CN109742446A - A kind of lithium/thinly chloride battery electrolyte and preparation method thereof - Google Patents
A kind of lithium/thinly chloride battery electrolyte and preparation method thereof Download PDFInfo
- Publication number
- CN109742446A CN109742446A CN201811570609.7A CN201811570609A CN109742446A CN 109742446 A CN109742446 A CN 109742446A CN 201811570609 A CN201811570609 A CN 201811570609A CN 109742446 A CN109742446 A CN 109742446A
- Authority
- CN
- China
- Prior art keywords
- lithium
- additive
- addition
- battery electrolyte
- purification
- 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
Links
Classifications
-
- 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
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M2300/0025—Organic electrolyte
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
Landscapes
- 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)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Primary Cells (AREA)
Abstract
The invention discloses a kind of lithium/thinly chloride battery electrolyte and preparation method thereof, the electrolyte includes thionyl chloride, electrolytic salt and additive, additive includes the first additive and Second addition, is somebody's turn to do the preparation method comprises the following steps: thionyl chloride is distilled, collection fraction；Electrolytic salt is weighed to be dissolved in thionyl chloride fraction；The purification of first additive；The purification of Second addition；The first additive of purifying and the Second addition of purifying are weighed, is added in the thionyl chloride solution of electrolytic salt to get lithium/thinly chloride battery electrolyte；The first additive and Second addition synergistic effect in lithium/thinly chloride battery electrolyte of the present invention, lithium/thinly chloride battery is set to achieve good discharge voltage and discharge capacity, the voltage delay phenomenon of lithium/thinly chloride battery is significantly improved, and there is preferable cycle performance and higher safety by lithium/thinly chloride battery prepared by the electrolyte.
Description
Technical field
The present invention relates to technical field of lithium ion, specifically a kind of lithium/thinly chloride battery electrolyte and its preparation
Method.
Background technique
Lithium/thinly chloride (Li/SOCl2) battery be one kind using lithium as anode, carbon makees cathode carrier, anhydrous tetrachloro-lithium aluminate
Thionyl chloride (SOCl2) solution makees the lithium battery of electrolyte.Lithium/thinly chloride battery is high with specific energy, specific power is big, puts
The characteristics such as piezoelectric voltage is steady, storage life is long, in aerospace, underawater ordnance, navigation equipment, geological prospecting, instrument and meter etc.
It is all widely used in military and civilian industry.Lithium/thinly chloride battery is specific energy and specific power in current battery field
A kind of highest battery.The overall reaction mechanism of lithium/thinly chloride battery are as follows: 4Li+2SOCl2→4LiCl+S+SO2, sulphur and dioxy
Change sulphur to be dissolved in excessive thionyl chloride electrolyte, and during electric discharge, due to generating sulfur dioxide, has to a certain degree
Pressure generate.During storage, cathode of lithium is contacted once with electrolyte, just generates LiCl with thionyl chloride electrolysis qualitative response,
Cathode of lithium is the protection by the LiCl film being formed thereon.This passivating film is beneficial to extend the storage life of battery, but
It can cause voltage delay when discharging and starting, the battery after long-term storage, discharges, voltage is stagnant at low ambient temperatures at high temperature
Phenomenon is especially apparent afterwards.
In order to eliminate lithium/thinly chloride battery voltage delay phenomenon, the afflux form for improving cathode and anode is mostly used greatly,
Or improve the impurity content and molar concentration of electrolyte, to reduce the internal resistance of cell；Electronic component is installed additional in inside battery or outside,
Battery is set to be in weak discharge state, to weaken the formation of passivating film；In cathode and electrolyte add metal phthalocyanine compound or
The modes such as sulfide, to improve voltage delay performance.The above method some can improve to a certain extent lithium/thinly chloride electricity
Certain performances in pond, but some then it weakens lithium/thinly chloride using the capacity of " sacrifice " lithium/thinly chloride battery as cost
The other performance of battery.
Electrolyte is one of the three elements for forming lithium/thinly chloride battery, hair of the physicochemical property to battery material performance
It waves and plays a crucial role, develop the electrolyte material to match with cathode and anode material and mean a great.
Summary of the invention
It is existing to solve the purpose of the present invention is to provide a kind of lithium/thinly chloride battery electrolyte and preparation method thereof
The problems in technology.
To achieve the above object, the invention provides the following technical scheme:
A kind of lithium/thinly chloride battery electrolyte, including thionyl chloride, electrolytic salt and additive, the thionyl of electrolytic salt
The molar concentration of solutions of chlorine is 0.1-1mol/L, and the quality of additive is the 0.01-0.5% of electrolyte gross mass.Additive adds
It is very little to enter amount, does not have the phenomenon that mitigating cell voltage lag, the additional amount of additive is too many, it will affect the gram volume of material,
And it causes to waste, does not have the phenomenon that mitigating cell voltage lag.
As optimization, additive includes the first additive and Second addition, the structural formula of the first additive are as follows:
；
Wherein, X is halogen；R1For itrile group, amido, hydroxyl or nitro；R2、R3It is hydrogen, monosubstituted or polysubstituted C1-C6 alkane
Base, aryl, C1-C6 alkoxy or halogenated C1-C6 alkoxy；R4For C1-C6 alkyl or the C1- being mono-or polysubstituted with halogens
C6 alkyl.
