CN112540102B - Device and method for in-situ detection of thermal stability of battery material - Google Patents
Device and method for in-situ detection of thermal stability of battery material Download PDFInfo
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- CN112540102B CN112540102B CN202011538153.3A CN202011538153A CN112540102B CN 112540102 B CN112540102 B CN 112540102B CN 202011538153 A CN202011538153 A CN 202011538153A CN 112540102 B CN112540102 B CN 112540102B
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- 239000000463 material Substances 0.000 title claims abstract description 70
- 238000001514 detection method Methods 0.000 title claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000012360 testing method Methods 0.000 claims abstract description 177
- 238000010438 heat treatment Methods 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 230000008859 change Effects 0.000 claims description 9
- 230000007613 environmental effect Effects 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 description 34
- 239000007789 gas Substances 0.000 description 31
- 239000007774 positive electrode material Substances 0.000 description 12
- 239000010405 anode material Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000006399 behavior Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- -1 separator Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
- G01N25/4806—Details not adapted to a particular type of sample
- G01N25/4813—Details not adapted to a particular type of sample concerning the measuring means
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
- G01N25/4806—Details not adapted to a particular type of sample
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
- G01N25/4806—Details not adapted to a particular type of sample
- G01N25/4826—Details not adapted to a particular type of sample concerning the heating or cooling arrangements
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Secondary Cells (AREA)
- Investigating Or Analyzing Materials Using Thermal Means (AREA)
Abstract
The invention belongs to the technical field of batteries, and particularly relates to a device and a method for in-situ detection of thermal stability of a battery material. The device comprises a testing environment cavity, a main testing cavity, an auxiliary testing cavity and a communicating pipe, wherein the main testing cavity, the auxiliary testing cavity and the communicating pipe are arranged in the testing environment cavity, the main testing cavity, the auxiliary testing cavity and the communicating pipe are connected through a connecting tee, and the tail end of the communicating pipe extends out of the testing environment cavity and is connected with a control ball valve; the bottoms of the main test cavity and the auxiliary test cavity are provided with a test cavity heating device; an environment cavity heating device is arranged on the inner wall of the test environment cavity. The invention can adopt larger experimental sample quantity, thereby greatly reducing the problems of accidental errors, weak detection signals and the like caused by too few samples; the influence of gas generated by the material A on the thermal stability and exothermic reaction of the material B can be detected on line in one experiment process.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a device and a method for in-situ detection of thermal stability of a battery material.
Background
Fully utilizing renewable energy sources (solar energy, wind energy, tidal energy and the like) has important significance for relieving the increasingly serious environmental problems at present. However, renewable energy sources are difficult to utilize due to the intermittence and unpredictability. Development of electrochemical energy storage devices is one of the effective schemes for solving the instability of renewable energy power generation. Secondary batteries represented by lithium ion batteries are widely used in various electronic products and electric vehicles due to their high energy density and long service life. Along with the high-speed development and popularization of the new energy automobile industry, the improvement of the energy density and the endurance mileage of the battery becomes the research focus of the current secondary battery. However, high energy density is accompanied by high safety risk, and safety accidents of lithium ion batteries, which are characterized by thermal runaway of the batteries, frequently occur in recent years, so that the confidence of consumers is seriously hit.
