CN106169608A - A kind of lithium thionyl chloride battery electrolyte manufacture method - Google Patents

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

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Publication number
CN106169608A
CN106169608A CN201610785033.0A CN201610785033A CN106169608A CN 106169608 A CN106169608 A CN 106169608A CN 201610785033 A CN201610785033 A CN 201610785033A CN 106169608 A CN106169608 A CN 106169608A
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China
Prior art keywords
lithium
thionyl chloride
manufacture method
lialcl
lithium salts
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CN201610785033.0A
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CN106169608B (en
Inventor
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)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Primary Cells (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a kind of lithium thionyl chloride battery electrolyte manufacture method, including step in detail below: take lithium salts LiAlCl4It is placed in drying receptacle, by SOCl2Rectification and purification；To lithium salts LiAlCl4In be passed through SO2Gas, has led to SO2Rear standing 15 20h；Water intaking, adds BrCL in water, obtains HCl and HBrO；The SOCl that rectification and purification is crossed2, HCl and HBrO join logical complete SO2After lithium salts product in, add lithium sheet, keep the humidity dew point value of container less than 35 DEG C, prepare electrolyte.A kind of lithium thionyl chloride battery electrolyte manufacture method of the present invention, adds appropriate halogen or halogen compounds, in the electrolytic solution according to BrCl+H2O=HCl+HBrO principle, improves halogen and the content of halogen compounds in electrolyte, can be efficiently modified the voltage delay of battery.

Description

A kind of lithium thionyl chloride battery electrolyte manufacture method
Technical field
The present invention relates to lithium battery manufacturing technology field, be specially a kind of lithium thionyl chloride battery electrolyte manufacture method.
Background technology
Lithium thionyl chloride cell is with lithium metal as negative pole, and liquid thionyl chloride is positive active material, and with porous charcoal Electrochemical system power supply for plus plate current-collecting body.Wherein, SOCl2Not only it is reacting substance but also be non-aqueous inorganic solvent, dissolves Solution after the additives such as LiAlCl4 is inorganic electrolyte liquid, and this system battery is the novel high-energy chemical-electrical that developed recently gets up Source.Overall reaction mechanism is: 4Li+2SOCl2→4LiCl+S+SO2, sulfur and sulfur dioxide are dissolved in the thionyl chloride electrolyte of excess In, and during discharging, owing to producing sulfur dioxide, have a certain degree of pressure and produce.During storing, cathode of lithium one Warp and electrolyte contact, just react generation LiCl, the LiCl that cathode of lithium is i.e. formed thereon with thionyl chloride electrolyte The protection of film.This passivating film is of value to the storage life extending battery, but can cause voltage delay, at height when electric discharge starts Battery after the lower long-term storage of temperature, discharges at low ambient temperatures, and its voltage delay phenomenon is especially apparent.To this end, develop a kind of lithium Thionyl chloride battery electrolyte manufacture method.
Summary of the invention
It is an object of the invention to provide a kind of lithium thionyl chloride battery electrolyte manufacture method, to solve above-mentioned background skill The problem proposed in art.
For achieving the above object, the present invention provides following technical scheme: a kind of lithium thionyl chloride battery electrolyte making side Method, including step in detail below:
A. take lithium salts LiAlCl4 to be placed in drying receptacle, by SOCl2Rectification and purification；
B. in lithium salts LiAlCl4, it is passed through SO2Gas, has led to SO2Rear standing 15-20h；
C. fetch water, in water, add BrCL, obtain HCl and HBrO；
D. SOCl rectification and purification crossed2, HCl and HBrO join logical complete SO2After lithium salts product in, add lithium sheet, Keep the humidity dew point value of container less than-35 DEG C, prepare electrolyte.
Further, described SO2Gas purity >=99.9999%, the weight of SO2 is the 2%-4% of solution.
Further, described SO2Gas is passed through the 20%-30% that quality is lithium salts LiAlCl4 mass.
Further, described lithium salts LiAlCl4 is anhydrous LiCl and AlCl3Melted prepared, the wherein mole ratio of LiCl Mole excess 0.1%-0.2% of AlCl 3.
Further, SO has been led to2After lithium salts product and SOCl2Mass ratio is 1:8-10.
Further, adding lithium tablet quality is LiAlCl40.01%-0.02%.
Compared with prior art, the invention has the beneficial effects as follows:
A kind of lithium thionyl chloride battery electrolyte manufacture method of the present invention, adds appropriate halogen or halogen in the electrolytic solution Element compound, according to BrCl+H2O=HCl+HBrO principle, improves halogen and the content of halogen compounds, Ke Yiyou in electrolyte Effect improves the voltage delay of battery.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, Obviously, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based in the present invention Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, all Belong to the scope of protection of the invention.
Embodiment 1
A kind of lithium thionyl chloride battery electrolyte manufacture method, including step in detail below:
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 SO2Rear standing 15h；
C. fetch water, in water, add BrCL, obtain HCl and HBrO；
D. SOCl rectification and purification crossed2, HCl and HBrO join logical complete SO2After lithium salts product in, add lithium sheet, Keep the humidity dew point value of container less than-35 DEG C, prepare electrolyte.
Described SO2Gas purity >=99.9999%, SO2Weight is solution 2%.
Described SO2It is lithium salts LiAlCl that gas is passed through quality4The 20% of quality.
Described lithium salts LiAlCl4For anhydrous LiCl and AlCl3Melted prepared, wherein the mole of LiCl compares AlCl3Rub You measure excess 0.1%.
Lead to SO2After lithium salts product and SOCl2Mass ratio is 1:8.
Adding lithium tablet quality is LiAlCl40.01%.
Embodiment 2
A kind of lithium thionyl chloride battery electrolyte manufacture method, including step in detail below:
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 SO2Rear standing 18h；
C. fetch water, in water, add BrCL, obtain HCl and HBrO；
D. SOCl rectification and purification crossed2, HCl and HBrO join logical complete SO2After lithium salts product in, add lithium sheet, Keep the humidity dew point value of container less than-35 DEG C, prepare electrolyte.
Described SO2Gas purity >=99.9999%, SO2Weight is solution 3%.
Described SO2It is lithium salts LiAlCl that gas is passed through quality4The 25% of quality.
Described lithium salts LiAlCl4For anhydrous LiCl and AlCl3Melted prepared, wherein the mole of LiCl compares AlCl3Rub You measure excess 0.15%.
Lead to SO2After lithium salts product and SOCl2Mass ratio is 1:9.
Adding lithium tablet quality is LiAlCl40.01%.
Embodiment 3
A kind of lithium thionyl chloride battery electrolyte manufacture method, including step in detail below:
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 SO2Rear standing 20h；
C. fetch water, in water, add BrCL, obtain HCl and HBrO；
D. SOCl rectification and purification crossed2, HCl and HBrO join logical complete SO2After lithium salts product in, add lithium sheet, Keep the humidity dew point value of container less than-35 DEG C, prepare electrolyte.
Described SO2Gas purity >=99.9999%, SO2Weight is solution 4%.
Described SO2It is lithium salts LiAlCl that gas is passed through quality4The 30% of quality.
Described lithium salts LiAlCl4 is anhydrous LiCl and AlCl3Melted prepared, wherein the mole of LiCl compares AlCl3Rub You measure excess 0.2%.
Lead to SO2After lithium salts product and SOCl2Mass ratio is 1:10.
Adding lithium tablet quality is LiAlCl40.02%.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, permissible Understand and these embodiments can be carried out multiple change without departing from the principles and spirit of the present invention, revise, replace And modification, the scope of the present invention be defined by the appended.

