CN113328109A - Heat slow-release element with laminated structure and application thereof in thermal battery - Google Patents

Heat slow-release element with laminated structure and application thereof in thermal battery Download PDF

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Publication number
CN113328109A
CN113328109A CN202110602929.1A CN202110602929A CN113328109A CN 113328109 A CN113328109 A CN 113328109A CN 202110602929 A CN202110602929 A CN 202110602929A CN 113328109 A CN113328109 A CN 113328109A
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lithium
solid solution
heat
layer
release element
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CN202110602929.1A
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CN113328109B (en
Inventor
曹勇
崔益秀
王超
阎红卫
刘鸿雁
魏晓春
崔艳华
兰伟
杨开敏
高晨阳
刘效疆
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Institute of Electronic Engineering of CAEP
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Institute of Electronic Engineering of CAEP
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    • 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
    • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
    • H01M6/5038—Heating or cooling of cells or batteries
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a heat slow-release element with a layered structure and application thereof in a thermal battery, belonging to the technical field of thermal batteries. The layered heat slow-release element disclosed by the invention is sequentially provided with the oxidant layer, the lithium permeable thin layer and the reducing agent layer, the lithium permeable thin layer is constructed by adopting an ion-electron conductor, and the transmission speed of lithium in the lithium permeable thin layer is controlled, so that the reaction speed between the oxidant and the reducing agent in the heat slow-release element is controlled, the heat release rate of the heat slow-release element is further controlled, and the accurate control of the internal temperature of a thermal battery is realized, so that when the layered heat slow-release element is applied to a thermal battery product, the performance of the thermal battery is obviously improved, and the layered heat slow-release element has a wide application prospect.

