CN112952126B - Thermally activated battery structure and application thereof - Google Patents
Thermally activated battery structure and application thereof Download PDFInfo
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- CN112952126B CN112952126B CN202110231483.6A CN202110231483A CN112952126B CN 112952126 B CN112952126 B CN 112952126B CN 202110231483 A CN202110231483 A CN 202110231483A CN 112952126 B CN112952126 B CN 112952126B
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- 239000003792 electrolyte Substances 0.000 claims abstract description 54
- 230000004888 barrier function Effects 0.000 claims abstract description 33
- 239000004698 Polyethylene Substances 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 16
- -1 Polyethylene Polymers 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 229920006254 polymer film Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920002367 Polyisobutene Polymers 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920000306 polymethylpentene Polymers 0.000 claims description 2
- 239000011116 polymethylpentene Substances 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 5
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 10
- 230000004913 activation Effects 0.000 description 8
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/36—Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal cells
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
The invention belongs to the field of electrochemistry, and particularly relates to a heat activated battery structure and application thereof. The invention discloses a heat activated battery structure, which solves the problem of overhigh heat activated temperature of a thermal battery. According to the invention, a layer of physical barrier layer is added between the anode and the electrolyte, between the cathode and the electrolyte or between the anode and the electrolyte, so that the battery is in an unactivated state in which the battery cannot be discharged, the temperature is raised, the barrier layer is melted, the ion passage in the battery is conducted, and the battery is activated to realize normal discharge.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a heat activated battery structure and application thereof.
Background
A thermal (heat activated) battery is an important reserve battery. The heating element is ignited by the activation system to generate heat, so that the internal temperature of the thermal battery is quickly increased to about 500 ℃, and the electrolyte is melted into a liquid conductive state and outputs electric energy.
However, common salts of halides have a high melting point, so that the activation temperature of the battery is mostly above 400 ℃, and this high activation temperature brings about a number of adverse effects: 1. more pyrotechnic material is needed inside the battery to reach the required activation temperature, which is not beneficial to miniaturization and energy density improvement of the battery; 2. the requirements on the heat insulation layer and the shell of the battery are higher, and the cost of the battery is increased; 3. the application scenes of lower temperature (below 300 ℃) such as oil gas exploitation are not applicable, so that the universality of the thermal battery is not strong; 4. the common battery positive electrode material pyrite (FeS 2) can decompose at higher temperatures, resulting in a loss of battery capacity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a heat activated battery structure and application thereof, and solves the problem of overhigh activation temperature of the heat activated battery in the prior art.
One of the technical schemes of the invention is to provide a heat activated battery structure: comprises a positive electrode, a negative electrode and an electrolyte, and further comprises a physical barrier layer positioned between the positive electrode and the electrolyte to separate the positive electrode from the electrolyte; or between the anode and the electrolyte to separate the anode from the electrolyte; or in the middle of the electrolyte, dividing the electrolyte into a first part contacting the positive electrode and a second part contacting the negative electrode, and separating the first part and the second part by the physical barrier layer; and below 300 ℃, the physical barrier is capable of changing from a solid phase to a liquid phase under heating conditions.
The electrolyte is a continuous phase having ion conducting properties.
The physical barrier layer is one of a polymer film capable of being converted from a solid phase to a liquid phase under heating and an organic substance in a solid state at room temperature.
The composition of the polymer film is preferably one of Polyethylene (PE), polypropylene (PP), polyvinyl chloride, polyimide poly, polyvinylidene chloride, polymethylpentene, polypropylene oxide, polyisobutylene, polyphosphate, polyvinylidene fluoride (PVDF), polyethylene terephthalate (PET), polyethylene oxide, polyethylene glycol, polymethyl methacrylate (PMMA), polyamide (PA), polytetrafluoroethylene, polysiloxane, polyacrylonitrile, polyvinyl acetal Ding Quanzhi (PVB) and Polyurethane (PU).
The organic matter is preferably one of Ethylene Carbonate (EC), paraffin and phenol.
The physical barrier layer is dense and does not have a pore structure.
The thickness of the physical barrier layer is 1nm-500 mu m.
The physical barrier layer is a polymer film and has a thickness of 1nm to 10 mu m.
The second technical scheme of the invention is to provide an application of the heat activated battery structure.
The technical scheme has the following beneficial effects:
1. The positive electrode and the negative electrode in the battery are isolated from the electrolyte part by adding the physical barrier layer, so that the battery is in an unactivated state which can not be discharged, the battery can not self-discharge, and the battery can be stored for a long time without losing electric quantity; the physical barrier layer melts when the temperature is raised, the ion passage in the battery is conducted, and the battery is activated to realize normal discharge.
2. The physical barrier layer is polymer or organic matter, the kind and molecular weight of the polymer film can be flexibly regulated, and the melting point can be controlled below 300 ℃, so that the reduction of the activation temperature of the thermal battery and the continuous regulation of the activation temperature can be realized.
