CN110459779A - A kind of high temperature high-energy battery and preparation method thereof - Google Patents

A kind of high temperature high-energy battery and preparation method thereof Download PDF

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Publication number
CN110459779A
CN110459779A CN201910806781.6A CN201910806781A CN110459779A CN 110459779 A CN110459779 A CN 110459779A CN 201910806781 A CN201910806781 A CN 201910806781A CN 110459779 A CN110459779 A CN 110459779A
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nitric acid
high temperature
lino
kno
alloy
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CN201910806781.6A
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赵宇宏
牛永强
侯华
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North University of China
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North University of China
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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
    • H01M6/005—Devices for making primary cells
    • 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

Abstract

The invention discloses a kind of high temperature high-energy batteries and preparation method thereof, belong to thermal cell technical field.A kind of high temperature high-energy battery, negative electrode material are Li-Mg-B alloy, Li (B) alloy, Li (Si) alloy or Li (Al) alloy；Electrolyte is LiNO3‑KNO3‑Mg(NO3)2Ternary nitric acid congruent melting salt or LiNO3‑KNO3‑Mg(NO3)2‑Ca(NO3)2Quaternary nitric acid congruent melting salt；Positive electrode is MnO2、V2O5、PbO2、LiCoO2、LiMn2O4、CrO2、Ag2CrO4The oxide anode material compatible with nitric acid congruent melting salt.Battery of the present invention can use in 150 ~ 400 DEG C of temperature ranges, while open-circuit voltage with higher and higher initial discharge voltage platform, have a wide range of application.