Claims (6)

1. a lithium thionyl chloride battery electrolyte manufacture method, it is characterised in that step is:
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 SO2Rear standing 15-20h；
C. fetch water, in water, add BrCL, obtain HCl and HBrO；
D. SOCl rectification and purification crossed2, HCl and HBrO join logical complete SO2After lithium salts product in, add lithium sheet, keep The humidity dew point value of container is less than-35 DEG C, prepares electrolyte.
2. a kind of lithium thionyl chloride battery electrolyte manufacture method as claimed in claim 1, it is characterised in that described SO2Gas Purity >=99.9999%, SO2The 2%-4% that weight is solution.
3. a kind of lithium thionyl chloride battery electrolyte manufacture method as claimed in claim 1 or 2, it is characterised in that described SO2 It is lithium salts LiAlCl that gas is passed through quality4The 20%-30% of quality.
4. a kind of lithium thionyl chloride battery electrolyte manufacture method as claimed in claim 1, it is characterised in that described lithium salts LiAlCl4For anhydrous LiCl and AlCl3Melted prepared, wherein the mole of LiCl compares AlCl3Mole excess 0.1%- 0.2%.
5. a kind of lithium thionyl chloride battery electrolyte manufacture method as claimed in claim 1, it is characterised in that led to SO2After Lithium salts product and SOCl2Mass ratio is 1:8-10.
6. a kind of lithium thionyl chloride battery electrolyte manufacture method as claimed in claim 1, it is characterised in that add lithium sheet matter 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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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109742446A (en) * 2018-12-21 2019-05-10 裴广华 A kind of lithium/thinly chloride battery electrolyte and preparation method thereof
CN115020728A (en) * 2022-07-12 2022-09-06 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） Method for eliminating voltage lag at initial discharge stage of lithium thionyl chloride battery
CN115020728B (en) * 2022-07-12 2024-06-07 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） Method for eliminating initial voltage hysteresis of lithium thionyl chloride battery in discharge stage

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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109742446A (en) * 2018-12-21 2019-05-10 裴广华 A kind of lithium/thinly chloride battery electrolyte and preparation method thereof
CN109742446B (en) * 2018-12-21 2020-09-08 乐清市华尊电气有限公司 Lithium/thionyl chloride battery electrolyte and preparation method thereof
CN115020728A (en) * 2022-07-12 2022-09-06 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） Method for eliminating voltage lag at initial discharge stage of lithium thionyl chloride battery
CN115020728B (en) * 2022-07-12 2024-06-07 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） Method for eliminating initial voltage hysteresis of lithium thionyl chloride battery in discharge stage

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Effective date of registration: 20220926

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.