As optimization, the structural formula of Second addition are as follows:
；
Wherein, X1For halogen；R11、R21、R31It is C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy or halogenated
C1-C10 alkoxy；R41For it is unsubstituted or or by the alkyl-substituted heterocycle of C1-C6, O, N, S element are contained on the heterocycle
One of or it is a variety of.
As optimization, electrolytic salt is bis- (fluorine sulphonyl) imine lithiums, di-oxalate lithium borate, trifluoromethanesulfonic acid lithium, three (trifluoros
Sulfonyloxy methyl) lithium methide, lithium hexafluoro phosphate, three oxalic acid lithium phosphates, difluoro dioxalic acid lithium phosphate, one in tetrafluoro oxalic acid lithium phosphate
Kind is a variety of.Li/SOCl2The major defect of battery is its voltage delay phenomenon, this phenomenon especially after high temperature storage,
It shows even more serious when using at normal temperature again, causes Li/SOCl2The reason of cell voltage lags is mainly in battery system
Tetrachloro-lithium aluminate (LiAlCl is used4) electrolytic salt, the electrolyte solution containing this salt generates spontaneous change in lithium anode
Learn reaction, product LiCl, and LiCl is covered in the form of a film on lithium anode surface hampers lithium and electrolyte solution
Contact, eventually leads to voltage delay, and the present invention replaces tetrachloro-lithium aluminate (LiAlCl using above-mentioned electrolytic salt4) electrolytic salt
The phenomenon that preparing lithium/thinly chloride battery electrolyte, can effectively mitigating cell voltage lag.
As optimization, the quality of the first additive is the 0.005-0.3% of electrolyte gross mass, the quality of Second addition
For the 0.005-0.2% of electrolyte gross mass.
A kind of preparation method of lithium/thinly chloride battery electrolyte, the preparation method the following steps are included:
(1) thionyl chloride is distilled, collects fraction；
(2) it weighs electrolytic salt to be placed in thionyl chloride fraction obtained by step (1), constant volume obtains the sulfurous of electrolytic salt
Solution of acid chloride；
The purification of (3) first additives: extracting the first additive using acetone, obtains the first additive leaching liquor, then
Leaching liquor is distilled, the first additive, the first additive of purifying obtained by drying are obtained；
(4) purification of Second addition: the purification of Second addition is purified using sublimation purification device:
(a) fused salt is added to heating interior by feeding inlet, using the first fused salt heating rod and the second fused salt heating rod to molten
Salt is heated；
(b) Second addition is fitted into distillation charging boat, in Second addition upper berth silica gel, is then placed in cylindrical tube, closes
Closed end passes through vacuum cooled pipe behind the door and is vacuumized by vacuum pump, and the purification of Second addition is completed after a period of time；
(5) Second addition for the purifying that the first additive and step (4) for weighing the purifying that step (3) obtains obtain, then
It is added in the thionyl chloride solution of step (2) obtained electrolytic salt, is stirred continuously until being completely dissolved to get lithium/Asia
Chlorosulfuric acid battery electrolyte.
As optimization, a kind of preparation method of lithium/thinly chloride battery electrolyte, the preparation method the following steps are included:
(1) thionyl chloride is placed in flask, heating is distilled, and 70-80 DEG C of fraction is collected；Thionyl chloride is distilled
It is the purpose for playing purification；
(2) electrolytic salt is weighed, under inert atmosphere conditions, by above-mentioned dissolving electrolyte salt sulfurous obtained by step (1)
In acyl chlorides fraction, constant volume is carried out, obtains the thionyl chloride solution for the electrolytic salt that molar concentration is 0.1-1mol/L；
The purification of (3) first additives: extracting the first additive using acetone, obtains the first additive leaching liquor, then
Leaching liquor is distilled, the first additive, the first additive of purifying obtained by drying are obtained；The temperature of extraction is 30-45 DEG C,
The time of extraction is 1-4h, and the distillation is carried out at 40-80 DEG C by the way of vacuum distillation；
(4) purification of Second addition: the purification of Second addition is purified using sublimation purification device: the method for purification
Process flow is short, easy to operate, and the purity of the Second addition after purification is greater than 99%；
(a) fused salt is added to heating interior by feeding inlet, using the first fused salt heating rod and the second fused salt heating rod to molten
Salt is heated, and temperature is made to reach 200-250 DEG C；
(b) Second addition is fitted into distillation charging boat, in Second addition upper berth silica gel, is then placed in cylindrical tube, closes
Closed end passes through vacuum cooled pipe by vacuum pump suction to 0.03-0.08KPa behind the door, completes Second addition by 6-15h
Purification；Silica gel mainly plays decolorization；
(5) Second addition for the purifying that the first additive and step (4) for weighing the purifying that step (3) obtains obtain, then
It is added in the thionyl chloride solution of step (2) obtained electrolytic salt, is stirred continuously until being completely dissolved to get lithium/Asia
Chlorosulfuric acid battery electrolyte.
First additive and Second addition are purified, impurity is reduced, utilizes the electricity of lithium/thinly chloride made from them
Pond electrolyte can more effectively mitigate the phenomenon that cell voltage lag.
As optimization, the sodium nitrite of quality and the mixtures of potassium nitrite such as the fused salt in step (a) is.
As optimization, leaching liquor is transferred in oscillator before distillation by step in (3), is shaken at 100-300r/min
30-60min.The purpose of concussion is that mix the first additive with acetone more uniform.