Description

A kind of high temperature high-energy battery and preparation method thereof
Technical field
The invention belongs to thermal cell technical field, it is related to a kind of high temperature high energy electricity of operating temperature between 150 ~ 400 DEG C Pond and preparation method thereof.
Background technique
21 century is that an energy accounts for the leading epoch, and with the reduction of the energy, people are to find new petroleum, just must Deeper stratum must be explored, the operating temperature of oil exploration at present may be up to 250 DEG C, but with the intensification of depth of exploration, exploration Operating temperature is also constantly increasing.Geothermal energy is stored in underground, not the influence of climate condition, can not only be used for base load energy, Also can be used as peak load can use, therefore from its development and utilization at originally, geothermal energy resources are relative to other renewable energy More there is development potentiality, and geothermal exploration operating temperature may be up to 250 ~ 400 DEG C.
The data in record exploration process are measured, just necessary promising recording equipment provides the battery of the energy.Business at present The operating temperatures such as electrochemical cell such as lithium ion battery, fuel cell are -55 ~ 70 DEG C, highest Li-Mg/SOCl2Battery is up to 180 DEG C, Li-Mg/SOCl2Battery operating temperature is up to 200 DEG C；And the battery that military field generally uses is thermal cell, work 350 ~ 600 DEG C are up to as temperature；But for the battery or blank out to work between 200 ~ 350 DEG C.
Currently, the battery for being applied to petroleum gas gun drilling exploring equipment is the Li-Mg/SOCl after improving2Battery, by The manufacture of Battery Engineering, Inc. (Canton, MA) company.Operating temperature in geothermal borehole can be more than 300 DEG C, using with Dewar bottles of expensive metal vacuum by Li-Mg/SOCl2The skill of battery and the isolation of high ambient temperatures environment Art, but this is also along with a large amount of consumption of production cost greatly improved with the energy.It would therefore be highly desirable to develop a kind of novel economy Practical high temperature high-energy battery come replace tradition fall behind battery technology, with meet in 150 ~ 350 DEG C or so working environments Exploring equipment stablizes energy supply, the demand to high-temperature battery such as Detection system for automobile tyre, underground manometer.
Thermal cell is also known as heat activated battery, it is to use fuse salt as electrolyte, reaches battery temperature with internal heat resource Predetermined work temperature and the former battery to work.Heat activation and long term storage are two big features of thermal cell, and thermal cell has Have it is very reliable, durable, if be sealed, storage life up to 25 years or more long；In addition thermal cell have specific energy it is high, The advantages that specific power is big, discharge rate is fast, use environment temperature is wide.
In order to solve defect of the existing technology, the present invention uses for reference thermoelectricity pool technology, develop one kind can be used for 150 ~ High temperature high-energy battery in 400 DEG C or so working environments.
Summary of the invention
The object of the present invention is to provide a kind of high temperature high-energy batteries.
It is a further object to provide the preparation methods of above-mentioned high temperature high-energy battery.
The present invention is achieved by the following technical solutions:
A kind of high temperature high-energy battery,
A kind of high temperature high-energy battery, negative electrode material are Li-Mg-B alloy, Li (B) alloy, Li (Si) alloy or Li (Al) alloy；
Electrolyte is LiNO3-KNO3-Mg(NO3)2Ternary nitric acid congruent melting salt or LiNO3-KNO3-Mg(NO3)2-Ca(NO3)2 Quaternary nitric acid congruent melting salt；
Positive electrode is MnO2、V2O5、PbO2、LiCoO2、LiMn2O4、CrO2、Ag2CrO4The oxide compatible with nitric acid congruent melting salt Positive electrode.
Further, the electrolyte is LiNO3-KNO3-Mg(NO3)2Ternary nitric acid congruent melting salt, and the ternary Nitric acid congruent melting salt is grouped as by each group of following mass fraction:
LiNO3, 5 ~ 65；
KNO3, 30 ~ 90；
Mg(NO3)2, 1 ~ 25.
The electrolyte is LiNO3-KNO3-Mg(NO3)2-Ca(NO3)2Quaternary nitric acid congruent melting salt, the quaternary nitric acid Congruent melting salt is grouped as by each group of following mass fraction:
LiNO3, 10 ~ 65%；
KNO3, 25 ~ 75%；
Mg(NO3)2, 1 ~ 15%；
Ca(NO3)2, 1 ~ 15%.
Further, it is prepared when preparation using piece type technique, step are as follows: alloy anode piece is made in negative electrode material；It will just Pole material, electrolyte, conductive additive are uniformly mixed, and are pressed into positive plate；It is the MgO and electricity of 3 ~ 4:6 ~ 7 by mass ratio Material is solved at 300 DEG C after melting 15-17 hours, grinding sieves with 100 mesh sieve, the electrolyte sheet of tabletted type.
Wherein, the conductive additive is one of graphite, carbon nanotube, graphene, acetylene black or any several Mixture.
304 stainless steel substrates using 0.1 mm thickness make flow collection sheet.
The thickness of alloy anode piece be preferably 0.3 ~ 1.0mm.
High temperature high-energy battery of the invention includes cathode, molten salt electrolyte and anode, and wherein negative electrode material is using Li- The lithium alloys such as Mg-B alloy, Li (B) alloy, Li (Si) alloy, Li (Al) alloy, but not limited to this；Electrolyte uses Be LiNO3-KNO3-Mg(NO3)2Ternary nitric acid congruent melting salt or LiNO3-KNO3-Mg(NO3)2-Ca(NO3)2Quaternary nitric acid congruent melting Salt；Positive electrode then can be MnO2、V2O5、PbO2、LiCoO2、LiMn2O4、CrO2、Ag2CrO4Deng the oxidation compatible with nitrate Object positive electrode, but not limited to this；In use, high temperature high-energy battery of the present invention can make in 150 ~ 400 DEG C of temperature ranges With, and higher open-circuit voltage and higher initial discharge voltage platform are generated, such as: Li-Mg-B alloy/LiNO3- KNO3-Mg (NO3)2/MnO2Monocell or Li-Mg-B alloy/LiNO3-KNO3- Mg(NO3)2-Ca(NO3)2/MnO2Monocell can produce The open-circuit voltage of 3.0 ~ 3.5 V, and in 5 mA/cm2Under discharge rate, initial discharge voltage platform can be higher than 3.0 V.
Compared with prior art, the invention has the following advantages that