Description

Heat slow-release element with laminated structure and application thereof in thermal battery
Technical Field
The invention relates to the technical field of thermal batteries, in particular to a heat slow-release element with a layered structure and application thereof in a thermal battery.
Background
The thermal battery is composed of positive electrode, electrolyte, negative electrode and heating material, and features short activation time, long storage time, wide working temp range and high specific power.
At present, the thermal battery mainly adopts Fe/KClO4As a heating material, the internal temperature of the thermal battery is rapidly raised to the working temperature by one-time heating. In the working process of the thermal battery, the internal heat of the thermal battery is gradually released outwards, and the internal temperature of the thermal battery is caused to continuously decrease, so that the discharge performance of the thermal battery is remarkably reduced. By adopting the aerogel, the vacuum heat-insulating shell and other heat-insulating materials, the internal temperature drop rate of the thermal battery can be slowed down, but the internal temperature drop rate of the thermal battery can still be reducedThe requirement of the medium-and long-service-life thermal battery on internal temperature control is difficult to meet, and the volume of the thermal battery is also obviously increased. In view of the above, the present invention provides a heat slow-release element capable of slowly and continuously supplying heat, which realizes continuous and slow supply of heat by controlling the oxidation reaction speed between an oxidant and a reductant in a lithium permeable thin film, so as to realize accurate control of the internal temperature of a thermal battery without significantly increasing the volume of the thermal battery, and further realize great improvement of the discharge performance of the thermal battery.
Disclosure of Invention
In view of the above disadvantages or shortcomings, an object of the present invention is to provide a heat slow-releasing element with a layered structure, which can effectively solve the problems of a fast internal temperature drop rate during the operation of a thermal battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a heat slow-release element with a layered structure, which is sequentially provided with an oxidant layer, a lithium permeable thin layer and a reducing agent layer.
Further, the oxidant layer includes an oxidant and a lithium ion conductor.
Further, the reducing agent layer includes an oxidizing agent and a lithium ion conductor.
Further, the "lithium-permeable" thin layer includes a lithium ion conductor and an electron conductor.
Further, the electron conductor is CeO2And its solid solution, Gd2O3And solid solution of the same, Sm2O3And solid solutions thereof.
Further, the lithium ion conductor includes a lithium metal salt and a functional assistant.
Specifically, the lithium metal salt in the oxidant layer, the lithium permeable thin layer and the reducing agent layer is respectively and independently selected from LiF, LiCl, LiBr, LiI and Li2CO3、Li2SO4、Li3PO4、LiPO3At least one of (1).
Specifically, functional auxiliary agents in the oxidant layer, the lithium permeable thin layer and the reducing agent layerEach independently selected from KF, KCl, KBr, KI and K2CO3、K2SO4、K3PO4、KPO3、NaF、NaCl、NaBr、NaI、Na2CO3、Na2SO4、Na3PO4、NaPO3At least one of (1).
Further, an oxidant of the oxidant layer of the heat slow-release element adopts FeS and a solid solution thereof, and FeS2And solid solution thereof, CoS and solid solution thereof, Co3S4And solid solution thereof, CoS2And solid solution thereof, NiS2And solid solution thereof, PbS and solid solution thereof, CuS and solid solution thereof, CuSe compound and solid solution thereof, CuO and solid solution thereof, Cu2O and its solid solution, Ag2S and its solid solution, Ag2O and solid solutions thereof.
Further, the reducing agent layer reducing agent of the heat slow-release element adopts at least one of Li and its alloy and alloy composite.
Further, the Li alloy is selected from Li-Si, Li-B, Li-Si, Li-Al, Li-Fe.
Furthermore, the mass ratio of the lithium ion conductor in the lithium permeable thin layer of the heat slow release element is 25-80 wt%, and the mass ratio of the electron conductor is 20-75 wt%.
Further, the proportion of the lithium metal salt in the lithium ion conductor is 20-100 wt.%, and the proportion of the functional auxiliary agent is 0-80 wt.%.
Furthermore, the mass ratio of the oxidant in the oxidant layer is 60-100 wt.%, and the mass ratio of the lithium ion conductor is 0-40 wt.%.
Furthermore, the mass ratio of the reducing agent in the reducing agent layer is 60-100 wt.%, and the mass ratio of the lithium ion conductor is 0-40 wt.%.
Further, the weight of the oxidant of the heat slow-release element per unit area is 0.01-5 g/cm2The weight per unit area of the lithium-permeable thin layer is 0.01 to 1g/cm2The weight of the reducing agent is 0.01-5 g/cm2。
The heat releasing element with a laminated structure can be prepared by adopting any one of the following modes:
1. adopting a layer-by-layer pressing method;
2. powder can be spread layer by layer and then integrally pressed;
3. it is also possible to use individual pressing of each layer and then assembling them together.
