CN108808089A - A kind of iron manganese phosphate lithium battery and its electrolyte - Google Patents
A kind of iron manganese phosphate lithium battery and its electrolyte Download PDFInfo
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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
- H01M10/0564—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
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- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The invention belongs to technical field of lithium ion, and in particular to a kind of iron manganese phosphate lithium battery and its electrolyte are added with fluoro-ether, 2- methyl maleic anhydrides and sulfate compound three classes additive in electrolyte of the present invention.Wherein, SEI films are formed in cathode by 2- methyl maleic anhydrides, avoids the use of fluorinated ethylene carbonate and nitrile solvents, effectively promotes the high-temperature behavior and cycle performance of battery；The electrochemical window of electrolyte is improved by fluoro-ether, ensures that electrolyte all will not be oxidized decomposition in 4.5V or more voltages；Protective film is formed in positive electrode surface by sulfate compound, inhibits the dissolution of anode Mn metal ions, improves the high temperature and cycle performance of battery；Therefore, synergistic effect caused by use of the present invention by fluoro-ether, 2- methyl maleic anhydrides and sulfate compound three classes additive so that iron manganese phosphate lithium battery has excellent cycle performance and high temperature performance in 2.5V~4.5V voltage ranges.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of iron manganese phosphate lithium battery and its electrolyte.
Background technology
LiFePO4 (LFP) battery is since its safety coefficient is relatively high, thus new energy commercial car mainstream is mating at present
Power battery be substantially ferric phosphate lithium cell, but the requirement with later stage country to power battery energy density steps up,
Demand of the integral new-energy passenger to energy density also can be promoted further.Due to LFP compacted density and operating voltage (3.2V) compared with
It is low, cause the space that LFP battery energy densities are further promoted extremely limited, it is clear that cannot be satisfied this requirement.
And it is all the iron manganese phosphate for lithium (LiMn of olivine structuralxFe1-xPO4, 0 < x < 1) then have operating voltage high
The characteristics of (3.9V), can make battery specific energy promote 10~15%, be next-generation more promising novel anode material.But phosphorus
The upper limit charging voltage that sour ferromanganese lithium is up to 4.5V has exceeded the electrochemical window range of conventional electrolysis liquid, and electrolyte can be in phosphoric acid
Ferromanganese lithium material surface occurs oxygenolysis side reaction and then deteriorates cycle life and bring certain safety risks.Separately
Outside, similar to spinel lithium manganate (LMO), there is also more serious Mn problems of dissolution, especially Mn under high temperature for iron manganese phosphate for lithium
It dissolves more serious, dissolves Mn in the electrolytic solution2+It is reduced into metal Mn on graphite cathode surface and SEI films are catalytically decomposed and break
Bad cathode interface causes battery capacity to decay.
The above feature of iron manganese phosphate for lithium proposes very high requirement to electrolyte, and iron manganese phosphate for lithium is electric on the market at present
Solution liquid technology is not yet ripe, and main cause is：In high voltage system, fluorinated ethylene carbonate (FEC) is due to higher
Oxidizing potential and excellent cathode film formation characteristic and be commonly used to ensure the cycle performance of battery, but its high-temperature stability compared with
Difference is easy under high temperature to decompose to generate hydrofluoric acid (HF), aggravates the dissolution of cathode metal ion, battery high-temperature is caused to store or follow
Flatulence after ring.In order to solve the problems, such as that fluorinated ethylene carbonate high temperature aerogenesis, common solution are to be added in the electrolytic solution
Nitrile solvents inhibit the aerogenesis of fluoro ethylene carbonate, but nitrile solvents are poor with the compatibility of graphite cathode, the later stage is caused to be followed
Ring decaying is big, cannot be satisfied the long circulating requirement of power and stored energy application.Therefore, electrolyte becomes restricts iron manganese phosphate at present
One important bottleneck of lithium battery practical application develops the inevitable approach that matched electrolyte is its industrialized development.
Invention content
It is an object of the invention to：In view of the deficiencies of the prior art, a kind of iron manganese phosphate lithium battery electrolytes are provided, are made
The iron manganese phosphate lithium battery prepared with the electrolyte has excellent cycle performance and height in 2.5V~4.5V voltage ranges
Warm nature energy.