1) compared with traditional commerce electrochemical cell (operating temperature -55 ~ 70 DEG C) and thermal cell (operating temperature is up to 350 ~ 550 DEG C), Battery of the present invention can use in 150 ~ 400 DEG C of temperature ranges, while open-circuit voltage with higher and higher initial discharge Voltage platform；
2) have a wide range of application, can not only stablize to exploring equipment and energize, but also can be used for Detection system for automobile tyre, underground survey pressure Meter etc.；
3) specific energy is high, specific power is big, discharge rate is fast, long service life.
Detailed description of the invention
Fig. 1 is the high temperature high-energy battery of the preparation of embodiment 1 in 150 DEG C and 5 mA/cm2Discharge rate under voltage-appearance Measure curve；
Fig. 2 is the high temperature high-energy battery of the preparation of embodiment 2 in 350 DEG C and 5 mA/cm2Discharge rate under voltage-capacity it is bent Line；
Fig. 3 is the high temperature high-energy battery of the preparation of embodiment 3 in 200 DEG C and 5 mA/cm2Discharge rate under voltage-capacity it is bent Line；
Fig. 4 is the high temperature high-energy battery of the preparation of embodiment 4 in 150 DEG C and 5 mA/cm2Discharge rate under voltage-capacity it is bent Line；
Fig. 5 is the high temperature high-energy battery of the preparation of embodiment 5 in 350 DEG C and 5 mA/cm2Discharge rate under voltage-capacity it is bent Line；
Fig. 6 is the high temperature high-energy battery of the preparation of embodiment 6 in 250 DEG C and 5 mA/cm2Discharge rate under voltage-capacity it is bent Line.
Specific embodiment
With reference to embodiments and attached drawing the present invention is described in further detail.
Embodiment 1
A kind of high temperature high-energy battery, negative electrode material are Li-Mg-B alloys, and positive electrode is MnO2, electrolyte is LiNO3-KNO3-Mg(NO3)2, mass percent is the ternary nitric acid congruent melting salt of 25%- 60%-15%.
When preparation, using 0.4 mm thickness, 16 mm diameters weigh 0.08 g, and mass percent is the Li- of 62%-4%-34% Mg-B alloy makees negative electrode tab；Use mass ratio for the LiNO of 35:653-KNO3-Mg(NO3)2(25:60:15) molten salt electrolyte exists After 300 DEG C melt 16 hours, grinds, sieve with 100 mesh sieve, and depress to the electrolyte sheet of 15.5 mm of diameter in 296 MPa pressure； The MnO for the use of mass ratio being 70:20:102: LiNO3-KNO3- Mg(NO3)2(25:60:15) molten salt electrolyte and graphite are 296 MPa pressure depresses to the positive plate of 15.5 mm of diameter；Using 0.1 mm thickness, 304 stainless steel substrates of 20 mm diameters make flow collection sheet.
Using LAND CT2001A battery test system to above-mentioned monocell at 150 DEG C, 5 mA/cm2Discharge rate under Discharge performance tested, test results are shown in figure 1, and the monocell open-circuit voltage is in 3.0 V or so, initial discharge voltage Platform is 2.5 V or so, while there is also a discharge voltage plateaus of 1.2 V or so.
Embodiment 2
A kind of high temperature high-energy battery, negative electrode material are Li-Mg-B alloys, and positive electrode is V2O5, electrolyte is LiNO3- KNO3-Mg(NO3)2, mass percent is the ternary nitric acid congruent melting salt of 65:30:1.
Using LAND CT2001A battery test system to above-mentioned monocell at 350 DEG C, 5 mA/cm2Discharge rate under Discharge performance tested, test results are shown in figure 2, and the monocell open-circuit voltage is in 3.3 V or so, initial discharge voltage Platform is 3.1 V or so, while there is also two discharge voltage plateaus of 2.7 V and 2.0 V or so.
Embodiment 3
A kind of high temperature high-energy battery, negative electrode material are Li-Mg-B alloys, and positive electrode is LiCoO2, electrolyte is LiNO3-KNO3-Mg(NO3)2(5:90:25) ternary nitric acid congruent melting salt.
Using LAND CT2001A battery test system to above-mentioned monocell at 200 DEG C, 5 mA/cm2Discharge rate under Discharge performance tested, test results are shown in figure 3, and the monocell open-circuit voltage is in 3.5 V or so, initial discharge voltage Platform is 3.0 V or so, while there is also two discharge voltage plateaus of 2.8 V and 2.0 V or so.
Embodiment 4
A kind of high temperature high-energy battery, negative electrode material are Li (Al) alloys, and positive electrode is LiMn2O4, electrolyte is LiNO3-KNO3-Mg(NO3)2-Ca(NO3)2(60:25:5:15) ternary nitric acid congruent melting salt.
Using 0.4 mm thickness, 16 mm diameters, Li (Al) Alloy for weighing 0.08 g makees negative electrode tab；Using 35% MgO With 65% LiNO3-KNO3-Mg(NO3)2-Ca(NO3)2(60:25:5:15) molten salt electrolyte is ground after 300 DEG C melt 16 hours It is broken, it sieves with 100 mesh sieve, and depress to the electrolyte sheet of 15.5 mm of diameter in 296 MPa pressure；Use LiMn2O4As positive plate； Using 0.1 mm thickness, 304 stainless steel substrates of 20 mm diameters make flow collection sheet.
Using LAND CT2001A battery test system to above-mentioned monocell at 150 DEG C, 5 mA/cm2Discharge rate under Discharge performance tested, test results are shown in figure 4, and the monocell open-circuit voltage is in 3.5 V or so, initial discharge voltage Platform is 2.9 V or so, while there is also a discharge voltage plateaus of 2.2 V or so.
Embodiment 5
A kind of high temperature high-energy battery, negative electrode material are Li (Si) alloys, and positive electrode is CrO2,
Electrolyte is LiNO3-KNO3-Mg(NO3)2-Ca(NO3)2(10:50:15:1) ternary nitric acid congruent melting salt.
Using LAND CT2001A battery test system to above-mentioned monocell at 350 DEG C, 5 mA/cm2Discharge rate under Discharge performance tested, test results are shown in figure 5, and the monocell open-circuit voltage is in 3.3 V or so, initial discharge voltage Platform is 2.9 V or so, while there is also a discharge voltage plateaus of 2.0 V or so.
Embodiment 6
A kind of high temperature high-energy battery, negative electrode material are Li (B) alloys, and positive electrode is Ag2CrO4, electrolyte is LiNO3-KNO3-Mg(NO3)2-Ca(NO3)2(65:75:1:10) ternary nitric acid congruent melting salt.
Using LAND CT2001A battery test system to above-mentioned monocell at 250 DEG C, 5 mA/cm2Discharge rate under Discharge performance tested,.Test results are shown in figure 6, and the monocell open-circuit voltage is in 3.4 V or so, initial discharge electricity Flattening bench is 3.2 V or so, while there is also two discharge voltage plateaus of 2.7V and 1.7V or so.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (7)

