CN105789652A - Preparation method of thin monomer thermal battery - Google Patents
Preparation method of thin monomer thermal battery Download PDFInfo
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- CN105789652A CN105789652A CN201410814111.6A CN201410814111A CN105789652A CN 105789652 A CN105789652 A CN 105789652A CN 201410814111 A CN201410814111 A CN 201410814111A CN 105789652 A CN105789652 A CN 105789652A
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Abstract
The invention relates to a preparation method of a thin monomer thermal battery. The preparation method is characterized by comprising the following steps: covering a layer of anode thin film which is formed by an anode sizing agent on one surface of a current collector, covering a layer of electrolyte thin film which is formed by an electrolyte sizing agent on the anode thin film, and forming a composite thin film by the anode thin film and the electrolyte thin film; covering a cathode layer on the electrolyte thin film of the composite thin film, or setting the cathode layer on the electrolyte thin film of the composite thin film to finish the preparation process of the thin film monomer thermal battery. According to the preparation method, the composite thin film formed by the anode thin film and the electrolyte thin film is prepared by adopting coverage, so that the thickness of the monomer thermal battery is decreased, the repeatability is good, the preparation of electrolyte sheets with large areas or irregular shapes is simplified, the stability and discharge performance of the thermal battery are improved, the activation time of the thermal battery is shortened to 100ms, and the large-scale batched production is facilitated.
Description
Technical field
The invention belongs to technical field of chemical power, the preparation method particularly relating to a kind of slim switch-board thermoelectric pond.
Background technology
Thermal cell is a kind of reserve cell utilizing thermal source electrolytic salt fusing to be activated, and is widely used in each field, such as the electrical source of power of electronics and navigation system, aircraft emergency power supply, fire alarm power supply etc..Thermal cell is to be made up of assemblies such as activated ignition element, heating element heater, pile, insulation heat preservation layer and housings, the parallel overlap assembly of cell that wherein pile is made up of heating plate, flow collection sheet, electrode slice and electrolytic thin-membrane forms, and fixing is under a certain pressure packaged in housing.
The activationary time of thermal cell is one of important indicator evaluating thermal cell overall performance, and it refers to and starts to the running voltage of battery to reach the time needed for regulation lower limit from input activation signal.The activationary time of thermal cell is a multi-step process, under room temperature, thermal cell is in off working state, need during use to adopt electricity or mechanical system activated ignition element to be activated, to light heating element heater, thus producing substantial amounts of heat electrolytic salt is melted the ion conductor forming high conductivity, making battery activated and producing voltage.The speed of these steps is to be determined by burning and rate of heat transfer, and wherein the melting rate of electrolytic salt and the speed reaching operating temperature are the rate-determining steps of activation process.
The positive pole of currently known single cell of thermo battery and electrolyte are all prepared by the technique adopting powder pressing, activationary time is more than 200ms, and the wafer thickness that conventional powder shapes is generally higher than 254 μm, its thickness can not be too thin, otherwise mechanical strength is poor, it is not easy to compacting and the assembling of thermal cell, limit the optimization of activationary time and the development of thermal cell slimming, and also it is loaded down with trivial details to there is technique, efficiency is low, production environment requires height, it is difficult to realize large area or the making of irregularly shaped thermal cell.
Summary of the invention
The present invention solves that the technical problem existed in known technology provides thickness thin, mechanical strength original text, reproducible, the preparation process of large area or irregularly shaped electrolyte sheet is simple, the stability of thermal cell and discharge performance are high, activationary time is short, the preparation method being conducive to the slim switch-board thermoelectric pond of large-scale batch production.
The present invention includes following technical scheme:
The preparation method in slim switch-board thermoelectric pond, it is characterized in: include covering, in collector one side, the anode thin film that lid layer is formed by anode sizing agent, laminated film is constituted at the electrolytic thin-membrane that anode thin film overlying lid layer is formed by electrolyte slurry, described anode thin film and electrolytic thin-membrane；At the electrolytic thin-membrane overlying lid layer negative electrode layer of laminated film, or on the electrolytic thin-membrane of laminated film, it is equipped with one layer of negative electrode layer, namely completes the preparation process in thin film switch-board thermoelectric pond.