To achieve the goals above, the present invention uses following technical scheme：
A kind of iron manganese phosphate lithium battery electrolytes, including Non-aqueous Organic Solvents, lithium salts and additive, the additive packet
Include fluoro-ether, 2- methyl maleic anhydrides and sulfate compound, general structure such as formula I and/or the formula of the sulfate compound
Shown in II：
Wherein, R1, R2, R3 it is separate be hydrogen atom, the straight chain that carbon atom number is 1~5 or branch alkyl in
It is any.
Preferably, the additive amount of the fluoro-ether accounts for the 0.5~10.0% of electrolyte gross mass, the 2- citraconic acids
The additive amount of acid anhydride accounts for the 0.1~3.0% of electrolyte gross mass, and the additive amount of the sulfate compound accounts for electrolyte gross mass
0.5~5.0%.
Preferably, the sulfate compound is sulfuric acid vinyl ester, 4- methylsulfuric acids vinyl acetate, 4- propyl sulfuric acid ethylene
It is one or more in ester, dimethyl suflfate, dithyl sulfate, sulfuric acid methyl ethyl ester, dipropyl sulfate, sulfuric acid diisopropyl ester.
Preferably, the fluoro-ether is 1,1,2,2- tetra- fluoro ethyl -2,2,3,3- tetrafluoro propyl ethers, 1,1,2,2- tetrafluoro second
Benzyl ethyl ether, fluoromethyl-1,1,1,3,3,3-hexafluoroisopropylether, tetra- fluoro ethyl methyl ethers of 1,1,2,2-, 1,1,2,2- tetrafluoro second
Base -4- methyl phenyl ethers, tetra- fluoro ethyl -2,2,2- trifluoroethyls ethers of 1,1,2,2-, 2,6- difluoroanisoles, 1,1,1,3,3,3-
At least one of hexafluoro isopropyl methyl ether, five fluoro- 2- trifluoromethylpropyls methyl ethers of 1,1,3,3,3-.
Preferably, the non-aqueous organic solvent is chain or cricoid carbonic ester, carboxylate and ethers, and described non-aqueous have
Solvent accounts for the 70.0~85.0% of electrolyte gross mass.
Preferably, the Non-aqueous Organic Solvents are dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propylene carbonate
Ester, ethylene carbonate, methyl propyl carbonate, ethyl propionate, propyl propionate, ethyl acetate, Ethyl formate, propyl butyrate, tetrahydrochysene furan
It mutters, the two or more mixtures mixed in any proportion in dioxy cycloalkanes, diethyl diethylene glycol diethyl ether, gamma-butyrolacton.
Preferably, the lithium salts is lithium hexafluoro phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, double fluorine sulfimides
At least one of lithium, LiBF4, double trifluoromethanesulfonimide lithiums；The lithium salts account for electrolyte gross mass 10.0~
15.0%.
Another object of the present invention is to provide a kind of iron manganese phosphate lithium batteries, including by positive plate, isolation film and cathode
For piece by lamination or the battery core and electrolyte of winding formation, the positive electrode active materials of the positive plate are LiMnxFe1-xPO4,
Wherein, 0 < x < 1, the electrolyte are the iron manganese phosphate lithium battery electrolytes described in any of the above-described section.
The beneficial effects of the present invention are：Added with fluoro-ether, 2- in a kind of iron manganese phosphate lithium battery electrolytes of the present invention
Methyl maleic anhydride and sulfate compound three classes additive.Wherein, SEI films are formed in cathode by 2- methyl maleic anhydrides,
The use of fluorinated ethylene carbonate and nitrile solvents is avoided, the high-temperature behavior and cycle performance of battery are effectively promoted；Pass through fluorine
The electrochemical window of electrolyte is improved for ether, ensures that electrolyte all will not be oxidized decomposition in 4.5V or more voltages；Pass through sulfuric acid
Ester compounds form protective film in positive electrode surface, inhibit the dissolution of anode Mn metal ions, improve the high temperature and cyclicity of battery
Energy；In addition, Non-aqueous Organic Solvents used in the present invention have higher oxygenolysis current potential and take into account certain high temperature and
Cryogenic property, to ensure the high-temperature storage and low temperature performance of battery.Therefore, the present invention passes through fluoro-ether, 2- methyl horses
Carry out synergistic effect caused by the use of acid anhydrides and sulfate compound three classes additive so that iron manganese phosphate lithium battery is in 2.5V
There is excellent cycle performance and high temperature performance in~4.5V voltage ranges.
