CN106169608B - A kind of lithium thionyl chloride battery electrolyte production method - Google Patents

A kind of lithium thionyl chloride battery electrolyte production method Download PDF

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Publication number
CN106169608B
CN106169608B CN201610785033.0A CN201610785033A CN106169608B CN 106169608 B CN106169608 B CN 106169608B CN 201610785033 A CN201610785033 A CN 201610785033A CN 106169608 B CN106169608 B CN 106169608B
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lithium
thionyl chloride
lialcl
added
production method
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CN106169608A (en
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祝德洪
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Hubei Aichaote New Energy Co.,Ltd.
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AHEAD CELL TECHNOLOGY Co Ltd
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Primary Cells (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a kind of lithium thionyl chloride battery electrolyte production methods, comprising the following specific steps taking lithium salts LiAlCl4It is placed in drying receptacle, by SOCl2Rectification and purification；To lithium salts LiAlCl4In be passed through SO2Gas has led to SO2After stand 15-20h；Water intaking, BrCl is added into water, obtains HCl and HBrO；The SOCl that rectification and purification is crossed2, HCl and HBrO be added to and led to SO2In lithium salts product afterwards, lithium piece is added, keeps the humidity dew point value of container lower than -35 DEG C, electrolyte is made.A kind of lithium thionyl chloride battery electrolyte production method of the invention, is added suitable halogen or halogen compounds, according to BrCl+H in the electrolytic solution2O=HCl+HBrO principle improves the content of halogen and halogen compounds in electrolyte, can be efficiently modified the voltage delay of battery.