1. a kind of high temperature high-energy battery, it is characterised in that:
Negative electrode material is Li-Mg-B alloy, Li (B) alloy, Li (Si) alloy or Li (Al) alloy；
Electrolyte is LiNO3-KNO3-Mg(NO3)2Ternary nitric acid congruent melting salt or LiNO3-KNO3-Mg(NO3)2-Ca(NO3)2Four First nitric acid congruent melting salt；
Positive electrode includes MnO2、V2O5、PbO2、LiCoO2、LiMn2O4、CrO2Or Ag2CrO4The oxygen compatible with nitric acid congruent melting salt Compound.
2. high temperature high-energy battery according to claim 1, it is characterised in that:
The electrolyte is LiNO3-KNO3-Mg(NO3)2Ternary nitric acid congruent melting salt, and the ternary nitric acid congruent melting salt is under The each group of column mass fraction is grouped as:
LiNO3, 5~65；
KNO3, 30~90；
Mg(NO3)2, 1~25.
3. high temperature high-energy battery according to claim 1, it is characterised in that:
The electrolyte is LiNO3-KNO3-Mg(NO3)2-Ca(NO3)2Quaternary nitric acid congruent melting salt, the quaternary nitric acid congruent melting Salt is grouped as by each group of following mass fraction:
LiNO3, 10~65；
KNO3, 25~75；
Mg(NO3)2, 1~15；
Ca(NO3)2, 1~15.
4. the preparation method of any one of the claim 1-3 high temperature high-energy battery, it is characterised in that it uses piece type technique system It is standby, step are as follows:
Alloy anode piece is made in negative electrode material；
Positive electrode, electrolyte, conductive additive are uniformly mixed, positive plate is pressed into；
By MgO and electrolyte that mass ratio is 3~4:6~7 at 300 DEG C after melting 15-17 hour, grinding, 100 mesh of mistake Sieve, the electrolyte sheet of tabletted type.
5. according to claim 4 high temperature high-energy battery preparation method, it is characterised in that: the conductive additive be stone One of ink, carbon nanotube, graphene, acetylene black or any several mixture.
6. according to claim 4 high temperature high-energy battery preparation method, it is characterised in that: using 0.1 mm it is thick 304 not Rust steel disc makees flow collection sheet.
7. according to claim 4 high temperature high-energy battery preparation method, it is characterised in that: alloy anode piece thickness For 0.3~1.0mm.
CN201910806781.6A 2019-08-29 2019-08-29 A kind of high temperature high-energy battery and preparation method thereof Pending CN110459779A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111916749A (en) * 2020-08-17 2020-11-10 贵州梅岭电源有限公司 Heating anode integrated material for thermal battery and preparation method thereof