The thermal runaway behavior of the battery is mainly that a series of irreversible exothermic reactions in the battery, which are caused by heat accumulation/temperature rise, occur successively to form a chained effect, and finally the internal temperature and pressure of the battery rise sharply to generate extremely runaway (dense smoke, combustion, explosion and the like) behaviors. At present, the research on the thermal runaway mechanism of the lithium ion battery mainly adopts equipment such as a Differential Scanning Calorimeter (DSC), a Thermogravimetric (TG), an isothermal calorimeter, an adiabatic calorimeter and the like. The adiabatic calorimeter is generally used for analyzing the whole battery and researching the runaway temperature and time of the whole battery. DSC and TG analyses are commonly used to study the interaction and thermal compatibility between components. However, DSC is generally not suitable for systems with severe chemical reactions, and TG testing generally cannot be performed in a closed container, and cannot be performed effectively for pressure data acquisition and control. In the exploration of the mechanism of thermal runaway of lithium ions, previous researchers proposed that the negative electrode and the positive electrode were both accompanied by the generation of different gases during the temperature rise, which may have shuttles and have an influence on the thermal runaway of the battery. In the prior art, the gas production behavior of the button or cylindrical battery in the circulation can be detected in situ, but the extremely out-of-control condition of the large battery or the battery can not be detected. In the prior art, a device for detecting the circulating gas production and the high-temperature gas production of the ion soft package battery is designed by a carrier gas method, a liquid discharge method and the like by utilizing a selection valve, a vacuum pump and other devices, but the methods can only simply collect and detect the gas production of the battery, and no effective device can perform online study and analysis on the gas shuttle generated by the internal materials of the battery at present.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a device and a method for in-situ detection of thermal stability of battery materials, so as to solve the problem of limitation of undefined gas production and interaction between components of battery materials in the current research process of thermal runaway mechanism of secondary batteries.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the device for in-situ detection of the thermal stability of the battery material comprises a testing environment cavity, a main testing cavity, an auxiliary testing cavity and a communicating pipe, wherein the main testing cavity, the auxiliary testing cavity and the communicating pipe are arranged in the testing environment cavity, the main testing cavity, the auxiliary testing cavity and the communicating pipe are connected through a connecting tee joint, and the tail end of the communicating pipe extends out of the testing environment cavity and is connected with a control ball valve;
The bottoms of the main test cavity and the auxiliary test cavity are provided with a test cavity heating device; an environment cavity heating device is arranged on the inner wall of the test environment cavity.
And a temperature sensor is inserted into the main test cavity.
The upper end of the temperature sensor is led out of the communicating pipe and is fixed through a sensor connecting nut.
The upper end of the communicating pipe is provided with a pressure sensor.
The test cavity heating device comprises a heating base I and a heating base II, wherein the heating base I is arranged at the bottom of the main test cavity; the heating base II is arranged at the bottom of the auxiliary testing cavity and is connected with the heating base I in series through a heating wire.
And a pipeline control valve I and a pipeline control valve II are respectively arranged at the air outlets of the main test cavity and the auxiliary test cavity.
The environment cavity heating device comprises a side heater, a bottom heater and a top heater which are arranged on the inner wall of the test environment cavity.
The in-situ detection method for the thermal stability of the battery material comprises the device for in-situ detection of the thermal stability of the battery material, and the device is used for detecting the thermal stability, exothermic reaction and temperature change of the single battery material component; or detecting the influence of the gas generated by the battery material A on the thermal stability, exothermic reaction and temperature change of the battery material B.
The device for detecting the thermal stability of the battery material in situ is used for detecting the thermal stability, exothermic reaction and temperature change conditions of the components of the single battery material, and comprises the following steps:
1) Placing the battery material A with the set content in a main test cavity, or placing the battery material A with the set content in the main test cavity and an auxiliary test cavity;
2) The main testing cavity and the auxiliary testing cavity are connected with the communicating pipe through the connecting tee joint and then are placed in the testing environment cavity;
3) The environment cavity heating device is used for heating the test environment cavity, and the bottoms of the main test cavity and the auxiliary test cavity are synchronously heated;
4) The test was started and a time-temperature profile of the battery material a in the main test cavity was obtained.
The device for detecting the thermal stability of the battery material in situ is used for detecting the influence of the gas generated by the battery material A on the thermal stability, exothermic reaction and temperature change of the battery material B, and comprises the following steps:
1) Placing the battery material A with the set content in a main testing cavity, and placing the battery material B with the set content in an auxiliary testing cavity;
2) The main test cavity, the auxiliary test cavity and the communicating pipe are connected through a connecting tee;
3) The environment cavity heating device is used for heating the test environment cavity, and the bottoms of the main test cavity and the auxiliary test cavity are synchronously heated;
4) The test was started and a time-temperature profile of the battery material a in the main test cavity was obtained.
Compared with the prior art, the invention has the following advantages:
1. the invention can online detect the influence of the gas generated by the material A on the thermal stability and exothermic reaction of the material B in one experiment process;
2. The invention can adopt larger experimental sample quantity (about 10 g), thereby greatly reducing the problems of accidental error caused by too few samples, weak detection signals and the like;
3. compared with DSC or TG, the device can be operated in a closed glove box, and the pollution problem of oxygen and moisture in the sample preparation and adding process can be reduced.
