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

A kind of high voltage lithium thermal cell Download PDF

Info

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
Authority
CN
China
Prior art keywords
electrolyte
solid electrolyte
nickel chloride
positive
thermal cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811059263.4A
Other languages
Chinese (zh)
Other versions
CN109167080B (en
Inventor
刘海萍
曹立新
毕四富
曹菲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology Weihai
Original Assignee
Harbin Institute of Technology Weihai
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology Weihai filed Critical Harbin Institute of Technology Weihai
Priority to CN201811059263.4A priority Critical patent/CN109167080B/en
Publication of CN109167080A publication Critical patent/CN109167080A/en
Application granted granted Critical
Publication of CN109167080B publication Critical patent/CN109167080B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

Landscapes

  • 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811059263.4A CN109167080B (en) 2018-09-12 2018-09-12 High-voltage lithium thermal battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811059263.4A CN109167080B (en) 2018-09-12 2018-09-12 High-voltage lithium thermal battery

Publications (2)

Publication Number Publication Date
CN109167080A true CN109167080A (en) 2019-01-08
CN109167080B CN109167080B (en) 2022-06-14

Family

ID=64895025

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811059263.4A Active CN109167080B (en) 2018-09-12 2018-09-12 High-voltage lithium thermal battery

Country Status (1)

Country Link
CN (1) CN109167080B (en)

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

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4207388A (en) * 1978-11-29 1980-06-10 The United States Of America As Represented By The Secretary Of The Air Force Copper (II) chloride-tetrachloroaluminate battery
US20030194602A1 (en) * 2002-04-12 2003-10-16 Sami Daoud Thermal battery
CN102148377A (en) * 2010-02-10 2011-08-10 上海空间电源研究所 Ultra-thin monomer battery used for high voltage thermal battery and preparation method thereof
CN102157722A (en) * 2011-03-21 2011-08-17 中国电子科技集团公司第十八研究所 Preparation method of positive pole material of thermal battery
CN102280618A (en) * 2011-07-06 2011-12-14 苏州大学 Anode material of lithium ion cell and preparation method thereof
EP2424017A2 (en) * 2010-08-31 2012-02-29 Samsung SDI Co., Ltd. Solid electrolyte and thermoelectric converter including the same
US20130078528A1 (en) * 2011-09-22 2013-03-28 Eaglepicher Technologies, Llc Electrolyte materials, thermal battery components, and thermal batteries for intermediate temperature applications
US20140065513A1 (en) * 2012-08-29 2014-03-06 Michael Edward Badding Ion-conducting composite electrolyte comprising path-engineered particles
US20140170465A1 (en) * 2004-02-06 2014-06-19 Polyplus Battery Company Protected lithium electrodes having a porous electrolyte interlayer and associated battery cells
CN104332651A (en) * 2014-11-06 2015-02-04 山东大学 Method for preparing garnet type Li7La3Zr2O12 electrolyte powder with molten-salt method
EP2856534A1 (en) * 2012-06-04 2015-04-08 EaglePicher Technologies, LLC Ceramic enclosed thermal battery
US20160049707A1 (en) * 2013-03-21 2016-02-18 Liox Power, Inc. Intermediate temperature alkali metal/oxygen batteries employing molten nitrate electrolytes
CN105470466A (en) * 2015-12-29 2016-04-06 中国电子科技集团公司第十八研究所 All-solid-state battery of skeleton supported alloy anode and preparation method thereof
CN105789653A (en) * 2016-04-13 2016-07-20 武汉理工大学 Preparation method of thermal battery electrolyte containing hollow magnesia powder
US20160365569A1 (en) * 2015-06-09 2016-12-15 Samsung Electronics Co., Ltd. Composite for anode active material, anode including the composite, lithium secondary battery including the anode, and method of preparing the composite
WO2017019163A1 (en) * 2015-07-28 2017-02-02 Seeo, Inc. Multi-phase electrolyte lithium batteries
WO2017038988A1 (en) * 2015-09-04 2017-03-09 国立大学法人東京工業大学 Thermoelectric power generation element, thermoelectric power generation module including same, and thermoelectric power generation method using same
KR101739803B1 (en) * 2017-04-06 2017-06-08 국방과학연구소 A thermal batteries using a eutectic salt coated solid-electrolyte and a manufacturing method therefor
CN106896103A (en) * 2015-12-18 2017-06-27 国联汽车动力电池研究院有限责任公司 SiO in a kind of Silicon-carbon composite material for lithium ion battery2, Si detection method of content
US20170214106A1 (en) * 2016-01-22 2017-07-27 Johnson Ip Holding, Llc Johnson lithium oxygen electrochemical engine
CN107437636A (en) * 2016-05-26 2017-12-05 中国科学院上海应用物理研究所 A kind of high-temperature molten salt battery
DE102016214399A1 (en) * 2016-08-04 2018-02-08 Bayerische Motoren Werke Aktiengesellschaft Electrochemical cell and method of making the electrochemical cell
US20180205112A1 (en) * 2017-01-17 2018-07-19 Samsung Electronics Co., Ltd. Solid electrolyte for a negative electrode of a secondary battery and methods for the manufacture of an electrochemical cell
US10756392B2 (en) * 2017-09-20 2020-08-25 Kabushiki Kaisha Toshiba Secondary battery, battery pack, and vehicle

