to the lower surface of the working electrode cover, and the test window corresponds to the hollow part of the through-hole insulating sleeve; the bottom end is gap-matched with the central cylinder of the lower mold with a cylinder; a cavity is formed inside the through-hole insulating sleeve between the working electrode cover and the central cylinder of the lower mold with a cylinder; the solid-state battery to be tested is placed in the cavity, and the solid-state battery to be tested comprises: a working electrode to be tested, a solid electrolyte and a counter electrode; wherein the working electrode to be tested is exposed below the test window; The heating plate is arranged in the base with the cylindrical lower mold; The pressure sensing and regulating device is arranged below the cylindrical lower mold; the pressure sensing and regulating device comprises a stress sensor.

2. The solid-state battery detection device according to claim 1, characterized in that: The pressure sensing and regulating device comprises: a stress sensor fixing assembly; The stress sensor fixing assembly specifically comprises: an upper clamping plate and a lower clamping plate; The stress sensor is arranged between the upper clamping plate and the lower clamping plate.

3. The solid-state battery detection device according to claim 2, characterized in that: The pressure sensing and regulating device comprises: a pressure regulating component; The pressure adjustment component includes an adjustable bolt set symmetrically arranged on four sides of the solid-state battery detection device and penetrating the working electrode cover, the base, the upper clamping plate and the lower clamping plate; The adjustable bolt set and the working electrode cover are isolated by an insulating sleeve.

4. The solid-state battery detection device according to claim 1, characterized in that: The working electrode cover and the cylindrical lower mold are respectively connected with conductive leads; and / or A microwave antenna penetrating the solid-state battery detection device is provided on the working electrode below the test window, and the microwave antenna is externally connected to a microwave source.

5. The solid-state battery detection device according to claim 1, characterized in that: The heating plate is connected to a temperature control processor arranged outside the solid-state battery detection device.

6. The solid-state battery detection device according to claim 1, characterized in that: The stress sensor is connected to a stacking stress signal receiving and processing device arranged outside the solid-state battery detection device.

7. The solid-state battery detection device according to claim 1, characterized in that: The through-hole insulating sleeve is provided with grooves at both ends thereof, and sealing rings are provided in the grooves; The working electrode cover and the through-hole insulating sleeve, as well as the through-hole insulating sleeve and the cylindrical lower mold are sealed by the sealing ring.

8. The solid-state battery detection device according to claim 1, characterized in that: The working electrode cover and the cylindrical lower mold are made of pressure-resistant conductive metal materials, including one of stainless steel, zinc, titanium, aluminum, copper and alloys thereof; The material of the test window is transparent acrylic plastic or optical quartz glass used for diamond nitrogen-vacancy (NV) color center quantum detection, or optical quartz glass used for Raman testing or optical microscope testing, wherein the diameter of the optical quartz glass is larger than the diameter of the light spot emitted by the test instrument; The through-hole insulating sleeve is made of a hard heat-resistant insulating material, including: one of insulating ceramics, polyvinyl chloride, polyethylene, polypropylene, polycarbonate fiber, polyoxymethylene, polyphenylene sulfide, polyetheretherketone, polyimide, and polysulfone; The heating plate is made of a high temperature and high pressure resistant material, including: a polyimide heating plate, a mica heating plate, a high temperature ceramic heating plate or a silicone rubber heating plate.

9. The solid-state battery detection device according to claim 1, characterized in that: The working electrode is a working electrode containing diamond NV color centers; The light emitted by the excitation light source for exciting the NV color center of diamond is incident on the working electrode to be tested near the microwave antenna from the outside of the test window; The fluorescence signal receiver receives the fluorescence emitted by the diamond NV color center and passing through the test window.

10. A solid-state battery detection system that uses light to characterize micro-area thermal, mechanical and magnetic in situ, characterized in that: The system comprises: the solid-state battery detection device according to claim 1, an excitation light source, a microwave source, a fluorescence signal receiver, a stack stress signal receiving and processing device, and a temperature control processor; The solid-state battery detection device is used for quantum detection of diamond NV color centers, Raman testing or optical microscope testing.

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