CN109167080A - A kind of high voltage lithium thermal cell - Google Patents

A kind of high voltage lithium thermal cell Download PDF

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Publication number
CN109167080A
CN109167080A CN201811059263.4A CN201811059263A CN109167080A CN 109167080 A CN109167080 A CN 109167080A CN 201811059263 A CN201811059263 A CN 201811059263A CN 109167080 A CN109167080 A CN 109167080A
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Prior art keywords
electrolyte
solid electrolyte
nickel chloride
positive
thermal cell
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CN201811059263.4A
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CN109167080B (en
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刘海萍
曹立新
毕四富
曹菲
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Harbin Institute of Technology Weihai
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Harbin Institute of Technology Weihai
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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
    • H01M6/30—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)

Abstract

The present invention relates to a kind of high voltage lithium thermal cell, which uses nickel chloride for positive electrode, and electrolyte uses solid electrolyte, and solid electrolyte is preferably Li7La3Zr2O12Or the solid electrolyte of its doping vario-property.Solid electrolyte is ground into electrolyte powder, the solid electrolyte no more than 20% is added in nickel chloride positive electrode to mix, positive powder is made in grinding, layering is pressed into after the piece of booth is made anode/electrolyte sheet together, is packed into battery case after compressing according to plus plate current-collecting body/anode/electrolyte sheet/negative electrode tab/negative current collector sequence.The battery step is simple, and raw material is cheap and easy to get, can eliminate the infiltration problem of nickel chloride and traditional electrolyte matter, effectively eliminate security risk, can give full play of the advantage that nickel chloride materials theory capacity is high, electrode potential is positive.