The present invention can also adopt following technical measures:
The described one method being covered as scraper cladding process, spray coating method, screen-printing deposition method or Best-Effort request cladding process.
The preparation process of described electrolytic thin-membrane:
(1) preparation binding agent
Polymer and organic solvent are configured to the binding agent that polymer residual is 5%-15%；
(2) electrolytic thin-membrane is prepared
It is 0.01-1:10 according to the mass ratio of polymer in 2 (1) binding agents Yu electrolytic salt, the binding agent (1) prepared and electrolytic salt are uniformly mixed into electrolyte slurry, electrolyte slurry is covered after on described anode thin film face, will be covered with the collector of electrolyte slurry and be placed in baking oven, heat 3-12 hour at 50-120 DEG C of temperature, after natural cooling, described anode thin film forms one layer of electrolytic thin-membrane.
Described polymeric material is cotton paper, polyimide fiber cloth, or the one that the mixing of cotton paper and polyimide fiber is weaved cotton cloth；Described inorganic material is the one of cellular glass fiber cloth, magnesia fibers cloth or alumina fibre cloth.
Described polymer is Kynoar (PVDF), Kynoar-hexafluoropropene (PVDF-HFP), politef (PTFE), polyethylene glycol oxide (PEO), sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone (PVP), polypropylene (PP), polyethylene (PE), polystyrene (PS), polyacrylonitrile (PAN), polrvinyl chloride (PVC), polyvinyl alcohol (PVA), the one of polyimides (PI) or polymethyl methacrylate (PMMA).
Described organic solvent is the one of N-Methyl pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, ethanol, acetonitrile, 1,3 dioxolanes, chloroform, oxolane.
Described electrolytic salt is the one of LiCl-KCl, LiCl-LiBr-LiF or LiCl-LiBr-LiI-KI-CsI.
The present invention has the advantage that and good effect:
The present invention adopts and covers the laminated film preparing anode thin film and electrolytic thin-membrane composition, reduce switch-board thermoelectric pond thickness, reproducible, simplify large area or the preparation of irregularly shaped electrolyte sheet, improve stability and the discharge performance of thermal cell, shorten the activationary time of thermal cell, to 100ms, large-scale batch production can be conducive to.
Accompanying drawing explanation
Fig. 1 is slim switch-board thermoelectric pool structure schematic diagram prepared by the present invention；
Fig. 2 is the cell constant-current discharge curve comparison figure that the present invention is prepared with known method.
In figure: 1-collector, 2-anode thin film, 3-electrolytic thin-membrane, 4-negative electrode layer.
Detailed description of the invention
For the summary of the invention of the present invention, feature and effect can be disclosed further, describe in detail as follows especially exemplified by following instance.
As shown in Figure 1, the preparation method in slim switch-board thermoelectric pond, it is characterized in: include covering, in collector 1 one side, the anode thin film 2 that lid layer is formed by anode sizing agent, laminated film is constituted at the electrolytic thin-membrane 3 that anode thin film overlying lid layer is formed by electrolyte slurry, described anode thin film and electrolytic thin-membrane；At the electrolytic thin-membrane overlying lid layer negative electrode layer 4 of laminated film, or on the electrolytic thin-membrane of laminated film, it is equipped with one layer of negative electrode layer, namely completes the preparation process in thin film switch-board thermoelectric pond.
The present invention can also adopt following technical measures:
The described one method being covered as scraper cladding process, spray coating method, screen-printing deposition method or Best-Effort request cladding process.
The preparation process of described electrolytic thin-membrane:
(1) preparation binding agent
Polymer and organic solvent are configured to the binding agent that polymer residual is 5%-15%；
(2) electrolytic thin-membrane is prepared
It is 0.01-1:10 according to the mass ratio of polymer in 2 (1) binding agents Yu electrolytic salt, the binding agent (1) prepared and electrolytic salt are uniformly mixed into electrolyte slurry, electrolyte slurry is covered after on described anode thin film face, will be covered with the collector of electrolyte slurry and be placed in baking oven, heat 3-12 hour at 50-120 DEG C of temperature, after natural cooling, described anode thin film forms one layer of electrolytic thin-membrane.