Specific implementation mode
To keep technical scheme of the present invention and advantage clearer, below in conjunction with specific embodiment, to the skill of the present invention
Art scheme is clearly and completely described, it is clear that and described embodiments are some of the embodiments of the present invention, rather than all
Embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art institute without creative efforts
The every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
The preparation of electrolyte：
In the glove box (moisture < 10ppm, oxygen < 1ppm) full of argon gas, by ethylene carbonate, propene carbonate,
Methyl ethyl carbonate, diethyl carbonate are with 30:5:30:35 mass ratioes are uniformly mixed, and mass fraction is added in mixed solution and is
The 1 of 3.0%, 1,2,2- tetra- fluoro ethyl -2,2,3,3- tetrafluoro propyl ethers, 1.0% sulfuric acid vinyl ester, 1.0% 2- methyl horses
Carry out acid anhydrides, then is slowly added to the LiPF that mass fraction is 13.0% into mixed solution6, stir and be completely dissolved to it, obtain reality
Apply the electrolyte of example 1.
The preparation of lithium ion battery：
By positive active material LiMn0.4Fe0.6PO4, conductive agent acetylene black, binder polyvinylidene fluoride (PVDF) press matter
After amount is thoroughly mixed uniformly than 96: 2: 2 in N-Methyl pyrrolidone dicyandiamide solution, it is coated on drying on Al foils, cold pressing,
Obtain positive plate.
By negative electrode active material graphite, conductive agent acetylene black, binder butadiene-styrene rubber (SBR), thickener carboxymethyl cellulose
After plain sodium (CMC) is thoroughly mixed uniformly according to mass ratio 96: 2: 1: 1 in deionized water solvent system, it is coated on Cu foils
Upper drying, cold pressing, obtain negative plate.
Using polyethylene (PE) be basement membrane and in the nano oxidized aluminized coating of coating on base films as isolation film.
Winding obtains naked battery core in the same direction after positive plate, isolation film, negative plate are stacked gradually, and uses aluminum plastic film
It is packed, the processes such as the battery after fluid injection is encapsulated, shelve, be melted into, aging, secondary encapsulation, partial volume obtain iron manganese phosphate for lithium
Battery.
Embodiment 2
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas
In 1ppm), by ethylene carbonate, propene carbonate, methyl ethyl carbonate, diethyl carbonate with 30:5:30:The mixing of 35 mass ratioes is equal
It is even, methyl fluoride -1,1 that mass fraction is 3.0%, 1,3,3,3- hexafluoroisopropyl ether, 1.0% 4- are added in mixed solution
Methylsulfuric acid vinyl acetate, 1.0% 2- methyl maleic anhydrides, then it is 13.0% to be slowly added to mass fraction into mixed solution
LiPF6, stir and be completely dissolved to it, obtain the electrolyte of embodiment 2.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 3
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas
In 1ppm), by ethylene carbonate, propene carbonate, methyl ethyl carbonate, diethyl carbonate with 30:5:30:The mixing of 35 mass ratioes is equal
1,1,2,2- tetra- fluoro ethyl -2,2 even, that addition mass fraction is 3.0% in mixed solution, 3,3- tetrafluoro propyl ethers, 1.0%
Sulfuric acid vinyl ester, 2.0% 2- methyl maleic anhydrides, then it is 13.0% to be slowly added into mixed solution mass fraction
LiPF6, stir and be completely dissolved to it, obtain the electrolyte of embodiment 3.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 4
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas
In 1ppm), by ethylene carbonate, propene carbonate, methyl ethyl carbonate, ethyl propionate with 30:5:30:The mixing of 35 mass ratioes is equal
1,1,2,2- tetra- fluoro ethyl -2,2 even, that addition mass fraction is 3.0% in mixed solution, 3,3- tetrafluoro propyl ethers, 1.0%
Sulfuric acid vinyl ester, 1.0% 2- methyl maleic anhydrides, then it is 13.0% to be slowly added into mixed solution mass fraction
LiPF6, stir and be completely dissolved to it, obtain the electrolyte of embodiment 4.