Patent Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4207388A (en) * 1978-11-29 1980-06-10 The United States Of America As Represented By The Secretary Of The Air Force Copper (II) chloride-tetrachloroaluminate battery
US20030194602A1 (en) * 2002-04-12 2003-10-16 Sami Daoud Thermal battery
US20140170465A1 (en) * 2004-02-06 2014-06-19 Polyplus Battery Company Protected lithium electrodes having a porous electrolyte interlayer and associated battery cells
CN102148377A (en) * 2010-02-10 2011-08-10 上海空间电源研究所 Ultra-thin monomer battery used for high voltage thermal battery and preparation method thereof
EP2424017A2 (en) * 2010-08-31 2012-02-29 Samsung SDI Co., Ltd. Solid electrolyte and thermoelectric converter including the same
CN102157722A (en) * 2011-03-21 2011-08-17 中国电子科技集团公司第十八研究所 Preparation method of positive pole material of thermal battery
CN102280618A (en) * 2011-07-06 2011-12-14 苏州大学 Anode material of lithium ion cell and preparation method thereof
US20130078528A1 (en) * 2011-09-22 2013-03-28 Eaglepicher Technologies, Llc Electrolyte materials, thermal battery components, and thermal batteries for intermediate temperature applications
CN103022526A (en) * 2011-09-22 2013-04-03 伊格皮切尔科技有限责任公司 Electrolyte materials, thermal battery components, and thermal batteries for intermediate temperature applications
EP2856534A1 (en) * 2012-06-04 2015-04-08 EaglePicher Technologies, LLC Ceramic enclosed thermal battery
US20140065513A1 (en) * 2012-08-29 2014-03-06 Michael Edward Badding Ion-conducting composite electrolyte comprising path-engineered particles
US20160049707A1 (en) * 2013-03-21 2016-02-18 Liox Power, Inc. Intermediate temperature alkali metal/oxygen batteries employing molten nitrate electrolytes
CN104332651A (en) * 2014-11-06 2015-02-04 山东大学 Method for preparing garnet type Li7La3Zr2O12 electrolyte powder with molten-salt method
US20160365569A1 (en) * 2015-06-09 2016-12-15 Samsung Electronics Co., Ltd. Composite for anode active material, anode including the composite, lithium secondary battery including the anode, and method of preparing the composite
WO2017019163A1 (en) * 2015-07-28 2017-02-02 Seeo, Inc. Multi-phase electrolyte lithium batteries
WO2017038988A1 (en) * 2015-09-04 2017-03-09 国立大学法人東京工業大学 Thermoelectric power generation element, thermoelectric power generation module including same, and thermoelectric power generation method using same
TW201725765A (en) * 2015-09-04 2017-07-16 國立大學法人東京工業大學 Thermoelectric element and thermoelectric module comprising the same, and method of thermoelectric generation using the same
CN106896103A (en) * 2015-12-18 2017-06-27 国联汽车动力电池研究院有限责任公司 SiO in a kind of Silicon-carbon composite material for lithium ion battery2, Si detection method of content
CN105470466A (en) * 2015-12-29 2016-04-06 中国电子科技集团公司第十八研究所 All-solid-state battery of skeleton supported alloy anode and preparation method thereof
US20170214106A1 (en) * 2016-01-22 2017-07-27 Johnson Ip Holding, Llc Johnson lithium oxygen electrochemical engine
CN105789653A (en) * 2016-04-13 2016-07-20 武汉理工大学 Preparation method of thermal battery electrolyte containing hollow magnesia powder
CN107437636A (en) * 2016-05-26 2017-12-05 中国科学院上海应用物理研究所 A kind of high-temperature molten salt battery
DE102016214399A1 (en) * 2016-08-04 2018-02-08 Bayerische Motoren Werke Aktiengesellschaft Electrochemical cell and method of making the electrochemical cell
US20180205112A1 (en) * 2017-01-17 2018-07-19 Samsung Electronics Co., Ltd. Solid electrolyte for a negative electrode of a secondary battery and methods for the manufacture of an electrochemical cell
KR101739803B1 (en) * 2017-04-06 2017-06-08 국방과학연구소 A thermal batteries using a eutectic salt coated solid-electrolyte and a manufacturing method therefor
US10756392B2 (en) * 2017-09-20 2020-08-25 Kabushiki Kaisha Toshiba Secondary battery, battery pack, and vehicle