As optimization, step (1), step (2) and step (3) be in relative humidity≤0.5-1% dry environment into
Row operation.The effect of lithium/thinly chloride battery electrolyte and water is very fierce, or even very micro water is also easy to occur therewith
Effect generates HCl gas, heavy corrosion is caused, so to carry out experimental implementation in dry environment when preparing electrolyte.
Compared with prior art, the beneficial effects of the present invention are:
First is that the first additive and Second addition synergistic effect in lithium/thinly chloride battery electrolyte of the present invention have preferably
The passivation of anti-thionyl chloride characteristic, the first additive and Second addition pass through cathode activity object in lithium/thinly chloride battery
The effect of matter thionyl chloride, it is suppressed that the formation of lithium metal anode surface " passivating film " achieves lithium/thinly chloride battery good
Good discharge voltage and discharge capacity, significantly improves the voltage delay phenomenon of lithium/thinly chloride battery.
Second is that the first additive and Second addition in lithium/thinly chloride battery electrolyte of the present invention have preferable resist
Nucleophillic attack ability, the two synergistic effect can effectively inhibit Li2The loss of O stabilizes the structure of lithium-rich anode material, effectively slow
Solved the generation of cell voltage hysteresis, at the same lithium/thinly chloride battery electrolyte of the invention have good in oxidation resistance and
Non-ignitable characteristic, therefore there is preferable cycle performance and higher safety by lithium/thinly chloride battery prepared by the electrolyte
Property.
Third is that the preparation method of lithium/thinly chloride battery electrolyte of the present invention is simple, and easy to operate, formula science, raw material
It is at low cost, it is practical, it has a wide range of applications.
Fourth is that being distilled in the preparation method of lithium/thinly chloride battery electrolyte of the present invention to thionyl chloride, to first
Additive and Second addition are purified, and keep the impurity content for the lithium/thinly chloride battery electrolyte being prepared less, electricity
The performance for solving liquid is more excellent.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1:
A kind of lithium/thinly chloride battery electrolyte, including thionyl chloride, bis- (fluorine sulphonyl) imine lithiums and additive, electrolytic salt
The molar concentration of thionyl chloride solution be 0.1mol/L, the quality of additive is the 0.01% of electrolyte gross mass, additive packet
The first additive and Second addition are included, wherein the quality of the first additive is the 0.005% of electrolyte gross mass, the second addition
The quality of agent is the 0.005% of electrolyte gross mass.
The structural formula of first additive are as follows:
；
Wherein, X Cl；R1For itrile group；R2、R3It is hydrogen；R4For methyl.
The structural formula of Second addition are as follows:
；
Wherein, X1For Cl；R11、R21、R31It is methyl；R41For pyrrole heterocyclic base.
A kind of preparation method of lithium/thinly chloride battery electrolyte, the preparation method the following steps are included:
(1) under the dry environment of relative humidity≤0.5%, thionyl chloride is placed in flask, heating is distilled, and collects 70
DEG C fraction；
(2) under the dry environment of relative humidity≤0.5%, electrolytic salt is weighed, under inert atmosphere conditions, by above-mentioned electrolysis
Matter salt is dissolved in thionyl chloride fraction obtained by step (1), carries out constant volume, obtains the electrolysis that molar concentration is 0.1mol/L
The thionyl chloride solution of matter salt；
The purification of (3) first additives: extracting the first additive using acetone, obtains the first additive leaching liquor, will
Leaching liquor is transferred in oscillator, 30min is shaken at 100r/min, then distill to leaching liquor, is removed acetone, is obtained first
Additive crude extract finally removes supernatant, the first additive of purifying obtained by drying；The temperature of extraction is 30 DEG C, extraction
Time is 1h, and distillation is carried out at 40 DEG C by the way of vacuum distillation；
(4) purification of Second addition: the purification of Second addition is purified using sublimation purification device:
(a) fused salt is added to the mixing for the sodium nitrites and potassium nitrite of quality such as heating is indoor, and fused salt is by feeding inlet
Object heats fused salt using the first fused salt heating rod and the second fused salt heating rod, temperature is made to reach 200 DEG C；
(b) Second addition is fitted into distillation charging boat, in Second addition upper berth silica gel, is then placed in cylindrical tube, closes
Closed end passes through vacuum cooled pipe by vacuum pump suction to 0.03KPa behind the door, and the purification of Second addition is completed by 6h；
(5) under the dry environment of relative humidity≤0.5%, the first additive and step of the purifying that step (3) obtains are weighed
(4) Second addition of the purifying obtained is then added in the thionyl chloride solution of step (2) obtained electrolytic salt,
It is stirred continuously until being completely dissolved to get lithium/thinly chloride battery electrolyte.
Embodiment 2:
A kind of lithium/thinly chloride battery electrolyte, including thionyl chloride, di-oxalate lithium borate and additive, the Asia of electrolytic salt
The molar concentration of sulfonyl solutions of chlorine is 0.4mol/L, and the quality of additive is the 0.1% of electrolyte gross mass, and additive includes the
One additive and Second addition, wherein the quality of the first additive is the 0.05% of electrolyte gross mass, the matter of Second addition
Amount is the 0.05% of electrolyte gross mass.
The structural formula of first additive are as follows:
；
Wherein, X Br；R1For amido；R2、R3It is chloromethyl；R4For ethyl.
The structural formula of Second addition are as follows:
；
Wherein, X1For Br；R11、R21、R31It is chloromethyl；R41For furans heterocycle.