Drawings
The invention is further described below with reference to the drawings and examples.
Fig. 1 shows a thermally activated cell structure with physical barrier films in three different positions in an embodiment of the invention.
Fig. 2 is a discharge curve of the battery in example 1 of the present invention.
FIG. 3 is a thermal analysis graph of PE sealing film in example 7 of the invention.
Detailed Description
The content of the present invention will be described in more detail by examples, but the scope of the present invention is not limited to these examples.
Example 1
A thermally activated battery comprising a battery structure as shown in fig. 1 (a) comprising a negative electrode 1a, a positive electrode 2a, a physical barrier 3a and an electrolyte 4a, wherein the physical barrier 3a is located between the negative electrode 1a and the electrolyte 4a and completely separates the negative electrode 1a and the electrolyte 4 a. In this embodiment, the positive electrode material is mainly V 2O5, the negative electrode material is mainly Li (B) alloy, and EO is provided between the positive electrode material and the negative electrode material: a PEO (LiTFSi) electrolyte membrane with Li + =15, a dense PE film with a thickness of 10 μm was added between the anode and the electrolyte membrane, completely separating the electrolyte from the anode. The battery was placed in an oven and warmed to 150 ℃ at 5 ℃/min, and the open circuit voltage of the battery during the warming was recorded with a multimeter, with the open circuit voltages at different temperatures as shown in table 1. And the battery was discharged at 0.2C under the condition of maintaining the temperature at 140C, the discharge curve of which is shown in fig. 2.
Table 1 open circuit voltage of thermally activated cells at different temperatures in example 1
Example 2
A thermally activated battery comprising a battery structure as shown in fig. 1 (b), the battery structure comprising a negative electrode 1b, a positive electrode 2b, a physical barrier 3b and an electrolyte 4b, the physical barrier 3b being located between the positive electrode 2b and the electrolyte 4b to completely separate the positive electrode 2b from the electrolyte 4 b. In the embodiment, the positive electrode material is mainly FeS 2, the negative electrode material is mainly Li (B) alloy, a LiTFSi-PMMA electrolyte film with the mol/L is arranged between the positive electrode material and the negative electrode material, and a PE compact film with the thickness of 10 mu m is added between the positive electrode plate and the electrolyte film to completely separate the electrolyte from the positive electrode plate. The cell was placed in an oven at 5C/min to 160C and incubated, and the open circuit voltage of the cell during the warming was recorded with a multimeter and discharged at 160C at 0.5C.
Example 3
A thermally activated battery comprising a battery structure as shown in fig. 1 (a) comprising a negative electrode 1a, a positive electrode 2a, a physical barrier 3a and an electrolyte 4a, wherein the physical barrier 3a is located between the negative electrode 1a and the electrolyte 4a and completely separates the negative electrode 1a and the electrolyte 4 a. In this embodiment, the positive electrode material is mainly V 2O5, the negative electrode material is mainly Li metal foil, and EO is provided between the positive electrode material and the negative electrode material: a PEO (LiTFSi) electrolyte membrane with Li + =15, a PP (polypropylene) dense film with a thickness of 8 μm was added between the anode and the electrolyte membrane, completely separating the electrolyte from the anode. The cell was placed in an oven at 5 ℃/min to 180 ℃ and incubated, the cell voltage at each temperature was recorded, and the cell was discharged at 160 ℃ at 1 ℃.
Example 4
A thermally activated battery comprising a battery structure as shown in fig. 1 (a) comprising a negative electrode 1a, a positive electrode 2a, a physical barrier 3a and an electrolyte 4a, wherein the physical barrier 3a is located between the negative electrode 1a and the electrolyte 4a and completely separates the negative electrode 1a and the electrolyte 4 a. In this embodiment, the positive electrode material is mainly V 2O5, the negative electrode material is mainly Li (B) alloy, and EO is provided between the positive electrode material and the negative electrode material: a 10 μm thick paraffin film was added between the anode and the electrolyte membrane to completely separate the electrolyte from the anode, for a PEO (LiTFSi) electrolyte membrane with Li + =15. The battery was placed in an oven and warmed to 100 ℃ at 5 ℃/min, and the open circuit voltage of the battery during the warming was recorded with a multimeter.
Example 5
A thermally activated battery comprising a battery structure as shown in fig. 1 (c), the battery structure comprising a negative electrode 1c, a positive electrode 2c, a physical barrier 3c and an electrolyte 4c, wherein the physical barrier 3c is located in the middle of the electrolyte 4c, the electrolyte 4c is divided into a first portion 5c in contact with the positive electrode 2c and a second portion 6c in contact with the negative electrode 1c, and the first portion 5c and the second portion 6c are separated by the physical barrier 3 c. In this embodiment, the positive electrode material is mainly FeS 2, the negative electrode material is mainly Li (B) alloy, a dense PE film with a thickness of 8 μm is arranged between the positive electrode material and the negative electrode material, and 1M LiTFSi-PMMA electrolyte is respectively filled between the positive electrode sheet and the PE film and between the negative electrode and the PE film, i.e. the electrolyte is separated by the PE film. The cell was placed in an oven at 5C/min to 160C and incubated, and the open circuit voltage of the cell during the warming was recorded with a multimeter and discharged at 160C at 0.5C.