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
LIU WJ等: "Variable-temperature preparation and performance of NiCl2 as a cathode material for thermal batteries", 《SCIENCE CHINA-MATERIALS》 *
LIU, XINGBING 等: "Porous Magnesia Fibers as an Immobilizing Agent for Molten Salt in Thermal Batteries", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 *
REDDY, M. V.等: "Molten salt synthesis and characterization of fast ion conductor Li6.75La3Zr1.75Ta0.25O12", 《JOURNAL OF SOLID STATE ELECTROCHEMISTRY》 *
刘文军 等: "热电池正极材料CoS2的研究进展", 《电源技术》 *

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

Also Published As

Publication number Publication date
CN109167080B (en) 2022-06-14

Similar Documents

Publication Publication Date Title
CN108767263B (en) Preparation method and application of modified metal lithium negative electrode copper foil current collector
CN101659443B (en) Preparation method of spherical lithium titanate used for lithium ion battery
CN108899486B (en) Sulfur electrolyte-coated positive electrode active material and preparation method thereof, and all-solid-state lithium sulfur battery and preparation method thereof
CN104617283B (en) The preparation method of a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode and the preparation method of positive pole
CN100583511C (en) Preparation method for anode material manganese magnesium silicate of rechargeable magnesium cell
CN102339979A (en) Method for preparing thin-film positive electrode for thermal batteries
CN107482209B (en) Positive electrode material for liquid and semi-liquid metal batteries
CN110289448B (en) Metal lithium cathode with artificially constructed SEI film and preparation method thereof
CN102983307A (en) Preparation method for graphite negative electrode of lithium ion battery
CN101409344A (en) Lithium ion battery cathode material and preparation method thereof
CN110729470A (en) Positive electrode material of liquid or semi-liquid metal battery, preparation method and application
CN109167080A (en) A kind of high voltage lithium thermal cell
CN108075181A (en) A kind of solid-state or colloidal state water-system alkali metal ion battery and preparation method thereof
CN102779989A (en) Method for preparing fluorine-doped spherical lithium titanate for lithium ion battery
CN110112459B (en) Preparation method of sulfide solid electrolyte and all-solid-state lithium-sulfur battery
CN109950640B (en) Metal graphite medium-temperature energy storage battery and preparation method thereof
CN105006601A (en) Liquid metal battery
CN110165286A (en) All-solid lithium-ion battery and its complex sintered preparation process of integration
CN108695553A (en) A kind of all solid state sodium rechargeable battery electrolyte, preparation method and its application
CN207459090U (en) A kind of lithium ion battery
CN108899211A (en) A kind of sodium ion capacitor and preparation method thereof having both high-energy density and high power density
CN111816853B (en) CuS-Cu7.2S4Nanocomposite, lithium battery and preparation method
CN104167538B (en) A kind of Li4Ti5O12The preparation method of/NiSn composite
CN106252601A (en) A kind of preparation method of sulfur composite foam Graphene positive plate
CN106129352A (en) A kind of method and application being improved sulfur charge and discharge cycles ability by dopen Nano aluminium sesquioxide

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant