CN112952126A - Thermally activated battery structure and application thereof - Google Patents
Thermally activated battery structure and application thereof Download PDFInfo
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- CN112952126A CN112952126A CN202110231483.6A CN202110231483A CN112952126A CN 112952126 A CN112952126 A CN 112952126A CN 202110231483 A CN202110231483 A CN 202110231483A CN 112952126 A CN112952126 A CN 112952126A
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- electrolyte
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- barrier layer
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- 239000003792 electrolyte Substances 0.000 claims abstract description 53
- 230000004888 barrier function Effects 0.000 claims abstract description 35
- 239000004698 Polyethylene Substances 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 16
- -1 Polyethylene Polymers 0.000 claims description 11
- 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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920002647 polyamide Polymers 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 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
- 229920001223 polyethylene glycol Polymers 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
- 229920002239 polyacrylonitrile 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
- 230000001131 transforming effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- 238000007725 thermal activation Methods 0.000 abstract description 4
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 2
- 239000012528 membrane Substances 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 238000001994 activation Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052960 marcasite Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 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
- 238000004321 preservation Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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
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- 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)
Abstract
The invention belongs to the field of electrochemistry, and particularly relates to a thermally activated battery structure and application thereof. The invention discloses a thermal activation battery structure, which solves the problem of overhigh thermal activation temperature of a thermal battery. According to the invention, a physical barrier layer is added between the anode and the electrolyte of the battery, between the cathode and the electrolyte or between the electrolyte, so that the battery is in an inactivated state incapable of discharging, the temperature is raised, the barrier layer is melted, the ion path in the battery is conducted, and the battery is activated to realize normal discharging.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a thermally activated battery structure and application thereof.
Background
A thermal (thermally activated) battery is an important reserve battery. The heating element is ignited by the activation system to generate heat, so that the temperature in the thermal battery is rapidly increased to about 500 ℃, the electrolyte is melted into a liquid conductive state, and electric energy is output.
However, the melting point of eutectic salt composed of common halide salt is high, so that the activation temperature of the battery is mostly above 400 ℃, and the high activation temperature brings many adverse effects: 1. more pyrotechnic material is required inside the battery to reach the required activation temperature, disadvantageouslyMiniaturization and improvement of energy density of a battery; 2. the requirements on the heat-insulating 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. common positive electrode material pyrite (FeS) of thermal battery2) And 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 thermal activation battery structure and application thereof, and solves the problem of overhigh activation temperature of the thermal activation battery in the prior art.
One of the technical solutions of the present invention is to provide a thermally activated battery structure: the lithium battery comprises a positive electrode, a negative electrode and an electrolyte, and further comprises a physical barrier layer, wherein the physical barrier layer is positioned between the positive electrode and the electrolyte and separates the positive electrode from the electrolyte; or between the negative electrode and the electrolyte to block the negative electrode from the electrolyte; or in the middle of the electrolyte, the electrolyte is divided into a first part in contact with the positive electrode and a second part in contact with the negative electrode, and the first part and the second part are separated by the physical barrier layer; and the physical barrier layer is capable of transforming from a solid phase to a liquid phase under heating at 300 ℃ or below.
The electrolyte is a continuous phase with ion conducting properties.
The physical barrier layer is one of a polymer film which can be converted into a liquid phase from a solid phase under heating and an organic matter which is in a solid state at room temperature.
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 butyral (PVB) and Polyurethane (PU).
The organic matter is preferably one of Ethylene Carbonate (EC), paraffin and phenol.
The physical barrier is dense and does not have a pore structure.
The thickness of the physical barrier layer is 1nm-500 μm.
The thickness of the physical barrier layer is 1nm-10 μm when the physical barrier layer is a polymer film.
The second technical scheme of the invention is to provide an application of a thermally activated battery structure.
The technical scheme has the following beneficial effects:
1. the positive electrode, the negative electrode and the electrolyte in the battery are separated by adding the physical barrier layer, so that the battery is in an inactivated state which can not discharge, the self-discharge of the battery can not occur, and the battery can be stored for a long time without losing electric quantity; the physical barrier layer is melted when the temperature is raised, the ion path in the battery is conducted, and the battery is activated to realize normal discharge.