Described polymeric material is cotton paper, polyimide fiber cloth, or the one that the mixing of cotton paper and polyimide fiber is weaved cotton cloth；Described inorganic material is the one of cellular glass fiber cloth, magnesia fibers cloth or alumina fibre cloth.
Described polymer is Kynoar (PVDF), Kynoar-hexafluoropropene (PVDF-HFP), politef (PTFE), polyethylene glycol oxide (PEO), sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone (PVP), polypropylene (PP), polyethylene (PE), polystyrene (PS), polyacrylonitrile (PAN), polrvinyl chloride (PVC), polyvinyl alcohol (PVA), the one of polyimides (PI) or polymethyl methacrylate (PMMA).
Described organic solvent is the one of N-Methyl pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone, ethanol, acetonitrile, 1,3 dioxolanes, chloroform, oxolane.
Described electrolytic salt is the one of LiCl-KCl, LiCl-LiBr-LiF or LiCl-LiBr-LiI-KI-CsI.
Embodiment 1:
Step 1: make anode thin film
By positive active material FeS2, binding agent PTFE and conductive agent graphite be mixed into anode sizing agent, being coated with in the aluminum foil current collector 1 of 30 μ m-thick after treatment by anode sizing agent by Best-Effort request, be placed in baking oven by collector, 60 DEG C are heated 6 hours, naturally cool to room temperature, form anode thin film 2；
Step 2: make electrolytic thin-membrane
(1) preparation electrolyte slurry binding agent
According to weighing PVDF and organic solvent N-Methyl pyrrolidone respectively containing the ratio that PVDF mass concentration is 10%, PVDF is sufficiently mixed uniformly with N-Methyl pyrrolidone, is configured to electrolyte slurry binding agent；
(2) electrolytic thin-membrane is prepared
According to the ratio that mass ratio is 1:8 of PVDF in step 2 (1) binding agent Yu electrolytic salt LiCl-KCl, binding agent step 2 (1) prepared stirs 5 hours with LiCl-KCl, is uniformly mixed into electrolyte slurry；After electrolyte slurry being formed on anode thin film prepared by step 1 with scraper cladding process, the collector having slurry is placed in baking oven, heat 6 hours at 60 DEG C of temperature, after natural cooling, forming one layer of electrolytic thin-membrane on anode thin film, anode thin film and electrolytic thin-membrane on collector form laminated film；
Step 3: make one layer of cathode size on the electrolytic thin-membrane of laminated film with scraper cladding process, heating, layer after natural cooling, the electrolytic thin-membrane of laminated film is formed one layer of negative pole, completes the preparation process in the thin film switch-board thermoelectric pond of a kind of integration.
Embodiment 2:
Step 1: make anode thin film
By positive active material FeS2, binding agent PTFE and conductive agent graphite be mixed into anode sizing agent, being coated with in the aluminum foil current collector 1 of 30 μ m-thick after treatment by anode sizing agent by Best-Effort request, be placed in baking oven by collector, 60 DEG C are heated 6 hours, naturally cool to room temperature, form anode thin film 2；
Step 2: make electrolytic thin-membrane
(1) preparation electrolyte slurry binding agent
Weigh polyethylene glycol oxide (PEO) and organic solvent ethanol respectively according to containing the ratio that polyethylene glycol oxide (PEO) mass concentration is 10%, PEO is sufficiently mixed uniformly with ethanol, is configured to electrolyte slurry binding agent；
(2) electrolytic thin-membrane is prepared
According to the ratio that mass ratio is 1:5 of PEO in step 2 (1) binding agent Yu electrolytic salt LiCl-LiBr-LiF, binding agent step 2 (1) prepared stirs 5 hours with LiCl-LiBr-LiF, is uniformly mixed into electrolyte slurry；After electrolyte slurry being formed on anode thin film prepared by step 1 with scraper cladding process, the collector having slurry is placed in baking oven, heat 5 hours at 60 DEG C of temperature, after natural cooling, forming one layer of electrolytic thin-membrane on anode thin film, anode thin film and electrolytic thin-membrane on collector form laminated film；
Step 3: positive pole and electrolytical laminated film are tailored into or go out the pole piece of required size and shape with sheet-punching machine, then carries out cell assembling with negative electrode layer, complete the preparation process in thin film switch-board thermoelectric pond.