Drawings
FIG. 1 is a schematic structural view of an apparatus for in situ detection of thermal stability of a battery material according to the present invention;
FIG. 2 is a graph showing time-temperature profile during temperature rise of the positive electrode material and the electrolyte in accordance with the first embodiment of the present invention;
FIG. 3 is a graph showing time-temperature profile during heating of the anode material and electrolyte in accordance with the second embodiment of the present invention;
FIG. 4 is a time-temperature graph of the effect of anode material and electrolyte on anode material and electrolyte gas shuttling in example III of the present invention;
Fig. 5 is a time-temperature plot of the gas shuttle effect of the positive electrode material and electrolyte on the negative electrode material and electrolyte in example four of the present invention.
In the figure: 1. testing the environment cavity; 2. a cavity wall; 3. a side heater; 4. heating the base I, 5 and the heating wire; 6. a bottom heater; 7. a main test cavity; 8. a temperature sensor; 9. card sleeve I; 10. a pipeline control valve I; 11. connecting a tee joint; 12. a fixing nut; 13. a pressure sensor; 14. a sensor coupling nut; 15. controlling a ball valve; 16. an air guide port, 17 and a top heater; 18. card sleeve II; 19. an auxiliary test cavity; 20. a pipeline control valve II; 21. heating a base II; 22. and communicating pipe.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1, the device for in-situ detection of thermal stability of battery materials provided by the invention comprises a testing environment cavity 1, a main testing cavity 7, an auxiliary testing cavity 19 and a communicating pipe 22, wherein the main testing cavity 7, the auxiliary testing cavity 19 and the communicating pipe 22 are arranged in the testing environment cavity 1, the main testing cavity 7, the auxiliary testing cavity 19 and the communicating pipe 22 are connected through a connecting tee 11, and the tail end of the communicating pipe 22 extends out of the testing environment cavity 1 and is connected with a control ball valve 15; the bottoms of the main test cavity 7 and the auxiliary test cavity 19 are provided with a test cavity heating device, and the inner wall of the test environment cavity 1 is provided with an environment cavity heating device.
In the embodiment of the invention, the main test cavity 7 is internally provided with the temperature sensor 8, and the upper end of the temperature sensor 8 is led out from the communicating pipe 22 and is fixed by the sensor connecting nut 14.
Further, the upper end of the communication pipe 22 is provided with a pressure sensor 13.
As shown in fig. 1, in the embodiment of the invention, the test cavity heating device includes a heating base i 4 and a heating base ii 21, wherein the heating base i 4 is disposed at the bottom of the main test cavity 7, and the heating base ii 21 is disposed at the bottom of the auxiliary test cavity 19 and is connected in series with the heating base i 4 through the heating wire 5.
Specifically, the same heating wire 5 is wound at the bottoms of the main test cavity 7 and the auxiliary test cavity 19 in the same manner, so that the main test cavity 7 and the auxiliary test cavity 19 can be uniformly heated, and the heating synchronism of the main test cavity 7 and the auxiliary test cavity 19 in the heat insulation cavity is ensured.
As shown in fig. 1, in the embodiment of the present invention, the environmental chamber heating device includes a side heater 3, a bottom heater 6 and a top heater 17 disposed on the inner wall of the test environmental chamber 1. An adiabatic or isothermal environment without heat loss is provided by controlling the temperature of the chamber and the temperature of the test chamber.
Further, the air outlets of the main test cavity 7 and the auxiliary test cavity 19 are respectively provided with a pipeline control valve I10 and a pipeline control valve II 20. The pipeline control valve I10 and the pipeline control valve II 20 are mainly controlled by a computer to switch on and off the valves at a specific temperature, and the gas shuttling in the main test cavity 7 and the auxiliary test cavity 19 is specifically regulated and controlled.
The end of the communicating pipe 22 is provided with a gas guide port 16, and the opening and the closing are controlled by a control ball valve 15. High-pressure gas can be injected into the inner pipeline and the testing cavity through the external device, or gas generated in the inner pipeline and the testing cavity can be led out.
In the embodiment of the invention, the main testing cavity 7 and the auxiliary testing cavity 19 are spherical, ellipsoidal, cuboid and other closed chambers with open pipelines, and are prepared from alloy/metal which does not react with battery materials chemically and has high-pressure resistance and good thermal conductivity. Specifically, the main test cavity 7 and the auxiliary test cavity 19 are reaction balls prepared from hastelloy, and a 1/4 inch open pipeline is reserved at the upper end.
