CN106785024A - A kind of long-life ferric phosphate lithium cell electrolyte of wide temperature range and compound method - Google Patents
A kind of long-life ferric phosphate lithium cell electrolyte of wide temperature range and compound method Download PDFInfo
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Abstract
The application discloses a kind of long-life ferric phosphate lithium cell electrolyte of wide temperature range and compound method in fact：Electrolyte is constituted：Lithium salts, carbonats compound, additive and ionic liquid；Wherein, the mass fraction of the carbonats compound is：60.0%~65.0%；The mass fraction of the ionic liquid is：10.0%~15.0%；The mass fraction of the additive is：5%~10%.Using under the conditions of 40 DEG C of the ferric phosphate lithium cell that the electrolyte shown in the embodiment of the present application is made, the rate of capacity performance first is higher than 80.0%, and capability retention is above 60.0%, 80.0%, 80.0% respectively after circulation 3000 times under the conditions of 40 DEG C, 25 DEG C, 60 DEG C according to 3C discharge and recharges system, it can be seen that, the ferric phosphate lithium cell being made of the electrolyte shown in the embodiment of the present application still has capability retention higher under normal temperature and height environmental condition after multiple high power charging-discharging system is circulated.
Description
Technical field
The application is related to energy technology field, more particularly to a kind of long-life ferric phosphate lithium cell electrolyte of wide temperature range and
Compound method.
Background technology
In traditional energy technical field, development and utilization environmental protection new energy, the rigidity as era development needs.Electricity
Pond is significant in terms of rationally the various novel environment friendly energy are utilized as a kind of energy storage and reforming unit；LiFePO4
Battery is nontoxic without any heavy metal and rare metal (Ni-MH battery needs rare metal), the advantages of non-pollution safety performance is good,
Had a wide range of applications in the field such as new energy passenger car and special-purpose vehicle, energy storage, startup power supply.
Ferric phosphate lithium cell is made up of positive pole, negative pole, barrier film, electrolyte, both positive and negative polarity infiltrate in the electrolytic solution, lithium ion with
Electrolyte is moved for medium between both positive and negative polarity, realizes the discharge and recharge of battery.Electrolyte in battery used as playing conduction
Ion conductor, the state of interface that electrolyte is formed with both positive and negative polarity largely influences the electric property of battery.LiFePO4 electricity
The electrolyte in pond is mostly liquid organic electrolyte, is mainly made up of organic solvent and lithium salts, wherein, generally using alkylcarbonic acid
Ester type compound is used as organic solvent.Use multicomponent mixed solvent, these mixed solvents, in low temperature mostly in actual applications
Under the conditions of, electrolysis fluid viscosity increase, electrical conductivity reduction.
This ferric phosphate lithium cell is in relatively low, the battery longevity by capability retention after the circulation of multiple high power charging-discharging system
Life is short.
The content of the invention
This application provides a kind of long-life ferric phosphate lithium cell electrolyte of wide temperature range and compound method, to solve now to adopt
With the ferric phosphate lithium cell of existing electrolyte, capability retention is relatively low after being circulated by multiple high power charging-discharging system, battery
The problem of short life.
The application first aspect shows a kind of long-life ferric phosphate lithium cell electrolyte of wide temperature range, the electrolyte composition
For：Lithium salts, carbonats compound, additive and ionic liquid；
The mass fraction of the carbonats compound is：60.0%~65.0%；
The mass fraction of the additive is 5.0%~10.0%；
The mass fraction of the ionic liquid is：10.0%~15.0%
The mass fraction of the lithium salts is：10%~25%.
Further, the carbonats compound is ethylene carbonate, propene carbonate, dimethyl carbonate, carbonic acid diethyl
One or more of ester, methyl ethyl carbonate, dibutyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, ethyl butyl carbonate.
Further, the structural formula of the fluorine-containing carbonic ester is：
Wherein, Rh is H or alkyl；Rf is H (CF2CF2)n1CH2 -, F (CF2CF2)n2CH2CH2 -Or CF3CF2CF2O(CF
(CF3)CF2O)n3CF(CF3)CH2 -；
Wherein, n1、n2It is positive integer；n3It is nonnegative integer.