The switch-board thermoelectric pond that the thin film switch-board thermoelectric pond made of embodiment 1 and currently known pressing are made is adopted to carry out constant-current discharge test respectively, as shown in Figure 2, in figure, a curve is the switch-board thermoelectric pond constant-current discharge curve adopting currently known method to prepare, b curve is thin film switch-board thermoelectric pond constant-current discharge curve prepared by the present invention, result shows, adopt thin film switch-board thermoelectric pond activationary time prepared by the present invention can reach 100ms, much smaller than the activationary time of switch-board thermoelectric pond more than 200ms prepared by currently known pressing.
Although above the preferred embodiments of the present invention being described; but the invention is not limited in above-mentioned detailed description of the invention; above-mentioned detailed description of the invention is merely schematic; it is not restrictive; those of ordinary skill in the art is under the enlightenment of the present invention; without departing under present inventive concept and scope of the claimed protection situation, it is also possible to make a lot of form.These belong within protection scope of the present invention.
Claims (7)
1. the preparation method in slim switch-board thermoelectric pond, it is characterized in that: include covering, in collector one side, the anode thin film that lid layer is formed by anode sizing agent, laminated film is constituted at the electrolytic thin-membrane that anode thin film overlying lid layer is formed by electrolyte slurry, described anode thin film and electrolytic thin-membrane；At the electrolytic thin-membrane overlying lid layer negative electrode layer of laminated film, or on the electrolytic thin-membrane of laminated film, it is equipped with one layer of negative electrode layer, namely completes the preparation process in thin film switch-board thermoelectric pond.
2. the preparation method in slim switch-board thermoelectric pond according to claim 1, it is characterised in that: described in be covered as the one method of scraper cladding process, spray coating method, screen-printing deposition method or Best-Effort request cladding process.
3. the preparation method in slim switch-board thermoelectric pond according to claim 1 or claim 2, it is characterised in that: the preparation process of described electrolytic thin-membrane:
(1) preparation binding agent
Polymer and organic solvent are configured to the binding agent that polymer residual is 5%-15%；
(2) electrolytic thin-membrane is prepared
It is 0.01-1:10 according to the mass ratio of polymer in 2 (1) binding agents Yu electrolytic salt, the binding agent (1) prepared and electrolytic salt are uniformly mixed into electrolyte slurry, electrolyte slurry is covered after on described anode thin film face, will be covered with the collector of electrolyte slurry and be placed in baking oven, heat 3-12 hour at 50-120 DEG C of temperature, after natural cooling, described anode thin film forms one layer of electrolytic thin-membrane.
4. the preparation method in slim switch-board thermoelectric pond according to claim 3, it is characterised in that: described polymeric material is cotton paper, polyimide fiber cloth, or the one that the mixing of cotton paper and polyimide fiber is weaved cotton cloth；Described inorganic material is the one of cellular glass fiber cloth, magnesia fibers cloth or alumina fibre cloth.
5. the preparation method in slim switch-board thermoelectric pond according to claim 3, it is characterized in that: described polymer is Kynoar (PVDF), Kynoar-hexafluoropropene (PVDF-HFP), politef (PTFE), polyethylene glycol oxide (PEO), sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone (PVP), polypropylene (PP), polyethylene (PE), polystyrene (PS), polyacrylonitrile (PAN), polrvinyl chloride (PVC), polyvinyl alcohol (PVA), the one of polyimides (PI) or polymethyl methacrylate (PMMA).
6. the preparation method in slim switch-board thermoelectric pond according to claim 3, it is characterized in that: described organic solvent is N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide, acetone, ethanol, acetonitrile, 1,3 dioxolane, chloroform, oxolane one.