Remaining is with embodiment 1, and which is not described herein again.
Embodiment 5
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas
In 1ppm), by ethylene carbonate, propene carbonate, methyl ethyl carbonate, diethyl carbonate with 30:5:30:The mixing of 35 mass ratioes is equal
1,1,2,2- tetra- fluoro ethyl -2,2 even, that addition mass fraction is 3.0% in mixed solution, 3,3- tetrafluoro propyl ethers, 1.0%
Sulfuric acid vinyl ester, 2.0% 2- methyl maleic anhydrides, then it is 13.0% to be slowly added into mixed solution mass fraction
LiPF6, stir and be completely dissolved to it, obtain the electrolyte of embodiment 3.
Remaining is with embodiment 1, and which is not described herein again.
Comparative example 1
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas
In 1ppm), by ethylene carbonate, propene carbonate, methyl ethyl carbonate, diethyl carbonate with 30:5:30:The mixing of 35 mass ratioes is equal
Fluorinated ethylene carbonate even, that addition mass fraction is 3.0% in mixed solution, 2.0% 1,3-propane sultone, then to
The LiPF that mass fraction is 13.0% is slowly added in mixed solution6, stir and be completely dissolved to it, obtain the electrolysis of comparative example 1
Liquid.
Remaining is with embodiment 1, and which is not described herein again.
Comparative example 2
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas
In 1ppm), by ethylene carbonate, propene carbonate, methyl ethyl carbonate, diethyl carbonate with 30:5:30:The mixing of 35 mass ratioes is equal
Fluorinated ethylene carbonate even, that addition mass fraction is 3.0% in mixed solution, 2.0% 1,3-propane sultone,
2.0% succinonitrile, then the LiPF that mass fraction is 13.0% is slowly added into mixed solution6, it stirs to it and is completely dissolved,
Obtain the electrolyte of comparative example 2.
Remaining is with embodiment 1, and which is not described herein again.
Comparative example 3
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas
In 1ppm), by ethylene carbonate, propene carbonate, methyl ethyl carbonate, diethyl carbonate with 30:5:30:The mixing of 35 mass ratioes is equal
1,1,2,2- tetra- fluoro ethyl -2,2 even, that addition mass fraction is 3.0% in mixed solution, 3,3- tetrafluoro propyl ethers, 1.0%
Sulfuric acid vinyl ester, then be slowly added into mixed solution the LiPF that mass fraction is 13.0%6, it stirs to it and is completely dissolved,
Obtain the electrolyte of comparative example 3.
Remaining is with embodiment 1, and which is not described herein again.
Comparative example 4
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas
In 1ppm), by ethylene carbonate, propene carbonate, methyl ethyl carbonate, diethyl carbonate with 30:5:30:The mixing of 35 mass ratioes is equal
1,1,2,2- tetra- fluoro ethyl -2,2 even, that addition mass fraction is 3.0% in mixed solution, 3,3- tetrafluoro propyl ethers, 1.0%
2- methyl maleic anhydrides, then be slowly added into mixed solution the LiPF that mass fraction is 13.0%6, stir completely molten to it
Solution, obtains the electrolyte of comparative example 4.
Remaining is with embodiment 1, and which is not described herein again.
Comparative example 5
The preparation of electrolyte as different from Example 1：In glove box (moisture < 10ppm, oxygen < full of argon gas
In 1ppm), by ethyl propionate, propyl propionate, methyl ethyl carbonate, diethyl carbonate with 30:5:30:35 mass ratioes are uniformly mixed,
The sulfuric acid vinyl ester that addition mass fraction is 1.0% in mixed solution, 1.0% 2- methyl maleic anhydrides, then it is molten to mixing
The LiPF that mass fraction is 13.0% is slowly added in liquid6, stir and be completely dissolved to it, obtain the electrolyte of comparative example 5.
Remaining is with embodiment 1, and which is not described herein again.
Following performance test experiment is carried out to the battery of Examples 1 to 5 and comparative example 1~5 respectively：
Room temperature 1C/1C loop tests are tested：Examples 1 to 5 and 1~5 gained battery of comparative example are charged to 1.0C
It is changed to constant-voltage charge after 4.5V limitation voltages to cut-off current 0.01C, stands 5min, then 1.0C is discharged to blanking voltage
2.5V stands 5min, by above-mentioned work step recycle within 1000 weeks, discharge capacity of the cell data such as 1 institute of table when being recycled to 1000 weeks
Show.