A kind of preparation method of lithium/thinly chloride battery electrolyte, the preparation method the following steps are included:
(1) under the dry environment of relative humidity≤0.6%, thionyl chloride is placed in flask, heating is distilled, and collects 72
DEG C fraction；
(2) under the dry environment of relative humidity≤0.6%, electrolytic salt is weighed, under inert atmosphere conditions, by above-mentioned electrolysis
Matter salt is dissolved in thionyl chloride fraction obtained by step (1), carries out constant volume, obtains the electrolysis that molar concentration is 0.4mol/L
The thionyl chloride solution of matter salt；
The purification of (3) first additives: extracting the first additive using acetone, obtains the first additive leaching liquor, will
Leaching liquor is transferred in oscillator, 35min is shaken at 150r/min, then distill to leaching liquor, is removed acetone, is obtained first
Additive crude extract finally removes supernatant, the first additive of purifying obtained by drying；The temperature of extraction is 32 DEG C, extraction
Time is 1.5h, and distillation is carried out at 50 DEG C by the way of vacuum distillation；
(4) purification of Second addition: the purification of Second addition is purified using sublimation purification device:
(a) fused salt is added to the mixing for the sodium nitrites and potassium nitrite of quality such as heating is indoor, and fused salt is by feeding inlet
Object heats fused salt using the first fused salt heating rod and the second fused salt heating rod, temperature is made to reach 210 DEG C；
(b) Second addition is fitted into distillation charging boat, in Second addition upper berth silica gel, is then placed in cylindrical tube, closes
Closed end passes through vacuum cooled pipe by vacuum pump suction to 0.04KPa behind the door, and the purification of Second addition is completed by 8h；
(5) under the dry environment of relative humidity≤0.6%, the first additive and step of the purifying that step (3) obtains are weighed
(4) Second addition of the purifying obtained is then added in the thionyl chloride solution of step (2) obtained electrolytic salt,
It is stirred continuously until being completely dissolved to get lithium/thinly chloride battery electrolyte.
Embodiment 3:
A kind of lithium/thinly chloride battery electrolyte, including thionyl chloride, trifluoromethanesulfonic acid lithium and additive, the Asia of electrolytic salt
The molar concentration of sulfonyl solutions of chlorine is 0.6mol/L, and the quality of additive is the 0.2% of electrolyte gross mass, and additive includes the
One additive and Second addition, wherein the quality of the first additive is the 0.1% of electrolyte gross mass, the matter of Second addition
Amount is the 0.2% of electrolyte gross mass.
The structural formula of first additive are as follows:
；
Wherein, X I；R1For hydroxyl；R2、R3It is phenyl；R4For chloromethyl.
The structural formula of Second addition are as follows:
；
Wherein, X1For I；R11、R21、R31It is methoxyl group；R41For thiophene heterocycle.
A kind of preparation method of lithium/thinly chloride battery electrolyte, the preparation method the following steps are included:
(1) under the dry environment of relative humidity≤0.7%, thionyl chloride is placed in flask, heating is distilled, and collects 74
DEG C fraction；
(2) under the dry environment of relative humidity≤0.7%, electrolytic salt is weighed, under inert atmosphere conditions, by above-mentioned electrolysis
Matter salt is dissolved in thionyl chloride fraction obtained by step (1), carries out constant volume, obtains the electrolysis that molar concentration is 0.6mol/L
The thionyl chloride solution of matter salt；
The purification of (3) first additives: extracting the first additive using acetone, obtains the first additive leaching liquor, will
Leaching liquor is transferred in oscillator, 40min is shaken at 200r/min, then distill to leaching liquor, is removed acetone, is obtained first
Additive crude extract finally removes supernatant, the first additive of purifying obtained by drying；The temperature of extraction is 34 DEG C, extraction
Time is 2h, and distillation is carried out at 60 DEG C by the way of vacuum distillation；
(4) purification of Second addition: the purification of Second addition is purified using sublimation purification device:
(a) fused salt is added to the mixing for the sodium nitrites and potassium nitrite of quality such as heating is indoor, and fused salt is by feeding inlet
Object heats fused salt using the first fused salt heating rod and the second fused salt heating rod, temperature is made to reach 220 DEG C；
(b) Second addition is fitted into distillation charging boat, in Second addition upper berth silica gel, is then placed in cylindrical tube, closes
Closed end passes through vacuum cooled pipe by vacuum pump suction to 0.05KPa behind the door, and the purification of Second addition is completed by 10h；
(5) under the dry environment of relative humidity≤0.7%, the first additive and step of the purifying that step (3) obtains are weighed
(4) Second addition of the purifying obtained is then added in the thionyl chloride solution of step (2) obtained electrolytic salt,
It is stirred continuously until being completely dissolved to get lithium/thinly chloride battery electrolyte.
Embodiment 4:
A kind of lithium/thinly chloride battery electrolyte, including thionyl chloride, three (trimethyl fluoride sulfonyl) lithium methides, lithium hexafluoro phosphate
And additive, the molar concentration of the thionyl chloride solution of electrolytic salt are 0.8mol/L, the quality of additive is the total matter of electrolyte
The 0.4% of amount, additive includes the first additive and Second addition, wherein the quality of the first additive is electrolyte gross mass
0.2%, the quality of Second addition is the 0.2% of electrolyte gross mass.
The structural formula of first additive are as follows:
；
Wherein, X F；R1For nitro；R2、R3It is methoxyl group；R4For propyl.