The main test cavity 7 and the auxiliary test cavity 19 are connected with the connecting pipeline through the detachable clamping sleeve and the nut, so that the gas can shuttle through the pipeline without direct contact of solid and liquid test objects. The detection part of the temperature sensor 8 is immersed in the bottom object to be detected of the main test chamber 7, but is not in contact with the inner wall of the main test chamber 7.
A method for in situ detection of thermal stability of a battery material, comprising the apparatus for in situ detection of thermal stability of a battery material according to any of the embodiments described above, by which thermal stability, exothermic reaction, temperature and gas production of a single battery material component or influence of gas generated by a battery material a on thermal stability, exothermic reaction and temperature change of a battery material B are detected.
The device for detecting the thermal stability of the battery material in situ is used for detecting the thermal stability, exothermic reaction and temperature change conditions of the components of the single battery material, and comprises the following steps:
1) Placing the battery material A with set content in the main test cavity 7, leaving the auxiliary test cavity 19 empty, and closing the pipeline control valve II 20 of the auxiliary test cavity 19;
or placing the battery material A with set content in the main test cavity 7 and the auxiliary test cavity 19;
2) The main testing cavity 7 and the auxiliary testing cavity 19 are connected with a communicating pipe 22 through a connecting tee 11 and then are placed in the testing environment cavity 1;
3) The environment cavity heating device is used for heating the test environment cavity 1, and simultaneously the bottoms of the main test cavity 7 and the auxiliary test cavity 19 are synchronously heated;
4) The test is started and a time-temperature profile of the battery material a in the main test chamber 7 is obtained.
The device for detecting the thermal stability of the battery material in situ is used for detecting the influence of the gas generated by the battery material A on the thermal stability, exothermic reaction and temperature change of the battery material B, and comprises the following steps:
1) Placing the battery material A with the set content in the main test cavity 7, and placing the battery material B with the set content in the auxiliary test cavity 19;
2) The main testing cavity 7, the auxiliary testing cavity 19 and the communicating pipe 22 are connected through the connecting tee 11;
3) The environment cavity heating device is used for heating the test environment cavity 1, and simultaneously the bottoms of the main test cavity 7 and the auxiliary test cavity 19 are synchronously heated;
4) The test is started and a time-temperature profile of the battery material a in the main test chamber 7 is obtained.
In this embodiment, the detection object is a material of a secondary battery (including a lithium ion battery, a lithium metal battery, a lithium sulfur battery, a sodium battery, a zinc battery, a magnesium battery, etc.) under a specific state of charge (SOC 0% -100%), including: any combination of one or more materials of current collector, positive electrode material, negative electrode material, separator, electrolyte (liquid, gel and solid), adhesive and other additives.
In this example, a double salt electrolyte was prepared in an argon glove box, specifically, lithium salt was: 0.6mol of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), 0.4mol of lithium difluorooxalato borate (LiDFOB), 0.05mol of lithium hexafluorophosphate (LiPF 6); the solvent is as follows: ethylene Carbonate (EC), propylene Carbonate (PC), methyl ethyl carbonate (EMC) are mixed according to a volume ratio of 1:1:3; the electrolyte is selected to prepare a 5Ah capacity NCM 532/graphite soft package battery, the battery is firstly formed and then pumped, then the battery is charged to 4.2V at 0.5 ℃, and then the battery is charged for 10 minutes at equal pressure, the full-charge battery is transferred into a glove box, and the anode material powder and the cathode material powder are scraped by a blade for standby.
Example 1
The experimental equipment was assembled according to the method described in the above examples, 1g of the positive electrode material powder was accurately weighed in an argon glove box, placed in the main test chamber 7, and then 0.5ml of the double salt electrolyte as described above was added; then, 1g of the cathode material powder and 0.5ml of a double salt electrolyte were also placed in the auxiliary test chamber 19. The main testing cavity 7 and the auxiliary testing cavity 19 are respectively connected into the connecting tee 11 by adopting a front cutting sleeve, a rear cutting sleeve and a nut, and then are arranged in the adiabatic isothermal testing environment cavity 1. Step heating is carried out by adopting a heating-waiting-searching mode, the testing temperature range is 40-250 ℃, the temperature of the step is 5 ℃, the waiting time is 20min, the detection limit is 0.03 ℃/min, and the maximum cut-off temperature is 500 ℃.