- 20 DEG C of discharge test experiments of low temperature：Examples 1 to 5 and 1~5 gained battery of comparative example are charged to 1.0C
It is changed to constant-voltage charge after 4.5V limitation voltages to cut-off current 0.01C, stands 5min, then 1.0C is discharged to blanking voltage
2.5V, released capacity are denoted as initial capacity；Constant-voltage charge is changed to cut-off current after charging to 4.5V limitation voltages with 1.0C
Battery is positioned over constant temperature in -20 DEG C of high-low temperature chambers and shelves 12h, then discharged with 1.0C by 0.01C, records low temperature discharge capacity.
Low temperature discharging efficiency is the percentage of low temperature 1.0C discharge capacities and room temperature 1.0C discharge capacities, low temperature discharging efficiency result such as table
Shown in 1.
High temperature storage test experiments：4.5V is charged to Examples 1 to 5 and 1~5 gained battery of comparative example with 1.0C to limit
It is changed to constant-voltage charge after voltage to cut-off current 0.01C, stands 5min, then 1.0C is discharged to blanking voltage 2.5V, is released
Capacity is denoted as initial capacity；Constant-voltage charge is changed to cut-off current 0.01C after charging to 4.5V limitation voltages with 1.0C, and open circuit is put
2h is set, original depth and initial internal resistance are measured；Battery core be stored in temperature be 60 DEG C ± 2 DEG C under conditions of open circuit storage 7 days after,
Battery core is taken out, tests the hot thickness of battery immediately, the internal resistance of cell is tested after shelving 2h coolings at room temperature；Then battery core first with
1.0C discharges, then with 1.0C charge and discharge, test residual capacity and recovery capacity.Calculate battery storage before and after hot Thickness Measurement by Microwave, internal resistance,
Residual capacity restores Capacitance Shift Rate, and the results are shown in Table 1.
7 days 1 battery 1C/1C cycle performances of table, -20 DEG C of electric discharges of low temperature and 60 DEG C of storages the performance test results
In comparative example 1 it can be seen from the test result of table 1, the normal-temperature circulating performance of battery is general, and after high-temperature storage
All very greatly, residual capacity and recovery capacity are also relatively low for the thickness of battery and internal resistance variation.Main cause is contained in electrolyte
Some FEC high-temperature stabilities are poor, are easy to decompose generation hydrofluoric acid (HF) under high temperature, aggravate the dissolution of cathode metal ion, lead
Flatulence after sending a telegraph pond high-temperature storage or recycling.In comparative example 2, due to the addition of nitrile additive SN, the high-temperature storage of battery
Performance is obviously improved, however nitrile solvents are poor with the compatibility of graphite cathode, causes later cycles decaying big, can not
Meet the long circulating requirement of power battery.
The lithium-ion electrolyte of Examples 1 to 5 is applied in iron manganese phosphate lithium battery, and cycle and high-temperature storage performance all obtain
Significant raising is arrived.Wherein embodiment 1 is compared with comparative example 3~5 as can be seen that fluoro-ether, 2- methyl maleic anhydrides and sulphur
It is good that the effect that any two is used in mixed way in ester compound is all used together reached effect less than three classes additive.This
It is to lay particular emphasis on improvement cycle performance because 2- methyl maleic anhydrides mainly form SEI films in cathode, play replacement fluorine for carbonic acid
The effect of vinyl acetate；Sulfate compound mainly forms protective film in positive electrode surface, inhibits the dissolution of cathode metal ion, stresses
In the high-temperature storage performance for improving battery；Fluoro-ether can improve the electrochemical window of electrolyte, ensure electrolyte 4.5V with
Upper voltage all will not be oxidized decomposition, while improve the high temperature and cycle performance of battery.
Comparative example 1 and 3 as can be seen that 2- methyl maleic anhydrides additive capacity be increased to 2% after low temperature discharge property
It can be substantially reduced, main cause is that its film forming is relatively thick, and impedance comparison is high under low temperature, therefore 2- methyl maleic anhydride additive amounts
It is unsuitable excessively high.
Comparative example 3 and 5 is as can be seen that use low temperature discharge property after ethyl propionate and propyl propionate in electrolyte solvent
Can have been significantly improved, mainly carboxylate has fusing point more lower than carbonic ester and viscosity, be conducive under low temperature lithium from
The migration of son.
It to sum up analyzes, the present invention is made by fluoro-ether, 2- methyl maleic anhydrides and sulfate compound three classes additive
With generated synergistic effect so that iron manganese phosphate lithium battery has excellent cycle performance in 2.5V~4.5V voltage ranges
And high temperature performance, thus have wide practical use in iron manganese phosphate for lithium positive polar body system lithium cell.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is changed.Therefore, the invention is not limited in above-mentioned specific implementation mode, every those skilled in the art exist
Made any conspicuously improved, replacement or modification all belongs to the scope of protection of the present invention on the basis of the present invention.This
Outside, although having used some specific terms in this specification, these terms are merely for convenience of description, not to the present invention
Constitute any restrictions.
Claims (8)
1. a kind of iron manganese phosphate lithium battery electrolytes, including Non-aqueous Organic Solvents, lithium salts and additive, it is characterised in that：Institute
It includes fluoro-ether, 2- methyl maleic anhydrides and sulfate compound to state additive, and the general structure of the sulfate compound is such as
Shown in formula I and/or formula II：
Wherein, R1, R2, R3 it is separate be hydrogen atom, the straight chain that carbon atom number is 1~5 or branch alkyl in appoint
It is a kind of.
2. a kind of iron manganese phosphate lithium battery electrolytes according to claim 1, it is characterised in that：The addition of the fluoro-ether
Amount accounts for the 0.5~10.0% of electrolyte gross mass, the additive amounts of the 2- methyl maleic anhydrides account for electrolyte gross mass 0.1~
3.0%, the additive amount of the sulfate compound accounts for the 0.5~5.0% of electrolyte gross mass.
3. a kind of iron manganese phosphate lithium battery electrolytes according to claim 1, it is characterised in that：The sulfate compound
For sulfuric acid vinyl ester, 4- methylsulfuric acids vinyl acetate, 4- propyl sulfuric acid vinyl ester, dimethyl suflfate, dithyl sulfate, sulfuric acid first and second
It is one or more in ester, dipropyl sulfate, sulfuric acid diisopropyl ester.
4. a kind of iron manganese phosphate lithium battery electrolytes according to claim 1, it is characterised in that：The fluoro-ether is 1,1,
Tetra- fluoro ethyl -2,2,3,3- tetrafluoros propyl ethers of 2,2-, 1,1,2,2- tetrafluoro ethyl diethyldithiocarbamates ether, methyl fluoride -1,1,1,3,3,3- six
Fluorine isopropyl ether, tetra- fluoro ethyl methyl ethers of 1,1,2,2-, tetra- fluoro ethyl -4- methyl phenyl ethers of 1,1,2,2-, 1,1,2,2- tetrafluoro second
Base -2,2,2- trifluoroethyls ether, 2,6- difluoroanisoles, 1,1,1,3,3,3- hexafluoro isopropyls methyl ether, 1,1,3,3,3- five
At least one of fluoro- 2- trifluoromethylpropyls methyl ether.
5. a kind of iron manganese phosphate lithium battery electrolytes according to claim 1, it is characterised in that：The non-aqueous organic solvent
For chain or cricoid carbonic ester, carboxylate and ethers, the Non-aqueous Organic Solvents account for electrolyte gross mass 70.0~
85.0%.
6. a kind of iron manganese phosphate lithium battery electrolytes according to claim 5, it is characterised in that：It is described non-aqueous organic molten
Agent is dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propene carbonate, ethylene carbonate, methyl propyl carbonate, propionic acid second
Ester, propyl propionate, ethyl acetate, Ethyl formate, propyl butyrate, tetrahydrofuran, dioxy cycloalkanes, diethyl diethylene glycol diethyl ether, γ-Ding Nei
The two or more mixtures mixed in any proportion in ester.
7. a kind of iron manganese phosphate lithium battery electrolytes according to claim 1, it is characterised in that：The lithium salts is hexafluoro phosphorus
Sour lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, double fluorine sulfimide lithiums, LiBF4, double trifluoromethanesulfonimides
At least one of lithium；The lithium salts accounts for the 10.0~15.0% of electrolyte gross mass.
8. a kind of iron manganese phosphate lithium battery, include the battery core formed by lamination or winding by positive plate, isolation film and negative plate,
And electrolyte, the positive electrode active materials of the positive plate are LiMnxFe1-xPO4, wherein 0 < x < 1, it is characterised in that：Institute
It is claim 1~7 any one of them iron manganese phosphate lithium battery electrolytes to state electrolyte.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109888390A (en) * | 2019-03-08 | 2019-06-14 | 东莞市坤乾新能源科技有限公司 | A kind of electrolyte and lithium battery that the dedicated high magnification high temperature resistant of electronic cigarette is taken into account |
| CN111200164A (en) * | 2020-01-09 | 2020-05-26 | 中南大学 | Lithium ion battery electrolyte and lithium ion battery |
| CN113036219A (en) * | 2021-03-05 | 2021-06-25 | 星恒电源股份有限公司 | Electrolyte and sodium ion battery with high and low temperature performance |
| CN113571770A (en) * | 2020-05-28 | 2021-10-29 | 深圳市研一新材料有限责任公司 | Electrolyte for natural graphite cathode lithium ion battery |
| CN114335717A (en) * | 2021-11-15 | 2022-04-12 | 上海大学 | High-voltage lithium battery electrolyte additive and application thereof |
| CN114665155A (en) * | 2022-05-23 | 2022-06-24 | 山东海科创新研究院有限公司 | Disubstituted dihalogen phosphate ester additive, preparation method and application thereof |
| CN115360429A (en) * | 2022-09-30 | 2022-11-18 | 苏州德加能源科技有限公司 | Novel low-temperature battery electrolyte and preparation method and application thereof |
| CN116435601A (en) * | 2023-06-14 | 2023-07-14 | 广州天赐高新材料股份有限公司 | Electrolyte and application thereof |
| CN117457987A (en) * | 2023-11-28 | 2024-01-26 | 广东聚圣科技有限公司 | Electrolyte additive, preparation method thereof and battery |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888390A (en) * | 2019-03-08 | 2019-06-14 | 东莞市坤乾新能源科技有限公司 | A kind of electrolyte and lithium battery that the dedicated high magnification high temperature resistant of electronic cigarette is taken into account |
| CN111200164A (en) * | 2020-01-09 | 2020-05-26 | 中南大学 | Lithium ion battery electrolyte and lithium ion battery |
| CN113571770A (en) * | 2020-05-28 | 2021-10-29 | 深圳市研一新材料有限责任公司 | Electrolyte for natural graphite cathode lithium ion battery |
| CN113571770B (en) * | 2020-05-28 | 2023-05-05 | 深圳市研一新材料有限责任公司 | Electrolyte for natural graphite negative electrode lithium ion battery |
| CN113036219A (en) * | 2021-03-05 | 2021-06-25 | 星恒电源股份有限公司 | Electrolyte and sodium ion battery with high and low temperature performance |
| CN114335717A (en) * | 2021-11-15 | 2022-04-12 | 上海大学 | High-voltage lithium battery electrolyte additive and application thereof |
| CN114665155A (en) * | 2022-05-23 | 2022-06-24 | 山东海科创新研究院有限公司 | Disubstituted dihalogen phosphate ester additive, preparation method and application thereof |
| CN114665155B (en) * | 2022-05-23 | 2022-08-02 | 山东海科创新研究院有限公司 | Disubstituted dihalogen phosphate additive and preparation method and application thereof |
| CN115360429A (en) * | 2022-09-30 | 2022-11-18 | 苏州德加能源科技有限公司 | Novel low-temperature battery electrolyte and preparation method and application thereof |
| CN116435601A (en) * | 2023-06-14 | 2023-07-14 | 广州天赐高新材料股份有限公司 | Electrolyte and application thereof |
| CN116435601B (en) * | 2023-06-14 | 2024-03-22 | 广州天赐高新材料股份有限公司 | Electrolyte and application thereof |
| CN117457987A (en) * | 2023-11-28 | 2024-01-26 | 广东聚圣科技有限公司 | Electrolyte additive, preparation method thereof and battery |
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Application publication date: 20181113 |