The structural formula of Second addition are as follows:
；
Wherein, X1For F；R11、R21、R31It is chloromethoxy；R41For 3- picoline heterocycle.
A kind of preparation method of lithium/thinly chloride battery electrolyte, the preparation method the following steps are included:
(1) under the dry environment of relative humidity≤0.8%, thionyl chloride is placed in flask, heating is distilled, and collects 78
DEG C fraction；
(2) under the dry environment of relative humidity≤0.8%, electrolytic salt is weighed, under inert atmosphere conditions, by above-mentioned electrolysis
Matter salt is dissolved in thionyl chloride fraction obtained by step (1), carries out constant volume, obtains the electrolysis that molar concentration is 0.8mol/L
The thionyl chloride solution of matter salt；
The purification of (3) first additives: extracting the first additive using acetone, obtains the first additive leaching liquor, will
Leaching liquor is transferred in oscillator, 50min is shaken at 250r/min, then distill to leaching liquor, is removed acetone, is obtained first
Additive crude extract finally removes supernatant, the first additive of purifying obtained by drying；The temperature of extraction is 40 DEG C, extraction
Time is 3h, and distillation is carried out at 70 DEG C by the way of vacuum distillation；
(4) purification of Second addition: the purification of Second addition is purified using sublimation purification device:
(a) fused salt is added to the mixing for the sodium nitrites and potassium nitrite of quality such as heating is indoor, and fused salt is by feeding inlet
Object heats fused salt using the first fused salt heating rod and the second fused salt heating rod, temperature is made to reach 240 DEG C；
(b) Second addition is fitted into distillation charging boat, in Second addition upper berth silica gel, is then placed in cylindrical tube, closes
Closed end passes through vacuum cooled pipe by vacuum pump suction to 0.07KPa behind the door, and the purification of Second addition is completed by 12h；
(5) under the dry environment of relative humidity≤0.8%, the first additive and step of the purifying that step (3) obtains are weighed
(4) Second addition of the purifying obtained is then added in the thionyl chloride solution of step (2) obtained electrolytic salt,
It is stirred continuously until being completely dissolved to get lithium/thinly chloride battery electrolyte.
Embodiment 5:
A kind of lithium/thinly chloride battery electrolyte, including thionyl chloride, three oxalic acid lithium phosphates, difluoro dioxalic acid lithium phosphate and add
Add agent, the molar concentration of the thionyl chloride solution of electrolytic salt is 1mol/L, and the quality of additive is electrolyte gross mass
0.5%, additive includes the first additive and Second addition, wherein the quality of the first additive is electrolyte gross mass
0.3%, the quality of Second addition is the 0.2% of electrolyte gross mass.
The structural formula of first additive are as follows:
；
Wherein, X Cl；R1For amido；R2、R3It is tolyl；R4For chloroethyl.
The structural formula of Second addition are as follows:
；
Wherein, X1For Cl；R11、R21、R31It is chloropropyl；R41For 2- chlorine furans heterocycle.
A kind of preparation method of lithium/thinly chloride battery electrolyte, the preparation method the following steps are included:
(1) under the dry environment of relative humidity≤1%, thionyl chloride is placed in flask, heating is distilled, and collects 80 DEG C
Fraction；
(2) under the dry environment of relative humidity≤1%, electrolytic salt is weighed, under inert atmosphere conditions, by above-mentioned electrolyte
Salt is dissolved in thionyl chloride fraction obtained by step (1), carries out constant volume, obtains the electrolytic salt that molar concentration is 1mol/L
Thionyl chloride solution；
The purification of (3) first additives: extracting the first additive using acetone, obtains the first additive leaching liquor, will
Leaching liquor is transferred in oscillator, 60min is shaken at 300r/min, then distill to leaching liquor, is removed acetone, is obtained first
Additive crude extract finally removes supernatant, the first additive of purifying obtained by drying；The temperature of extraction is 45 DEG C, extraction
Time is 4h, and distillation is carried out at 80 DEG C by the way of vacuum distillation；
(4) purification of Second addition: the purification of Second addition is purified using sublimation purification device:
(a) fused salt is added to the mixing for the sodium nitrites and potassium nitrite of quality such as heating is indoor, and fused salt is by feeding inlet
Object heats fused salt using the first fused salt heating rod and the second fused salt heating rod, temperature is made to reach 250 DEG C；
(b) Second addition is fitted into distillation charging boat, in Second addition upper berth silica gel, is then placed in cylindrical tube, closes
Closed end passes through vacuum cooled pipe by vacuum pump suction to 0.08KPa behind the door, and the purification of Second addition is completed by 15h；
(5) under relative humidity≤0.5-1% dry environment, the first additive and step of the purifying that step (3) obtains are weighed
(4) Second addition of the purifying obtained is then added in the thionyl chloride solution of step (2) obtained electrolytic salt,
It is stirred continuously until being completely dissolved to get lithium/thinly chloride battery electrolyte.
Comparative example:
Commercially available lithium/thinly chloride battery electrolyte is using the thionyl chloride solution of tetrachloro-lithium aluminate as electrolyte, and thionyl chloride was both
It is solvent is positive active material again, electrolytic salt is tetrachloro-lithium aluminate, lithium salt 1.7mol/L.