The preparation method of the lithium permeable thin-layer material is to mix the lithium ion conductor, the electronic conductor and the additive which can better realize the beneficial effects of the invention, the mixing method comprises three-dimensional mixing, ball milling mixing, hand milling and the like, and all methods for uniformly mixing the materials can be used.
The preparation method of the oxidant layer and the reducing agent layer comprises the step of mixing the oxidant or the reducing agent and the additive which can better realize the beneficial effect of the invention, wherein the mixing method comprises three-dimensional mixing, ball milling, hand milling and the like, and all methods for uniformly mixing materials can be used.
The invention further discloses the application of the heat slow-release element with the laminated structure in a thermal battery.
The invention has the following advantages:
the invention adopts a method of mixing an electronic conductor and an ionic conductor to construct an ion-electron conductive mixed thin layer, controls the transmission rate of lithium ions and electrons in the thin layer through the design of the components of the thin layer, thereby regulating and controlling the diffusion rate of lithium, controlling the oxidation-reduction speed between an oxidant layer oxidant and a reductant layer reductant in a heat slow-release element, further realizing the continuous slow supply of the heat slow-release element in a thermal battery, slowing down the temperature reduction rate in the thermal battery and realizing the relatively accurate regulation and control of the temperature in the thermal battery, and greatly improving the performance of the thermal battery when the heat slow-release element with a layered structure is applied to a thermal battery product.
Drawings
FIG. 1 is a schematic structural view of a heat-releasing element having a layered structure according to the present invention, which is composed of an oxidant layer, a lithium-permeable thin layer, and a reductant layer;
FIG. 2 is a graph showing the heat release rate of the layered heat releasing element according to example 1 of the present invention at 450 ℃ in Ar over time;
fig. 3 is a graph comparing the internal temperature of a thermal battery using the layered heat release member in examples 1 and 2 of the present invention with the internal temperature of a thermal battery without the layered heat release member.
Detailed Description
The design idea of the heat slow-release element is to control the oxidation-reduction reaction speed by building a lithium permeable thin layer between an oxidant and a reducing agent, thereby playing the roles of temperature regulation and control and heat supply in a thermal battery. Specifically, the invention controls the lithium penetration rate of lithium in the lithium-permeable thin layer by controlling the conductivity characteristic of the lithium-permeable thin layer, and controls the supply speed of a reducing agent reactant lithium when the reducing agent reactant lithium contacts with an oxide, thereby controlling the reaction speed of an oxidizing agent and a reducing agent.
Example 1
The embodiment provides a heat slow-release element with a laminated structure and application thereof in a thermal battery, comprising:
1) heat-releasing element having a layered structure: the lithium-ion battery is prepared by pressing 0.2g of reducing agent powder, 0.3g of lithium-permeable thin-layer powder and 0.3g of oxidant powder in a cold isostatic pressing mode, wherein the reducing agent is Li-Si alloy (44 wt.% Li), and the lithium-permeable thin-layer powder is prepared from 40 wt.% of LiCl-37 wt.% of LiBr-52 wt.% of KBr and 60 wt.% of CeO2The oxidant powder consists of 80 wt.% CuO and 20 wt.% LiCl-KCl-LiBr.
2) Thermal battery containing layered heat release element: except that two layered heat slow-release elements are respectively arranged at two ends of a thermal battery unit cell stack body, the manufacturing and assembling processes of the traditional thermal battery are kept consistent in other aspects.
Example 2
The embodiment provides a heat slow-release element with a laminated structure and application thereof, comprising:
1) heat-releasing element having a layered structure: 0.3g of reducing agent powder and 0.4g of lithium-permeable filmLayer powder, 0.4g oxidant powder, pressed in cold isostatic pressing mode, where the reducer is Li-B alloy (55 wt.% Li), and the Li-permeable thin layer powder is formed by 50 wt.% LiCl-55 wt.% KCl and 50 wt.% Sm2O3The oxidant powder is CuO;
2) thermal battery containing layered heat release element: except that two layered heat slow release elements are respectively arranged at two ends of a thermal battery unit cell stack body, and one layered heat slow release element is arranged in the middle of the thermal battery stack body, the manufacturing and assembling processes of the traditional thermal battery are kept consistent in other aspects.
The foregoing is merely exemplary and illustrative of the present invention and it is within the purview of one skilled in the art to modify or supplement the embodiments described or to substitute similar ones without the exercise of inventive faculty, and still fall within the scope of the claims.