7. the preparation method in slim switch-board thermoelectric pond according to claim 3, it is characterised in that: described electrolytic salt is the one of LiCl-KCl, LiCl-LiBr-LiF or LiCl-LiBr-LiI-KI-CsI.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058147A (en) * | 2016-08-12 | 2016-10-26 | 中国科学院过程工程研究所 | Method for preparing CoS2 positive film of thermal battery through silk-screen printing |
| CN106207213A (en) * | 2016-09-09 | 2016-12-07 | 贵州梅岭电源有限公司 | A kind of quickly activation heat cell composite anode and preparation method thereof |
| CN106299397A (en) * | 2016-09-26 | 2017-01-04 | 贵州梅岭电源有限公司 | A kind of based on axis ignition channel design quickly respond thermal cell |
| CN107069059A (en) * | 2017-01-18 | 2017-08-18 | 沈阳理工大学 | Thermal battery activating device based on PVDF thin film |
| CN107293763A (en) * | 2017-06-16 | 2017-10-24 | 沈阳崇华电子科技有限公司 | One kind carries the poroid filming switch-board thermoelectric pool preparation method in center |
| CN109616678A (en) * | 2018-12-03 | 2019-04-12 | 华中科技大学 | A kind of high Seebeck coefficient water system heat chemistry battery and device |
| CN110890564A (en) * | 2019-11-29 | 2020-03-17 | 贵州梅岭电源有限公司 | Preparation method of co-heating multi-monomer for thermal battery |
| CN114927711A (en) * | 2022-05-16 | 2022-08-19 | 中国工程物理研究院电子工程研究所 | Thermal battery flexible electrolyte sheet, preparation method thereof and thermal battery |
| CN114927711B (en) * | 2022-05-16 | 2024-04-26 | 中国工程物理研究院电子工程研究所 | Thermal battery flexible electrolyte sheet, preparation method thereof and thermal battery |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058147B (en) * | 2016-08-12 | 2019-05-24 | 中国科学院过程工程研究所 | A kind of silk-screen printing prepares thermal cell CoS2The method of anode thin film |
| CN106058147A (en) * | 2016-08-12 | 2016-10-26 | 中国科学院过程工程研究所 | Method for preparing CoS2 positive film of thermal battery through silk-screen printing |
| CN106207213A (en) * | 2016-09-09 | 2016-12-07 | 贵州梅岭电源有限公司 | A kind of quickly activation heat cell composite anode and preparation method thereof |
| CN106207213B (en) * | 2016-09-09 | 2018-09-07 | 贵州梅岭电源有限公司 | A kind of quick activation heat cell composite anode and preparation method thereof |
| CN106299397A (en) * | 2016-09-26 | 2017-01-04 | 贵州梅岭电源有限公司 | A kind of based on axis ignition channel design quickly respond thermal cell |
| CN107069059A (en) * | 2017-01-18 | 2017-08-18 | 沈阳理工大学 | Thermal battery activating device based on PVDF thin film |
| CN107069059B (en) * | 2017-01-18 | 2023-05-09 | 沈阳理工大学 | Thermal battery activation device based on PVDF film |
| CN107293763B (en) * | 2017-06-16 | 2019-03-26 | 沈阳崇华电子科技有限公司 | One kind having the poroid filming switch-board thermoelectric pool preparation method in center |
| CN107293763A (en) * | 2017-06-16 | 2017-10-24 | 沈阳崇华电子科技有限公司 | One kind carries the poroid filming switch-board thermoelectric pool preparation method in center |
| CN109616678A (en) * | 2018-12-03 | 2019-04-12 | 华中科技大学 | A kind of high Seebeck coefficient water system heat chemistry battery and device |
| CN109616678B (en) * | 2018-12-03 | 2020-10-02 | 华中科技大学 | high-Seebeck-coefficient water-based thermochemical battery and device |
| CN110890564A (en) * | 2019-11-29 | 2020-03-17 | 贵州梅岭电源有限公司 | Preparation method of co-heating multi-monomer for thermal battery |
| CN110890564B (en) * | 2019-11-29 | 2021-01-05 | 贵州梅岭电源有限公司 | Preparation method of co-heating multi-monomer for thermal battery |
| CN114927711A (en) * | 2022-05-16 | 2022-08-19 | 中国工程物理研究院电子工程研究所 | Thermal battery flexible electrolyte sheet, preparation method thereof and thermal battery |
| CN114927711B (en) * | 2022-05-16 | 2024-04-26 | 中国工程物理研究院电子工程研究所 | Thermal battery flexible electrolyte sheet, preparation method thereof and thermal battery |
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