Effect example:
Make lithium/thinly chloride battery:
At room temperature by graphite positive electrode, conductive agent carbon black (SP), bonding agent Kynoar (PVDF) according to 8:1:1 ratio
Example is homogenized, and solvent is n-methyl-2-pyrrolidone (NMP), and solid content 25% is evenly applied to the aluminium foil of 0.02mm thickness
On, by drying, roll-in, cut-parts, carbon electrode film is made；
Anode is used uniformly carbon electrode film, and cathode uses metal lithium electrode, and electrolyte successively uses the embodiment of the present invention 1 to 5
Electrolyte in obtained lithium/thinly chloride battery electrolyte and comparative example produces lithium/thinly chloride battery respectively,
3.87V carries out charge-discharge test with 0.05C circulation 200 weeks, to battery, and test result is shown in Table 1, between 0.025-2C
Under any multiplying power, charge-discharge test is carried out to battery, test result is shown in Table 2.
1 battery of table carries out charge-discharge performance test result
From the test data of table 1 it is found that the battery of lithium/thinly chloride battery electrolyte obtained by the embodiment of the present invention 1 to 5 fills
After discharge cycles 200 weeks, capacity retention ratio 90% or more, up to 93.7%, electric discharge average voltage be respectively 3.36V,
3.34V, 3.32V, 3.35V, 3.37, and after the battery charging and discharging of comparative example lithium/thinly chloride battery electrolyte recycles 200 weeks,
Capacity retention ratio is 76.3%, electric discharge average voltage be 3.12V, the results showed that using lithium obtained by the embodiment of the present invention 1 to 5/
The cycle performance of the battery of thionyl chloride battery electrolyte is better than the battery of comparative example lithium/thinly chloride battery electrolyte, and
Voltage delay phenomenon is also obviously improved.
Battery carries out charge-discharge performance test result under 2 different multiplying of table
From the test data of table 2 it is found that the battery of lithium/thinly chloride battery electrolyte obtained by the embodiment of the present invention 1 is put down
Platform voltage and capacity are above the platform voltage of the battery of comparative example lithium/thinly chloride battery electrolyte, the results showed that using this
The battery of lithium/thinly chloride battery electrolyte obtained by inventive embodiments 1 has good discharge voltage and discharge capacity.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
Claims (10)
1. a kind of lithium/thinly chloride battery electrolyte, it is characterised in that: described including thionyl chloride, electrolytic salt and additive
The molar concentration of the thionyl chloride solution of electrolytic salt is 0.1-1mol/L, and the quality of the additive is electrolyte gross mass
0.01-0.5%。
2. a kind of lithium/thinly chloride battery electrolyte according to claim 1, which is characterized in that the additive includes
First additive and Second addition, the structural formula of first additive are as follows:
；
Wherein, X is halogen；R1For itrile group, amido, hydroxyl or nitro；R2、R3It is hydrogen, monosubstituted or polysubstituted C1-C6 alkane
Base, aryl, C1-C6 alkoxy or halogenated C1-C6 alkoxy；R4For C1-C6 alkyl or the C1- being mono-or polysubstituted with halogens
C6 alkyl.
3. a kind of lithium/thinly chloride battery electrolyte according to claim 2, which is characterized in that the Second addition
Structural formula are as follows:
；
Wherein, X1For halogen；R11、R21、R31It is C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy or halogenated C1-
C10 alkoxy；R41For it is unsubstituted or or by the alkyl-substituted heterocycle of C1-C6, containing in O, N, S element on the heterocycle
It is one or more.
4. a kind of lithium/thinly chloride battery electrolyte according to any one of claim 1 to 3, it is characterised in that: described
Electrolytic salt be bis- (fluorine sulphonyl) imine lithiums, di-oxalate lithium borate, trifluoromethanesulfonic acid lithium, three (trimethyl fluoride sulfonyl) lithium methides,
One of lithium hexafluoro phosphate, three oxalic acid lithium phosphates, difluoro dioxalic acid lithium phosphate, tetrafluoro oxalic acid lithium phosphate are a variety of.
5. a kind of lithium/thinly chloride battery electrolyte according to claim 4, it is characterised in that: first additive
Quality be electrolyte gross mass 0.005-0.3%, the quality of the Second addition is the 0.005- of electrolyte gross mass
0.2%。
6. a kind of preparation method of lithium/thinly chloride battery electrolyte, which is characterized in that the preparation method the following steps are included:
Thionyl chloride is distilled, fraction is collected；
It weighs electrolytic salt to be placed in thionyl chloride fraction obtained by step (1), constant volume obtains the thionyl chloride of electrolytic salt
Solution；
The purification of first additive: extracting the first additive using acetone, obtains the first additive leaching liquor, then to leaching
Extract is distilled, and the first additive, the first additive of purifying obtained by drying are obtained；
The purification of Second addition: the purification of Second addition is purified using sublimation purification device:
(a) fused salt is added to heating interior by feeding inlet, using the first fused salt heating rod and the second fused salt heating rod to molten
Salt is heated；
(b) Second addition is fitted into distillation charging boat, in Second addition upper berth silica gel, is then placed in cylindrical tube, closes
Closed end passes through vacuum cooled pipe behind the door and is vacuumized by vacuum pump, and the purification of Second addition is completed after a period of time；
(5) Second addition for the purifying that the first additive and step (4) for weighing the purifying that step (3) obtains obtain, then
It is added in the thionyl chloride solution of step (2) obtained electrolytic salt, is stirred continuously until being completely dissolved to get lithium/Asia
Chlorosulfuric acid battery electrolyte.