Description

A kind of lithium thionyl chloride battery electrolyte production method
Technical field
The present invention relates to lithium battery manufacturing technology field, specially a kind of lithium thionyl chloride battery electrolyte production method.
Background technique
Lithium thionyl chloride cell is using lithium metal as cathode, and liquid thionyl chloride is positive active material, and with porous charcoal For the electrochemical system power supply of plus plate current-collecting body.Wherein, SOCl2Not only it had been reactive material but also had been non-aqueous inorganic solvent, had dissolved LiAlCl4Solution after equal additives is inorganic electrolyte liquid, which is the novel high-energy chemical-electrical that developed recently gets up Source.Overall reaction mechanism are as follows: 4Li+2SOCl2→4LiCl+S+SO2, sulphur and sulfur dioxide are dissolved in excessive thionyl chloride electrolyte In, and during electric discharge, due to generating sulfur dioxide, has a degree of pressure and generate.During storage, cathode of lithium one Through contacting with electrolyte, LiCl just is generated with thionyl chloride electrolysis qualitative response, cathode of lithium is i.e. by the LiCl being formed thereon The protection of film.This passivating film is beneficial to extend the storage life of battery, but can cause voltage delay when discharging and starting, in height Battery after the lower long-term storage of temperature, discharges, voltage delay phenomenon is especially apparent at low ambient temperatures.For this purpose, developing a kind of lithium Thionyl chloride battery electrolyte production method.
Summary of the invention
The purpose of the present invention is to provide a kind of lithium thionyl chloride battery electrolyte production methods, to solve above-mentioned background skill The problem of being proposed in art.
To achieve the above object, the invention provides the following technical scheme: a kind of lithium thionyl chloride battery electrolyte production side Method, comprising the following specific steps
A. lithium salts LiAlCl is taken4It is placed in drying receptacle, by SOCl2Rectification and purification；
B. to lithium salts LiAlCl4In be passed through SO2Gas has led to SO2After stand 15-20h；
C. it fetches water, BrCl is added into water, obtain HCl and HBrO；
D. SOCl rectification and purification crossed2, HCl and HBrO be added to and led to SO2In lithium salts product afterwards, lithium piece is added, It keeps the humidity dew point value of container to be lower than -35 DEG C, electrolyte is made.
Further, the SO2Gas purity >=99.9999%, SO2Weight be electrolyte 2%-4%.
Further, the SO2It is lithium salts LiAlCl that gas, which is passed through quality,4The 20%-30% of quality.
Further, the lithium salts LiAlCl4For anhydrous LiCl and AlCl3Melting is made, wherein the mole ratio of LiCl AlCl3Mole excess 0.1%-0.2%.
Further, SO has been led to2Lithium salts product and SOCl afterwards2Mass ratio is 1:(8-10).
Further, it is LiAlCl that lithium piece quality, which is added,40.01%-0.02%.
Compared with prior art, the beneficial effects of the present invention are:
A kind of lithium thionyl chloride battery electrolyte production method of the invention, is added suitable halogen or halogen in the electrolytic solution Plain compound, according to BrCl+H2O=HCl+HBrO principle improves the content of halogen and halogen compounds in electrolyte, Ke Yiyou Effect improves the voltage delay of battery.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described, Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all Belong to the scope of protection of the invention.
Embodiment 1
A kind of lithium thionyl chloride battery electrolyte production method, comprising the following specific steps
A. lithium salts LiAlCl is taken4It is placed in drying receptacle, by SOCl2Rectification and purification；
B. to lithium salts LiAlCl4In be passed through SO2Gas has led to SO2After stand 15h；
C. it fetches water, BrCl is added into water, obtain HCl and HBrO；
D. SOCl rectification and purification crossed2, HCl and HBrO be added to and led to SO2In lithium salts product afterwards, lithium piece is added, It keeps the humidity dew point value of container to be lower than -35 DEG C, electrolyte is made.
The SO2Gas purity >=99.9999%, SO2Weight be electrolyte 2%.
The SO2It is lithium salts LiAlCl that gas, which is passed through quality,4The 20% of quality.
The lithium salts LiAlCl4For anhydrous LiCl and AlCl3Melting is made, wherein the mole ratio AlCl of LiCl3Mole Amount excessive 0.1%.
SO is led to2Lithium salts product and SOCl afterwards2Mass ratio is 1:8.
Addition lithium piece quality is LiAlCl40.01%.
Embodiment 2
A kind of lithium thionyl chloride battery electrolyte production method, comprising the following specific steps
A. lithium salts LiAlCl is taken4It is placed in drying receptacle, by SOCl2Rectification and purification；
B. to lithium salts LiAlCl4In be passed through SO2Gas has led to SO2After stand 18h；
C. it fetches water, BrCl is added into water, obtain HCl and HBrO；
D. SOCl rectification and purification crossed2, HCl and HBrO be added to and led to SO2In lithium salts product afterwards, lithium piece is added, It keeps the humidity dew point value of container to be lower than -35 DEG C, electrolyte is made.
The SO2Gas purity >=99.9999%, SO2Weight be electrolyte 3%.
The SO2It is lithium salts LiAlCl that gas, which is passed through quality,4The 25% of quality.
The lithium salts LiAlCl4For anhydrous LiCl and AlCl3Melting is made, wherein the mole ratio AlCl of LiCl3Mole Amount excessive 0.15%.
SO is led to2Lithium salts product and SOCl afterwards2Mass ratio is 1:9.
Addition lithium piece quality is LiAlCl40.01%.
Embodiment 3
A kind of lithium thionyl chloride battery electrolyte production method, comprising the following specific steps
A. lithium salts LiAlCl is taken4It is placed in drying receptacle, by SOCl2Rectification and purification；
B. to lithium salts LiAlCl4In be passed through SO2Gas has led to SO2After stand 20h；
C. it fetches water, BrCl is added into water, obtain HCl and HBrO；
D. SOCl rectification and purification crossed2, HCl and HBrO be added to and led to SO2In lithium salts product afterwards, lithium piece is added, It keeps the humidity dew point value of container to be lower than -35 DEG C, electrolyte is made.
The SO2Gas purity >=99.9999%, SO2Weight be electrolyte 4%.
The SO2It is lithium salts LiAlCl that gas, which is passed through quality,4The 30% of quality.
The lithium salts LiAlCl4For anhydrous LiCl and AlCl3Melting is made, wherein the mole ratio AlCl of LiCl3Mole Amount excessive 0.2%.
SO is led to2Lithium salts product and SOCl afterwards2Mass ratio is 1:10.
Addition lithium piece quality is LiAlCl40.02%.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding And modification, the scope of the present invention is defined by the appended.