Example 6
A conductivity test device, in which PEO electrolyte with ion conducting effect is sandwiched between two steel sheets, a physical barrier PE film is placed between one of the steel sheets and PEO, the device is placed in an oven, the temperature is raised to 180 ℃ at a rate of 5 ℃/min, and the conductivity of the new electrolyte system at different temperatures is tested and recorded as shown in Table 2. From the test results, it can be also shown that the electrolyte has no ion transmission function at normal temperature due to the blocking of the PE film, the PE film melts at high temperature, the ion passage is conducted, and the system has ion conductivity.
TABLE 2 conductivity of electrolytes at different temperatures in example 6
Example 7
The physical barrier films PE used in examples 1,3 and 5 were subjected to thermal analysis, and the results are shown in fig. 3.
Table 3 shows the melting point ranges of several different polymers used as physical separators. Because different polymers have different melting points, and thus the separator has different phase transition temperatures, the activation temperature and the working temperature of the heat-activated battery can be flexibly adjusted by selecting different separators.
TABLE 3 melting Point ranges for different polymers
| Polymer species | PE | PP | PVDF | PMMA | PA | PET |
| Melting point (. Degree. C.) | 120-136 | 148-176 | 156-170 | 130-140 | 215-260 | 225-260 |
The foregoing is provided for the purpose of illustration only, and is not intended to limit the scope of the invention in any way, i.e., the modifications made by the claims and specification should be considered as falling within the scope of the invention.
Claims (6)
1. A thermally activated battery structure comprising a positive electrode, a negative electrode, and an electrolyte, characterized in that: further comprising a physical barrier layer between the positive electrode and the electrolyte to separate the positive electrode from the electrolyte; or between the anode and the electrolyte to separate the anode from the electrolyte; or in the middle of the electrolyte, dividing the electrolyte into a first part contacting the positive electrode and a second part contacting the negative electrode, and separating the first part and the second part by the physical barrier layer; and below 300 ℃, the physical barrier layer is capable of transitioning from a solid phase to a liquid phase under heating conditions; the physical barrier layer is one of a polymer film and an organic matter which can be converted from a solid phase to a liquid phase under the heating condition; the physical barrier layer is dense and does not have a pore structure.
2. A thermally activated battery construction as set forth in claim 1 wherein: the electrolyte is a continuous phase having ion conducting properties.
3. A thermally activated battery construction as set forth in claim 1 wherein: the polymer film comprises one of Polyethylene (PE), polypropylene (PP), polyvinyl chloride, polyimide poly, polyvinylidene chloride, polymethylpentene, polypropylene oxide, polyisobutylene, polyphosphate, polyvinylidene fluoride (PVDF), polyethylene terephthalate (PET), polyethylene oxide, polyethylene glycol, polymethyl methacrylate (PMMA), polyamide (PA), polytetrafluoroethylene, polysiloxane, polyacrylonitrile, polyvinyl acetal Ding Quanzhi (PVB) and Polyurethane (PU).
4. A thermally activated battery construction as set forth in claim 1 wherein: the organic matter is one of Ethylene Carbonate (EC), paraffin and phenol.
5. A thermally activated battery construction as set forth in claim 1 wherein: the thickness of the physical barrier layer is 1nm-500 mu m.
6. A thermally activated battery construction as set forth in claim 1 wherein: the physical barrier layer is a polymer film and has a thickness of 1nm to 10 mu m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110231483.6A CN112952126B (en) | 2021-03-02 | 2021-03-02 | Thermally activated battery structure and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110231483.6A CN112952126B (en) | 2021-03-02 | 2021-03-02 | Thermally activated battery structure and application thereof |
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| Publication Number | Publication Date |
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| CN112952126A CN112952126A (en) | 2021-06-11 |
| CN112952126B true CN112952126B (en) | 2024-07-02 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200041165A (en) * | 2018-10-11 | 2020-04-21 | 주식회사 엘지화학 | A solid electrolyte membrane and an all solid type battery comprising the same |
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| CN105048004A (en) * | 2015-06-18 | 2015-11-11 | 中国科学院青岛生物能源与过程研究所 | Thermally activated secondary battery using low-temperature molten salt electrolyte |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200041165A (en) * | 2018-10-11 | 2020-04-21 | 주식회사 엘지화학 | A solid electrolyte membrane and an all solid type battery comprising the same |
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| CN112952126A (en) | 2021-06-11 |
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