7. a kind of preparation method of lithium/thinly chloride battery electrolyte according to claim 6, which is characterized in that the system
Preparation Method the following steps are included:
(1) thionyl chloride is placed in flask, heating is distilled, and 70-80 DEG C of fraction is collected；
(2) electrolytic salt is weighed, under inert atmosphere conditions, by above-mentioned dissolving electrolyte salt sulfurous obtained by step (1)
In acyl chlorides fraction, constant volume is carried out, obtains the thionyl chloride solution for the electrolytic salt that molar concentration is 0.1-1mol/L；
The purification of (3) first additives: extracting the first additive using acetone, obtains the first additive leaching liquor, then
Leaching liquor is distilled, the first additive, the first additive of purifying obtained by drying are obtained；The temperature of the extraction is 30-
45 DEG C, the time of the extraction is 1-4h, and the distillation is carried out at 40-80 DEG C by the way of vacuum distillation；
(4) purification of Second addition: the purification of Second addition is purified using sublimation purification device:
(a) fused salt is added to heating interior by feeding inlet, using the first fused salt heating rod and the second fused salt heating rod to molten
Salt is heated, and temperature is made to reach 200-250 DEG C；
(b) Second addition is fitted into distillation charging boat, in Second addition upper berth silica gel, is then placed in cylindrical tube, closes
Closed end passes through vacuum cooled pipe by vacuum pump suction to 0.03-0.08KPa behind the door, completes Second addition by 6-15h
Purification；
The Second addition for the purifying that the first additive and step (4) for weighing the purifying that step (3) obtains obtain, is then added
Into the thionyl chloride solution of step (2) obtained electrolytic salt, it is stirred continuously until being completely dissolved to get lithium/thionyl
Chlorine battery electrolyte.
8. a kind of preparation method of lithium/thinly chloride battery electrolyte according to claim 6 or 7, it is characterised in that: institute
Stating fused salt in step (a) sodium nitrite of quality and the mixture of potassium nitrite such as is.
9. a kind of preparation method of lithium/thinly chloride battery electrolyte according to claim 8, it is characterised in that: described
Leaching liquor is transferred in oscillator before distillation by step in (3), shakes 30-60min at 100-300r/min.
10. a kind of preparation method of lithium/thinly chloride battery electrolyte according to claim 9, it is characterised in that: described
Step (1), step (2) and step (3) are operated in relative humidity≤0.5-1% dry environment.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811570609.7A CN109742446B (en) | 2018-12-21 | 2018-12-21 | Lithium/thionyl chloride battery electrolyte and preparation method thereof |
| CN202010736012.6A CN112072177A (en) | 2018-12-21 | 2018-12-21 | Lithium/thionyl chloride battery electrolyte |
| CN202010737131.3A CN112072178A (en) | 2018-12-21 | 2018-12-21 | Lithium/thionyl chloride battery electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811570609.7A CN109742446B (en) | 2018-12-21 | 2018-12-21 | Lithium/thionyl chloride battery electrolyte and preparation method thereof |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010736012.6A Division CN112072177A (en) | 2018-12-21 | 2018-12-21 | Lithium/thionyl chloride battery electrolyte |
| CN202010737131.3A Division CN112072178A (en) | 2018-12-21 | 2018-12-21 | Lithium/thionyl chloride battery electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109742446A true CN109742446A (en) | 2019-05-10 |
| CN109742446B CN109742446B (en) | 2020-09-08 |
Family
ID=66360901
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010737131.3A Pending CN112072178A (en) | 2018-12-21 | 2018-12-21 | Lithium/thionyl chloride battery electrolyte |
| CN201811570609.7A Active CN109742446B (en) | 2018-12-21 | 2018-12-21 | Lithium/thionyl chloride battery electrolyte and preparation method thereof |
| CN202010736012.6A Pending CN112072177A (en) | 2018-12-21 | 2018-12-21 | Lithium/thionyl chloride battery electrolyte |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010737131.3A Pending CN112072178A (en) | 2018-12-21 | 2018-12-21 | Lithium/thionyl chloride battery electrolyte |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010736012.6A Pending CN112072177A (en) | 2018-12-21 | 2018-12-21 | Lithium/thionyl chloride battery electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN112072178A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115863534A (en) * | 2022-12-29 | 2023-03-28 | 武汉昊诚锂电科技股份有限公司 | Lithium-ion battery positive plate and preparation device and preparation process thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4307160A (en) * | 1980-12-17 | 1981-12-22 | The United States Of America As Represented By The Secretary Of The Navy | Lithium-thionyl chloride battery with niobium pentachloride electrolyte |
| US4309490A (en) * | 1976-10-08 | 1982-01-05 | Honeywell Inc. | Long life thionyl chloride cell |
| US4355086A (en) * | 1981-10-01 | 1982-10-19 | Honeywell Inc. | Lithium thionyl chloride battery |
| CN101102000A (en) * | 2007-07-17 | 2008-01-09 | 中国地质大学（武汉） | Lithium thionyl chloride battery electrolyte and its making method |
| 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 |