Further, the anion chemical constitution of the ionic liquid is：
Further, the cation of the ionic liquid includes：Quaternary ammonium ion, piperidines ion, pyrrolidinium ion, quaternary phosphines ion,
One or more in pyrazolium ion, imidazol ion；
Wherein, the structure of the quaternary ammonium ion is：
The structure of the piperidines ion is：
The structure of the pyrrolidinium ion is：
The structure of the quaternary phosphine ion is：
The structural formula of the pyrazolium ion is：
The structural formula of the imidazol ion is：
Wherein, the carbon number of R1~R4 and R18~R21 is 1~8 alkyl or substitution alkyl；
R5, R6, R12, R13, R26 and R31 are respectively the alkyl that carbon number is 1~6；
R7~R11, R14~R17, R22~R25, R27~R30 are 1~6 for hydrogen atom, halogen atom or carbon number
Alkyl or substitution alkyl.
Further, the additive includes：Film for additive and stability additive.
Further, the film for additive includes：One kind or two in vinylene carbonate, vinyl vinylene carbonate
Kind.
Further, the stability additive includes：HMDS, seven methyl disilazanes, phosphorous triphenyl phosphate
One or more in ester.
The application second aspect shows a kind of compound method of the long-life ferric phosphate lithium cell electrolyte of wide temperature range, described
Method includes：
Carbonates chemical combination and ionic liquid are weighed, mechanical agitation is well mixed in humidity is less than 8ppm environment, obtains
Electrolyte solvent；
To lithium salts is added in the electrolyte solvent, at room temperature, lithium salts dissolving is subsequently adding additive and stirred by stirring
Mix after being completely dissolved, stand 12h, obtain electrolyte.
The embodiment of the present application shows a kind of long-life ferric phosphate lithium cell electrolyte of wide temperature range and compound method；The electricity
Solution liquid constitutes and is：Lithium salts, carbonats compound, additive and ionic liquid；Wherein, the quality of the carbonats compound
Fraction is：60.0%~65.0%；The mass fraction of the ionic liquid is：10.0%~15.0%；The matter of the additive
Measuring fraction is；5%~10%.The application by optimizing the species of electrolyte contained substance and the mass fraction of every kind of material, from
The parameters such as control adjustment electrolyte system viscosity, moisture, acidity value, compatibility and electrical conductivity are with the change of use environment
Micro change.Using under the conditions of -40 DEG C of the ferric phosphate lithium cell that the electrolyte shown in the embodiment of the present application is made, capacity is sent out first
Rate is waved higher than 80.0%, and capability retention is higher than 60.0% after circulating 3000 times according to 3C discharge and recharges system；Under the conditions of 25 DEG C
Capability retention is higher than 80.0% after circulating 3000 times according to 3C discharge and recharges system, is followed according to 3C discharge and recharge systems under the conditions of 60 DEG C
Capability retention is higher than 80.0% after ring 3000 times.The ferric phosphate lithium cell being made of the electrolyte shown in the embodiment of the present application
By still there is capability retention higher after the circulation of multiple high power charging-discharging system under normal temperature and height environmental condition.
Brief description of the drawings
In order to illustrate more clearly of the technical scheme of the application, letter will be made to the accompanying drawing to be used needed for embodiment below
Singly introduce, it should be apparent that, for those of ordinary skills, without having to pay creative labor,
Other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is a kind of flow chart of the long-life ferric phosphate lithium cell electrolyte collocation method of wide temperature range of the application.
Specific embodiment
The embodiment of the present application shows a kind of long-life ferric phosphate lithium cell electrolyte of wide temperature range：The electrolyte composition
For：Lithium salts, carbonats compound, additive and ionic liquid；
Wherein, the mass fraction of the carbonats compound is：60.0%~65.0%；
Further, the mass fraction of the additive is 5.0%~10.0%；
The mass fraction of the ionic liquid is：10.0%~15.0%；
The mass fraction of the lithium salts is：10%~25%.
Further, the cation of described ionic liquid includes：Quaternary ammonium ion：Piperidines ion：Pyrrolidinium ion：Quaternary phosphine ion：
Pyrazolium ion：Imidazol ion
Wherein, R1~R4 and R18~R21 selection carbon number independently are 1~8 alkyl or substitution alkyl；R5、
R6, R12, R13, R26, R31 selection carbon number independently are 1~6 alkyl；R7~R11, R14~R17, R22~
R25, R27~R30 selection hydrogen atom, halogen atom or carbon numbers independently are 1~6 alkyl or substitution alkyl.