Claims (6)

1. a kind of lithium thionyl chloride battery electrolyte production method, it is characterised in that step are as follows:
A. lithium salts LiAlCl is taken4It is placed in drying receptacle, by SOCl2Rectification and purification；
B. to lithium salts LiAlCl4In be passed through SO2Gas has led to SO2After stand 15-20h；
C. it fetches water, BrCl is added into water, obtain HCl and HBrO；
D. SOCl rectification and purification crossed2, HCl and HBrO be added to and led to SO2In lithium salts product afterwards, lithium piece is added, is kept The humidity dew point value of container is lower than -35 DEG C, and electrolyte is made.
2. a kind of lithium thionyl chloride battery electrolyte production method as described in claim 1, which is characterized in that the SO2Gas Purity >=99.9999%, SO2Weight be electrolyte 2%-4%.
3. a kind of lithium thionyl chloride battery electrolyte production method as claimed in claim 1 or 2, which is characterized in that the SO2 It is lithium salts LiAlCl that gas, which is passed through quality,4The 20%-30% of quality.
4. a kind of lithium thionyl chloride battery electrolyte production method as described in claim 1, which is characterized in that the lithium salts LiAlCl4For anhydrous LiCl and AlCl3Melting is made, wherein the mole ratio AlCl of LiCl3Mole excess 0.1%- 0.2%.
5. a kind of lithium thionyl chloride battery electrolyte production method as described in claim 1, which is characterized in that led to SO2Afterwards Lithium salts product and SOCl2Mass ratio is 1:(8-10).
6. a kind of lithium thionyl chloride battery electrolyte production method as described in claim 1, which is characterized in that lithium piece matter is added Amount is LiAlCl40.01%-0.02%.
CN201610785033.0A 2016-08-31 2016-08-31 A kind of lithium thionyl chloride battery electrolyte production method Active CN106169608B (en)

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CN112072178A (en) * 2018-12-21 2020-12-11 裴广华 Lithium/thionyl chloride battery electrolyte

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4262065A (en) * 1979-07-30 1981-04-14 Altus Corporation Additive for lithium batteries
CN1622383A (en) * 2004-12-13 2005-06-01 武汉孚特电子科技有限公司 Preparing method of electrolyte for lithium thionyl chloride cell
CN101345306A (en) * 2008-08-29 2009-01-14 上海电力学院 Lithium/thionyl chloride(Li/SOCl2) battery containing bromine chloride
CN101499526A (en) * 2009-03-06 2009-08-05 武汉孚安特科技有限公司 Lithium-thionyl chloride cell cathode with improved battery voltage hysteretic properties
CN104835971A (en) * 2015-03-25 2015-08-12 武汉孚安特科技有限公司 A preparing method of an electrolyte of a lithium-thionyl chloride cell

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4262065A (en) * 1979-07-30 1981-04-14 Altus Corporation Additive for lithium batteries
CN1622383A (en) * 2004-12-13 2005-06-01 武汉孚特电子科技有限公司 Preparing method of electrolyte for lithium thionyl chloride cell
CN101345306A (en) * 2008-08-29 2009-01-14 上海电力学院 Lithium/thionyl chloride(Li/SOCl2) battery containing bromine chloride
CN101499526A (en) * 2009-03-06 2009-08-05 武汉孚安特科技有限公司 Lithium-thionyl chloride cell cathode with improved battery voltage hysteretic properties
CN104835971A (en) * 2015-03-25 2015-08-12 武汉孚安特科技有限公司 A preparing method of an electrolyte of a lithium-thionyl chloride cell

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Address after: No. 7 Harmony Road, Nancheng, Zaoyang City, Xiangyang City, Hubei Province 441200

Patentee after: Hubei Aichaote New Energy Co.,Ltd.

Address before: Harmony Road, Nancheng Sub-district Office, Zaoyang City, Xiangfan City, Hubei Province 441200

Patentee before: AHEAD CELL TECHNOLOGY Co.,Ltd.