| CN106129467A (en) * | 2016-08-31 | 2016-11-16 | 襄阳艾克特电池科技股份有限公司 | A kind of lithium thionyl chloride battery electrolyte manufacture method |
| CN106169608A (en) * | 2016-08-31 | 2016-11-30 | 襄阳艾克特电池科技股份有限公司 | A kind of lithium thionyl chloride battery electrolyte manufacture method |
-
2018
- 2018-12-21 CN CN202010737131.3A patent/CN112072178A/en active Pending
- 2018-12-21 CN CN201811570609.7A patent/CN109742446B/en active Active
- 2018-12-21 CN CN202010736012.6A patent/CN112072177A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4309490A (en) * | 1976-10-08 | 1982-01-05 | Honeywell Inc. | Long life thionyl chloride cell |
| US4307160A (en) * | 1980-12-17 | 1981-12-22 | The United States Of America As Represented By The Secretary Of The Navy | Lithium-thionyl chloride battery with niobium pentachloride electrolyte |
| US4355086A (en) * | 1981-10-01 | 1982-10-19 | Honeywell Inc. | Lithium thionyl chloride battery |
| CN101102000A (en) * | 2007-07-17 | 2008-01-09 | 中国地质大学（武汉） | Lithium thionyl chloride battery electrolyte and its making method |
| 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 |
| CN106129467A (en) * | 2016-08-31 | 2016-11-16 | 襄阳艾克特电池科技股份有限公司 | A kind of lithium thionyl chloride battery electrolyte manufacture method |
| CN106169608A (en) * | 2016-08-31 | 2016-11-30 | 襄阳艾克特电池科技股份有限公司 | A kind of lithium thionyl chloride battery electrolyte manufacture method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112072177A (en) | 2020-12-11 |
| CN109742446B (en) | 2020-09-08 |
| CN112072178A (en) | 2020-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105826607B (en) | A kind of electrolyte and the lithium ion battery including the electrolyte | |
| CN108306048A (en) | A kind of lithium-ion battery electrolytes and its lithium ion battery of preparation | |
| CN106356562A (en) | Electrolyte for ternary cathode material lithium ion battery and ternary cathode material lithium ion battery | |
| CN105731399A (en) | Preparation method of difluoro-sulfonyl imide lithium | |
| JP2018530852A (en) | Electrolytic solution for high voltage lithium ion battery, its preparation method and its application | |
| CN106058319B (en) | One kind has the electrolyte and the preparation method and application thereof of polyanionic functional group | |
| CN105390742A (en) | High-voltage lithium-ion battery electrolyte as well as preparation method and application thereof | |
| CN103560270B (en) | A kind of electrolyte for lithium ion battery | |
| CN107011371A (en) | A kind of siliceous glyoxaline ion liquid and its preparation method and application | |
| CN103035947A (en) | Novel electrolyte of lithium-ion battery and preparation method thereof | |
| CN107845831B (en) | A kind of electrolyte for lithium-sulfur cell | |
| CN106129473A (en) | A kind of nonaqueous electrolytic solution of silicon-based anode lithium ion battery | |
| CN108281700A (en) | A kind of electrolyte and preparation method with use the secondary lithium-sulfur battery of the electrolyte | |
| WO2023217091A1 (en) | Electrolyte additive, battery electrolyte and use thereof | |
| CN107819152A (en) | A kind of reference electrolyte and preparation method that can improve lithium-sulfur cell cycle performance | |
| CN103539168B (en) | The purification process of lithium hexafluoro phosphate | |
| Liu et al. | Research progress on preparation and purification of fluorine-containing chemicals in lithium-ion batteries | |
| CN105449139A (en) | Method for solving high-temperature flatulence of lithium titanate negative lithium-ion battery | |
| CN109742446A (en) | A kind of lithium/thinly chloride battery electrolyte and preparation method thereof | |
| CN107180998B (en) | A kind of electrolyte and lithium ion battery | |
| CN103996873B (en) | The lithium ion battery nonaqueous electrolytic solution of coupling BTR918 graphite cathode | |
| CN110627742B (en) | Preparation method and purification method of compound containing at least one cyclic ligand structure | |
| CN108767315A (en) | A kind of electrolysis additive, lithium battery electrolytes and lithium ion battery | |
| CN105633463B (en) | A kind of electrolyte of lithium-ion secondary battery suitable for low temperature environment electric discharge | |
| CN109346763B (en) | Electrolyte and lithium ion battery |
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 | ||
| CB02 | Change of applicant information |
Address after: 215000 LongLi and Building 1201, No. 59 Suli Road, Wuzhong District, Suzhou City, Jiangsu Province Applicant after: Pei Guanghua Address before: 325600 Xuyang Road, Yueqing City, Wenzhou City, Zhejiang Province, Confidence in Platinum Bay 1205 Applicant before: Pei Guanghua |
|
| CB02 | Change of applicant information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200812 Address after: 325600 No.531 Danxia Road, Leqing City, Wenzhou City, Zhejiang Province Applicant after: YUEQING HUAZUN ELECTRIC Co.,Ltd. Address before: 215000 LongLi and Building 1201, No. 59 Suli Road, Wuzhong District, Suzhou City, Jiangsu Province Applicant before: Pei Guanghua |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220811 Address after: No. 66, Xingyu Road, Haiyu Town, Changshu City, Suzhou City, Jiangsu Province 215000 Patentee after: Jiangsu Zhongluman New Material Technology Co., Ltd. Address before: 325600 No.531 Danxia Road, Yueqing City, Wenzhou City, Zhejiang Province Patentee before: YUEQING HUAZUN ELECTRIC Co.,Ltd. |
|
| TR01 | Transfer of patent right |