2. The introduced physical barrier layer is a polymer or an organic matter, the type and the molecular weight of a polymer film can be flexibly adjusted, and the melting point can be controlled below 300 ℃, so that the reduction of the activation temperature of the thermal battery and the continuous adjustment of the activation temperature can be realized.
Drawings
The invention is further illustrated by the following figures and examples.
Fig. 1 is a diagram of a thermally activated cell configuration with a physical barrier in three different positions according to an embodiment of the present invention.
Fig. 2 is a discharge curve of the battery in example 1 of the present invention.
FIG. 3 thermal analysis curve of PE sealing film in example 7 of the present invention.
Detailed Description
The present invention will be described in more detail by way of 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),the battery structure includes a negative electrode 1a, a positive electrode 2a, a physical barrier film 3a, and an electrolyte 4a, wherein the physical barrier film 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 V2O5The cathode material is mainly Li (B) alloy, and EO: li+15-peo (litfsi) electrolyte membrane, a PE dense film with a thickness of 10 μm was added between the negative electrode and the electrolyte membrane to completely separate the electrolyte from the negative electrode. The cell was placed in an oven at 5 ℃/min to 150 ℃ and the open circuit voltage of the cell during the temperature ramp was recorded with a multimeter and the open circuit voltages at different temperatures are shown in table 1. And the battery is subjected to 0.2C discharge under the condition of 140 ℃ heat preservation, and the discharge curve is shown in figure 2.
Table 1 open circuit voltage of heat activated battery at different temperatures in example 1
Example 2
A thermally activated battery comprising a battery structure as shown in fig. 1(b) comprising a negative electrode 1b, a positive electrode 2b, a physical barrier film 3b and an electrolyte 4b, the physical barrier film 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 this embodiment, the cathode material is mainly FeS2The anode material is mainly Li (B) alloy, a 1mol/L LiTFSi-PMMA electrolyte membrane is arranged between the anode material and the cathode material, and a PE dense film with the thickness of 10 mu m is added between the anode plate and the electrolyte membrane to completely separate the electrolyte from the anode plate. The cell was placed in an oven at 5 ℃/min to 160 ℃ and held at temperature, and the open circuit voltage of the cell during the temperature ramp was recorded with a multimeter and discharged at a temperature of 160 ℃ at 0.5 ℃.
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 film 3a and an electrolyte 4a, wherein the physical barrier film3a is located between the anode 1a and the electrolyte 4a and completely separates the anode 1a and the electrolyte 4 a. In this embodiment, the positive electrode material is mainly V2O5The negative electrode material is mainly Li metal foil, and EO: li+Peo (litfsi) electrolyte membrane 15, a PP (polypropylene) dense film with a thickness of 8 μm was added between the negative electrode and the electrolyte membrane to completely separate the electrolyte from the negative electrode. The cell was placed in an oven at 5 ℃/min to 180 ℃ and held at temperature, 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 film 3a and an electrolyte 4a, wherein the physical barrier film 3a is located between the negative electrode 1a and the electrolyte 4a and completely separates the negative electrode 1a from the electrolyte 4 a. In this embodiment, the positive electrode material is mainly V2O5The cathode material is mainly Li (B) alloy, and EO: li+A 10 μm thick paraffin film was added between the negative electrode and the electrolyte membrane to completely block the electrolyte from the negative electrode. The cell was placed in an oven at 5 ℃/min to 100 ℃ and the open circuit voltage of the cell during the temperature ramp was recorded with a multimeter.
Example 5
A thermally activated battery comprising a battery structure as shown in fig. 1(c) comprising a negative electrode 1c, a positive electrode 2c, a physical barrier film 3c and an electrolyte 4c, wherein the physical barrier film 3c is located in the middle of the electrolyte 4c, dividing the electrolyte 4c 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 layer 3 c. In this embodiment, the cathode material is mainly FeS2The negative electrode material is mainly Li (B) alloy, a compact PE film with the thickness of 8 mu M is arranged between the positive electrode material and the negative electrode material, and 1M LiTFSi-PMMA electrolyte is respectively filled between the positive electrode plate and the PE film and between the negative electrode and the PE film, namely the PE film is used for separating the electrolyte. The cell was placed in a bakeThe temperature in the chamber was raised to 160 ℃ at 5 ℃/min and maintained, and the open circuit voltage of the cell during the temperature rise was recorded with a multimeter and discharged at a temperature of 160 ℃ at 0.5 ℃.
Example 6
A conductivity testing device, in which a PEO electrolyte with ion conducting function is sandwiched between two steel sheets, a physical barrier layer PE film is placed between one of the steel sheets and the PEO, the device is placed in an oven, the temperature is raised to 180 ℃ at the speed of 5 ℃/min, the conductivity of a new electrolyte system at different temperatures is tested and recorded, as shown in Table 2. The test result also shows that the PE film has the obstruction effect, so that the electrolyte does not have the ion transmission effect at normal temperature, the PE film is melted at high temperature, the ion path is conducted, and the system has the ion conductivity.
Table 2 conductivity of electrolyte at different temperatures in example 6
Example 7
The physical separation film PE films used in examples 1, 3 and 5 were used for thermal analysis, and the results are shown in fig. 3.
Table 3 shows the melting point ranges for several different polymers used as physical separators. Because different polymers have different melting points, and therefore the membranes have different phase transition temperatures, the activation temperature and the working temperature of the thermally activated battery can be flexibly adjusted by selecting different membranes.
TABLE 3 melting Point ranges for different polymers
| Class of polymers | 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 for illustrative purposes only, and therefore the scope of the invention should not be limited by this description, and all modifications made within the scope of the invention and the contents of the description should be considered within the scope of the invention.
Claims (8)
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 separating the positive electrode and the electrolyte; or between the negative electrode and the electrolyte to block the negative electrode from the electrolyte; or in the middle of the electrolyte, the electrolyte is divided into a first part in contact with the positive electrode and a second part in contact with the negative electrode, and the first part and the second part are separated by the physical barrier layer; and the physical barrier layer is capable of transforming from a solid phase to a liquid phase under heating at 300 ℃ or below.
2. A thermally activated battery structure as claimed in claim 1, wherein: the electrolyte is a continuous phase with ion conducting properties.
3. A thermally activated battery structure as claimed in claim 1, wherein: the physical barrier layer is one of a polymer film and an organic substance which can be converted from a solid phase to a liquid phase under heating.
4. A thermally activated battery structure as claimed in claim 3, wherein: the polymer film is composed of one of Polyethylene (PE), polypropylene (PP), polyvinyl chloride, polyimide poly, polyvinylidene chloride, polymethylpentene, polypropylene oxide, polyisobutylene, polyphosphate, polyvinylidene fluoride (PVDF), polyethylene glycol terephthalate (PET), polyethylene oxide, polyethylene glycol, polymethyl methacrylate (PMMA), Polyamide (PA), polytetrafluoroethylene, polysiloxane, polyacrylonitrile, polyvinyl butyral (PVB) and Polyurethane (PU).
5. A thermally activated battery structure as claimed in claim 3, wherein: the organic matter is one of Ethylene Carbonate (EC), paraffin and phenol.
6. A thermally activated battery structure as claimed in claim 1, wherein: the physical barrier is dense and does not have a pore structure.
7. A thermally activated battery structure as claimed in claim 1, wherein: the thickness of the physical barrier layer is 1nm-500 μm.
8. A thermally activated battery structure as claimed in claim 1, wherein: the thickness of the physical barrier layer is 1nm-10 μm when the physical barrier layer is a polymer film.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110231483.6A CN112952126A (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 CN112952126A (en) | 2021-03-02 | 2021-03-02 | Thermally activated battery structure and application thereof |
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| CN112952126A true CN112952126A (en) | 2021-06-11 |
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| CN202110231483.6A Pending CN112952126A (en) | 2021-03-02 | 2021-03-02 | Thermally activated battery structure and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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- 2021-03-02 CN CN202110231483.6A patent/CN112952126A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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