As shown in fig. 2, the time versus temperature profile of the positive electrode material and the electrolyte in the main test chamber 7, wherein T csh =134 ℃, i.e. the initial exotherm temperature is 134 ℃; t tr = 318 ℃, i.e. the thermal runaway temperature is 318 ℃. The curve shows that before 134 ℃, the ternary positive electrode material and the electrolyte have no obvious exothermic reaction, and the positive electrode material and the electrolyte start to undergo slow exothermic reaction from 134 ℃ to 318 ℃ at a self-exothermic speed of 1 ℃/min.
Example two
The experimental equipment was assembled according to the method described in the above example, 1g of the negative electrode material powder was accurately weighed in an argon glove box under an inert gas atmosphere, placed in the main test chamber 7, and then 0.5ml of the double salt electrolyte as described above was added; also placed in the auxiliary test chamber 19 are 1g of negative electrode material powder and 0.5ml of double salt electrolyte. The main testing cavity 7 and the auxiliary testing cavity 19 are respectively connected into the connecting tee 11 by adopting a front cutting sleeve, a rear cutting sleeve and a nut, and then are arranged in the adiabatic isothermal testing environment cavity 1. Step heating is carried out by adopting a heating-waiting-searching mode, the testing temperature range is 40-250 ℃, the temperature of the step is 5 ℃, the waiting time is 20min, the detection limit is 0.03 ℃/min, and the maximum cut-off temperature is 500 ℃.
As shown in fig. 3, the time versus temperature curves of the anode material and the electrolyte in the main test chamber 7, wherein T csh = 95 ℃, i.e. the initial exothermic temperature is 95 ℃; t tr = 306 ℃, i.e. the thermal runaway temperature is 306 ℃. The curve shows that before 95 ℃, the ternary cathode material has no obvious exothermic reaction with the electrolyte. Starting from 95 ℃, the negative electrode material and the electrolyte start to undergo a slow exothermic reaction to 306 ℃, and the self-exothermic speed reaches 1 ℃/min.
Example III
The experimental equipment was assembled according to the method described in the above examples, 1g of positive electrode material powder was accurately weighed in an argon glove box, placed in the main test chamber 7, and then 0.5ml of the double salt electrolyte as described above was added; then, 1g of the anode material powder and 0.5ml of the double salt electrolyte were placed in the auxiliary test chamber 19. The main testing cavity 7 and the auxiliary testing cavity 19 are respectively connected into the connecting tee 11 by adopting a front cutting sleeve, a rear cutting sleeve and a nut, and then are arranged in the adiabatic isothermal testing environment cavity 1. Step heating is carried out by adopting a heating-waiting-searching mode, the testing temperature range is 40-250 ℃, the temperature of the step is 5 ℃, the waiting time is 20min, the detection limit is 0.03 ℃/min, and the maximum cut-off temperature is 500 ℃.
As shown in fig. 4, the effect of the negative electrode material and the electrolyte gas production in the main test chamber 7 on the positive electrode material and the electrolyte. The graph illustrates that the positive electrode material and the electrolyte self-exotherm began at 116 ℃. Unlike in example one, there is a significant temperature rise of the cathode material and the electrolyte in the range of 195-285 c, indicating that the gas generated by the anode material and the electrolyte shuttles to the cathode side and promotes or reacts newly with the cathode material and the electrolyte.
Example IV
The experimental equipment was assembled according to the method described in the above examples, 1g of negative electrode material powder was accurately weighed in an argon glove box, placed in the main test chamber 7, and then 0.5ml of the double salt electrolyte as described above was added; then, 1g of the positive electrode material powder and 0.5ml of the double salt electrolyte were placed in the auxiliary test chamber 19. The main testing cavity 7 and the auxiliary testing cavity 19 are respectively connected into the connecting tee 11 by adopting a front cutting sleeve, a rear cutting sleeve and a nut, and then are arranged in the adiabatic isothermal testing environment cavity 1. Step heating is carried out by adopting a heating-waiting-searching mode, the testing temperature range is 40-250 ℃, the temperature of the step is 5 ℃, the waiting time is 20min, the detection limit is 0.03 ℃/min, and the maximum cut-off temperature is 500 ℃.
As shown in fig. 5, the effect of the positive electrode material and the electrolyte gas production in the main test chamber 7 on the negative electrode material and the electrolyte. The curves show that the self-exotherm of the anode material and the electrolyte starts from 95 ℃ and is similar to that of the anode material in the second embodiment, but the temperature for the self-exotherm to be 1 ℃/min in the second embodiment is slightly lower (247 ℃), which shows that the influence of the gas production of the anode material and the electrolyte on the anode material and the electrolyte is mainly in the stage of rapid temperature rise.