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CN102645700A (en) * 2012-05-04 2012-08-22 上海光芯集成光学股份有限公司 Fabrication method of glass substrate buried optical waveguide
CN103401001A (en) * 2013-04-18 2013-11-20 中国科学院上海微系统与信息技术研究所 High-energy battery
CN107312502A (en) * 2016-04-27 2017-11-03 中国科学院青海盐湖研究所 A kind of ternary nitric acid fused salt heat accumulating and preparation method thereof
CN110054206A (en) * 2019-06-05 2019-07-26 中国科学院青海盐湖研究所 A kind of preparation method of magnesium nitrate and magnesium nitrate Quito member fused salt

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102645700A (en) * 2012-05-04 2012-08-22 上海光芯集成光学股份有限公司 Fabrication method of glass substrate buried optical waveguide
CN103401001A (en) * 2013-04-18 2013-11-20 中国科学院上海微系统与信息技术研究所 High-energy battery
CN107312502A (en) * 2016-04-27 2017-11-03 中国科学院青海盐湖研究所 A kind of ternary nitric acid fused salt heat accumulating and preparation method thereof
CN110054206A (en) * 2019-06-05 2019-07-26 中国科学院青海盐湖研究所 A kind of preparation method of magnesium nitrate and magnesium nitrate Quito member fused salt

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111916749A (en) * 2020-08-17 2020-11-10 贵州梅岭电源有限公司 Heating anode integrated material for thermal battery and preparation method thereof
CN111916749B (en) * 2020-08-17 2023-03-17 贵州梅岭电源有限公司 Heating anode integrated material for thermal battery and preparation method thereof

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Application publication date: 20191115