Claims (10)

1. A heat-spreading element having a layered structure, characterized in that: the heat slow release element is sequentially provided with an oxidant layer, a lithium permeable thin layer and a reducing agent layer.
2. A heat-spreading element having a layered structure as claimed in claim 1 wherein: the oxidant layer includes an oxidant and a lithium ion conductor; the reducing agent layer includes an oxidizing agent and a lithium ion conductor; the lithium-permeable thin layer includes a lithium ion conductor and an electron conductor.
3. A heat quantity release member having a layered structure as claimed in claim 1 or 2, wherein: the lithium ion conductor comprises a lithium metal salt and a functional auxiliary agent; the lithium metal salt in the oxidant layer, the lithium permeable thin layer and the reducing agent layer are respectively and independently selected from LiF, LiCl, LiBr, LiI and Li2CO3、Li2SO4、Li3PO4、LiPO3At least one of; the functional additives in the oxidant layer, the lithium-permeable thin layer and the reducing agent layer are respectively and independently selected from KF, KCl, KBr, KI and K2CO3、K2SO4、K3PO4、KPO3、NaF、NaCl、NaBr、NaI、Na2CO3、Na2SO4、Na3PO4、NaPO3At least one of (1).
4. A heat quantity release element having a layered structure as claimed in any one of claims 1 to 3, wherein: the electron conductor in the lithium-permeable thin layer is CeO2And its solid solution, Gd2O3And solid solution of the same, Sm2O3And solid solutions thereof.
5. A heat releasing element having a layered structure as claimed in any one of claims 1 to 4, wherein: the oxidant of the oxidant layer adopts FeS and solid solution thereof, FeS2And solid solution thereof, CoS and solid solution thereof, Co3S4And solid solution thereof, CoS2And solid solution thereof, NiS2And solid solution thereof, PbS and solid solution thereof, CuS and solid solution thereof, CuSe compound and solid solution thereof, CuO and solid solution thereof, Cu2O and its solid solution, Ag2S and its solid solution and Ag2O and solid solutions thereof.
6. A heat releasing element having a layered structure as claimed in any one of claims 1 to 5, wherein: the reducing agent layer reducing agent adopts at least one of Li, Li alloy and Li alloy composite; the Li alloy is selected from Li-Si, Li-B, Li-Si, Li-Al and Li-Fe.
7. A heat quantity release element with laminated structure according to any one of claims 2 to 6, wherein the lithium ion conductor in said lithium permeable thin layer accounts for 25 to 80 wt.%; the mass ratio of the electronic conductor is 20-75 wt.%.
8. A heat releasing element having a layered structure as claimed in any one of claims 3 to 7, wherein: the proportion of the lithium metal salt in the lithium ion conductor is 20-100 wt.%, and the proportion of the functional auxiliary agent is 0-80 wt.%.
9. A heat releasing element having a layered structure as claimed in any one of claims 1 to 8, wherein: the unit area weight of the lithium-permeable thin layer of the heat slow-release element is 0.01-1 g/cm2(ii) a The weight per unit area of the reducing agent layer is 0.01-5 g/cm2(ii) a The weight per unit area of the oxidant layer is 0.01 to 5g/cm2。
10. Use of a heat slow-release element having a layered structure according to any one of claims 1 to 9 in a thermal battery.
CN202110602929.1A 2021-05-25 2021-05-31 Heat slow-release element with laminated structure and application thereof in thermal battery Active CN113328109B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114735359A (en) * 2022-04-12 2022-07-12 南京艾科美热能科技有限公司 Long-time heat release type vessel

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5539132A (en) * 1978-09-11 1980-03-18 Matsushita Electric Ind Co Ltd Thermal battery
JPS6077362A (en) * 1983-10-04 1985-05-01 Nippon Kayaku Co Ltd Heating element for molten salt battery and its manufacture
CN107732268A (en) * 2017-11-23 2018-02-23 上海空间电源研究所 A kind of cell of carrier rocket thermal cell
CN108039468A (en) * 2017-12-06 2018-05-15 贵州梅岭电源有限公司 One kind is suitable for long-time end heavy-current discharge thermal cell composite positive pole
CN108878917A (en) * 2018-06-28 2018-11-23 贵州梅岭电源有限公司 A kind of thermal cell sustained release heating plant
CN111613797A (en) * 2020-05-27 2020-09-01 贵州梅岭电源有限公司 Self-heat-release high-potential cathode material for thermal battery and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5539132A (en) * 1978-09-11 1980-03-18 Matsushita Electric Ind Co Ltd Thermal battery
JPS6077362A (en) * 1983-10-04 1985-05-01 Nippon Kayaku Co Ltd Heating element for molten salt battery and its manufacture
CN107732268A (en) * 2017-11-23 2018-02-23 上海空间电源研究所 A kind of cell of carrier rocket thermal cell
CN108039468A (en) * 2017-12-06 2018-05-15 贵州梅岭电源有限公司 One kind is suitable for long-time end heavy-current discharge thermal cell composite positive pole
CN108878917A (en) * 2018-06-28 2018-11-23 贵州梅岭电源有限公司 A kind of thermal cell sustained release heating plant
CN111613797A (en) * 2020-05-27 2020-09-01 贵州梅岭电源有限公司 Self-heat-release high-potential cathode material for thermal battery and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114735359A (en) * 2022-04-12 2022-07-12 南京艾科美热能科技有限公司 Long-time heat release type vessel

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