In the above embodiments, after the experimental equipment is assembled, air tightness detection is needed, high-pressure air is introduced into the closed pipeline, so that the pressure of the testing cavity is ensured not to drop to be qualified within 30 minutes, otherwise, the nut is screwed again, and the detection is repeated until the air tightness is qualified; the test environment cavity 1 is heated in a selected mode, and a step heating (heating-waiting-searching) mode, a specific speed linear heating mode or a specific temperature isothermal mode can be adopted for testing; the experimental cut-off condition is that the set temperature or the set time is reached, and the experiment is automatically stopped. After the system is cooled, non-condensed gas can be collected through the gas guide port 16 at the tail end of the communicating pipe 22 for detection, or the non-condensed gas can be directly communicated with corresponding detection equipment for in-situ gas detection system.
The device and the method for in-situ detection of the thermal stability of the battery material are mainly used for detecting the thermal stability and the gas shuttle action mechanism among different battery material components of the secondary battery. The device can avoid interference reaction caused by direct contact of different battery materials, and gas products generated by the battery material components can mutually shuttle. The invention can effectively detect the gas production and the reciprocal shuttle action of different components of the battery material in the heating process, and has important effect on researching and understanding the thermal stability and the thermal runaway mechanism of the battery material.
The foregoing is merely an embodiment of the present invention and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, expansion, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.
Claims (5)
1. The method for in-situ detection of the thermal stability of the battery material is characterized by comprising a device for in-situ detection of the thermal stability of the battery material, and the device is used for detecting the influence of gas generated by the battery material A on the thermal stability, exothermic reaction and temperature change of the battery material B;
The device for in-situ detection of the thermal stability of the battery material comprises a testing environment cavity (1), and a main testing cavity (7), an auxiliary testing cavity (19) and a communicating pipe (22) which are arranged in the testing environment cavity (1), wherein the main testing cavity (7), the auxiliary testing cavity (19) and the communicating pipe (22) are connected through a connecting tee joint (11), and the tail end of the communicating pipe (22) extends out of the testing environment cavity (1) and is connected with a control ball valve (15); the bottoms of the main test cavity (7) and the auxiliary test cavity (19) are provided with a test cavity heating device, and the inner wall of the test environment cavity (1) is provided with an environment cavity heating device; a temperature sensor (8) is inserted in the main test cavity (7);
The test cavity heating device comprises a heating base I (4) and a heating base II (21), wherein the heating base I (4) is arranged at the bottom of the main test cavity (7); the heating base II (21) is arranged at the bottom of the auxiliary test cavity (19) and is connected with the heating base I (4) in series through a heating wire (5);
the device for detecting the thermal stability of the battery material in situ is used for detecting the influence of the gas generated by the battery material A on the thermal stability, exothermic reaction and temperature change of the battery material B, and comprises the following steps:
1) Placing the battery material A with the set content in a main test cavity (7), and placing the battery material B with the set content in an auxiliary test cavity (19);
2) The main test cavity (7), the auxiliary test cavity (19) and the communicating pipe (22) are connected through the connecting tee joint (11);
3) The environment cavity heating device is used for heating the test environment cavity (1), and simultaneously, the bottoms of the main test cavity (7) and the auxiliary test cavity (19) are synchronously heated;
4) The test is started to obtain a time-temperature curve of the battery material A in the main test cavity (7).
2. The method for in-situ detection of thermal stability of battery material according to claim 1, characterized in that the upper end of the temperature sensor (8) is led out of the communication tube (22) and is fixed by a sensor connection nut (14).
3. The method for in-situ detection of thermal stability of battery material according to claim 1, wherein the upper end of the communicating tube (22) is provided with a pressure sensor (13).
4. The method for in-situ detection of thermal stability of battery materials according to claim 1, wherein the air outlets of the main test cavity (7) and the auxiliary test cavity (19) are respectively provided with a pipeline control valve I (10) and a pipeline control valve II (20).
5. The method for in-situ detection of thermal stability of battery material according to claim 1, wherein the environmental chamber heating means comprises a side heater (3), a bottom heater (6) and a top heater (17) arranged on the inner wall of the test environmental chamber (1).
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