Description

A kind of high voltage lithium thermal cell
Technical field
The present invention relates to a kind of high voltage lithium thermal cells.Belong to lithium thermal cell technical field.
Background technique
Thermal cell is called molten salt battery, with specific energy and specific power are high, environment-adapting ability is strong, period of storage is long, activation Speed is fast, does not need the advantages that maintenance, and quick development has been obtained since World War II latter stage is by invention, becomes military The preferred power supply of device equipment.However, sophisticated weapon is to thermoelectricity cell voltage, power etc., more stringent requirements are proposed, compares weapon Equipment makes rapid progress, the obvious lag of thermoelectricity pool technology development.
Current study show that battery performance depends primarily on the raising of positive active material performance, function admirable is explored Positive electrode is the key that obtain high-performance thermal cell.Cobalt disulfide is common thermal cell positive electrode in recent years, is had interior Hinder that low, load capacity is strong, high current polarizes small, output voltage feature with high accuracy under varying load.However, CoS2The thermoelectricity of preparation Pond is limited by the lower voltage of 2.0V or so, and the space that specific energy is further increased on the basis of existing is limited.Therefore, Ren Menyi Directly constantly seeking thermal cell novel anode material.Chlorination nickel material is high with theoretical capacity, discharge current density is big, electrode is electric The features such as position is just, discharge platform is steady, for decomposition temperature at 900 DEG C or more, thermal stability is good.NiCl2Material and lithium alloy are negative Pole matching uses, and voltage reaches 2.5V, shows excellent performance, it is considered to be the ideal material of alternative sulphur system positive electrode One of.
Unfortunately, electrolyte used in current thermal cell is mostly the molten salt electrolytes such as LiCl-LiBr-LiF, this kind of For electrolyte in high temperature discharge, after electrolyte melting, chlorination nickel electrode material and electrolyte " infiltration ", overflow goes out electrode slice, draws It sends out battery short circuit and affects the practical application of nickel chloride to cause serious security problem.
Summary of the invention
In view of the shortcomings of the prior art, the present invention prepares high voltage thermoelectricity using solid electrolyte and nickel chloride anode matching Pond.This method step is simple, and raw material is cheap and easy to get, can eliminate the infiltration problem of nickel chloride and traditional electrolyte matter, effectively eliminate this Security risk gives full play of the advantage that nickel chloride materials theory capacity is high, electrode potential is positive.
Technical scheme is as follows:
A kind of high voltage lithium thermal cell, preparation method includes the following steps:
(1) solid electrolyte is ground into electrolyte powder；
(2) a certain proportion of solid electrolyte is added in nickel chloride positive electrode to mix, positive powder is made in grinding；
(3) layering after the piece of the powder of step (2) and step (1) booth is pressed into and anode/electrolyte sheet is made together；
(4) battery case is packed into after compressing according to plus plate current-collecting body/anode/electrolyte sheet/negative electrode tab/negative current collector sequence.
Currently preferred, step (1) solid electrolyte is Li7La3Zr2O12Solid electrolyte or its doping vario-property Solid electrolyte afterwards.
Currently preferred, step (2) a certain proportion of solid electrolyte accounts for positive powder no more than 20%.
Currently preferred, Li-Si alloy or lithium boron alloy, more preferably lithium boron can be used in step (4) described negative electrode tab Alloy.
Single cell of thermo voltage according to above technical scheme preparation is 2.5V or so, positive electrode and electrolyte when electric discharge Molten leaching phenomenon will not be generated.
Beneficial effects of the present invention are as follows:
The present invention prepares thermal cell using solid electrolyte and nickel chloride matching, and monomer battery voltage is higher, reachable 2.5V or so, And this method step is simple, it is not necessary that existing improvement of manufacturing line, raw material is cheap and easy to get, can eliminate nickel chloride and traditional electrolyte matter Infiltration problem, effectively eliminate the security risk, it is excellent to give full play of that nickel chloride materials theory capacity is high, electrode potential is positive Gesture.
Detailed description of the invention
Fig. 1 solid electrolyte (LLZO) and the molten excessive situation of full lithium electrolyte (LiCl-LiBr-LiF), (a) LLZO electrolysis Matter, (b) full lithium electrolyte
By battery made from embodiment 1 at 550 DEG C, 80 mAcm of current density-2Disassembled after discharge test, and with comparative example 1 Molten salt electrolyte thermal cell compares, as a result as shown in Figure 1.From Fig. 1 it will be seen that with Li7La3Zr2O12Solid electricity After solution matter (LLZO) does the lithium thermoelectricity tank discharge of electrolyte, mica spacer edge is clean, and LLZO still keeps original solid shape Fusing and flowing do not occur for shape, and there is no overflow phenomenas for positive plate.And with traditional full lithium electrolyte (LiCl-LiBr- LiF lithium thermal cell) can observe obvious melting phenomenon in nickel sheet and mica sheet, show high temperature after completing high temperature discharge After electric discharge, electrode material overflow goes out electrode slice.
Specific embodiment
The present invention is described in more detail combined with specific embodiments below.These embodiments are merely to illustrate the present invention, but not Limit to the scope of the present invention.In addition, those skilled in the art can be to this after having read specific embodiment set forth in the present invention Invention is made an amendment and is changed, but such equivalent forms equally belong in the application patent book limited range.
Embodiment 1
(1) by Li7La3Zr2O12Solid electrolyte is ground into electrolyte powder and crosses 200 meshes；
(2) 10% solid electrolyte is added in nickel chloride positive electrode to mix, positive powder is made in grinding；
(3) 0.9 gram of positive powder and 0.1 gram of electrolyte powder are weighed, layering is pressed into after the piece of booth is made anode/electrolyte sheet together；
(4) battery case is packed into after compressing according to plus plate current-collecting body/anode/electrolyte sheet/negative electrode tab/negative current collector sequence.
By battery obtained at 550 DEG C, 80 mAcm of current density-2It is disassembled after discharge test, there is no overflowing for positive plate Flow phenomenon.
Embodiment 2
It (1) will be with the Li of Fe doping vario-property6.7Fe0.1La3Zr2O12Solid electrolyte is ground into electrolyte powder and crosses 200 meshes；
(2) 8% solid electrolyte is added in nickel chloride positive electrode to mix, positive powder is made in grinding；
(3) 0.9 gram of positive powder and 0.1 gram of electrolyte powder are weighed, layering is pressed into after the piece of booth is made anode/electrolyte sheet together；
(4) battery case is packed into after compressing according to plus plate current-collecting body/anode/electrolyte sheet/negative electrode tab/negative current collector sequence.
By battery obtained at 550 DEG C, 80 mAcm of current density-2It is disassembled after discharge test, there is no overflowing for positive plate Flow phenomenon.
Comparative example 1
(1) magnesia that full lithium electrolyte is added 20% is ground into electrolyte powder and crosses 200 meshes；
(2) 8% electrolyte powder is added in nickel chloride positive electrode to mix, positive powder is made in grinding；
(3) 0.9 gram of positive powder and 0.1 gram of electrolyte powder are weighed, layering is pressed into after the piece of booth is made anode/electrolyte sheet together；
Battery case is packed into after compressing according to plus plate current-collecting body/anode/electrolyte sheet/negative electrode tab/negative current collector sequence.
By battery obtained at 550 DEG C, 80 mAcm of current density-2Discharge test, battery are quickly invalidated, electric after dismantling Obvious overflow phenomena occurs for pole piece.

Claims (4)

1. a kind of high voltage lithium thermal cell, it is characterised in that its electrolyte uses solid electrolyte.
2. a kind of high voltage lithium thermal cell according to claim 1, it is characterised in that it uses nickel chloride for positive electrode.
3. a kind of high voltage lithium thermal cell according to claim 1, it is characterised in that solid electrolyte Li7La3Zr2O12 The solid electrolyte of solid electrolyte or its doping vario-property.
4. a kind of high voltage lithium thermal cell according to claim 1, it is characterised in that its cathode uses lithium boron alloy.
CN201811059263.4A 2018-09-12 2018-09-12 High-voltage lithium thermal battery Active CN109167080B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109802080A (en) * 2019-01-14 2019-05-24 贵州梅岭电源有限公司 A kind of high conductance composite diaphragm material of thermal cell
CN114388756A (en) * 2021-12-27 2022-04-22 武汉理工大学 High-performance thermal battery composite positive electrode material and preparation method thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109802080A (en) * 2019-01-14 2019-05-24 贵州梅岭电源有限公司 A kind of high conductance composite diaphragm material of thermal cell
CN109802080B (en) * 2019-01-14 2021-08-17 贵州梅岭电源有限公司 High-conductivity composite diaphragm material for thermal battery
CN114388756A (en) * 2021-12-27 2022-04-22 武汉理工大学 High-performance thermal battery composite positive electrode material and preparation method thereof

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