Further, the carbonats compound includes：Ethylene carbonate, propene carbonate, dimethyl carbonate, carbonic acid two
In ethyl ester, methyl ethyl carbonate, dibutyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, ethyl butyl carbonate, fluorine-containing carbonic ester one
Plant or several.
Embodiment one：
Propene carbonate, dibutyl carbonate, ionic liquid are taken respectively, the mechanical agitation mixing in humidity is less than 8ppm environment
Uniformly, solution temperature control is configured to electrolyte solvent at 25 ± 2 DEG C；Again to lithium hexafluoro phosphate is added in electrolyte solvent, treat
It is quiet after continuation addition vinylene carbonate, triphenyl phosphite are uniformly mixed in electrolyte solvent after it is completely dissolved
The electrolyte of the ferric phosphate lithium cell of the present embodiment is obtained after putting 12 hours.
The mass fraction of the electrolyte propene carbonate is 30.0%, and the mass fraction of the dibutyl carbonate is
35.0%, the mass fraction of the ionic liquid is 15.0%, and the mass fraction of the lithium hexafluoro phosphate is 10.0%, the carbon
The mass fraction of sour vinylene is 4.0%, and the mass fraction of the triphenyl phosphite is 6.0%.
It is worth noting that：Carbonats compound includes propene carbonate and dibutyl carbonate, therefore the carbonic ester
The mass fraction of class compound is 65.0%.
It is in the intermediate ion aqueous chemical structural formula of embodiment one：
Wherein, R1 is CH3CHFCH2 -, R2 is CH3CH2 -, R3 is BrCH2CH2 -, R4 is CH3CH2CH2CH2CH2 -。
Comparative example one：
The electrolyte of comparative example one, the electrolyte and embodiment of comparative example one are prepared under the conditions of with the identical of embodiment one
The component of one electrolyte is identical, only difference is that the mass fraction of propene carbonate that uses of comparative example one for
35.0%th, the mass fraction of dibutyl carbonate is 50.0%, and the mass fraction of lithium hexafluoro phosphate is 5.0%, carbonic acid Asia second
The mass fraction of alkene ester is 5.0%, and the mass fraction of the triphenyl phosphite is 5.0%.
It is worth noting that, carbonats compound includes propene carbonate and dibutyl carbonate, therefore the carbonic ester
The mass fraction of class compound is 85.0%.
By in the electrolyte compounding of the electrolyte of above-described embodiment one and comparative example one to ferric phosphate lithium cell, monomer is prepared
Capacity is 25.0AH aluminum hull square batteries, and battery performance survey is carried out according to GB T31484-2015, GB T31485-2015 standards
Examination, test result is as follows：
As can be seen that using the embodiment of the present application one show under the conditions of -40 DEG C of the ferric phosphate lithium cell that electrolyte is made by
Capability retention is 60.8% after circulating 3000 times according to 3C discharge and recharges system, is circulated according to 3C discharge and recharges system under the conditions of 25 DEG C
Capability retention is 81.20% after 3000 times, capability retention after circulating 3000 times according to 3C discharge and recharges system under the conditions of 60 DEG C
It is 81.38%.And according to 3C discharge and recharge systems under the conditions of -40 DEG C of the ferric phosphate lithium cell that the electrolyte shown in comparative example one is made
Capability retention is only 28.29% after circulating 3000 times, is held after circulating 3000 times according to 3C discharge and recharges system under the conditions of 25 DEG C
Amount conservation rate is 52.80%, and capability retention is 55.10% after circulating 3000 times according to 3C discharge and recharges system under the conditions of 60 DEG C.
It can be seen that the ferric phosphate lithium cell that the electrolyte shown in use the embodiment of the present application is made is passed through under the conditions of normal temperature and high and low temperature environment
Still there is capability retention higher after crossing multiple high power charging-discharging system circulation.
Embodiment two：
Ethylene carbonate, dibutyl carbonate, fluorine-containing carbonic ester, ionic liquid are taken respectively, in humidity is less than 8ppm environment
Mechanical agitation is well mixed, and solution temperature is controlled at 25 ± 2 DEG C, is configured to electrolyte solvent；Added in electrolyte solvent again
Hexafluoroarsenate lithium, after it is completely dissolved, vinyl vinylene carbonate and hexamethyl two is added to continuation in electrolyte solvent
After silicon amine alkane is uniformly mixed, the electrolyte of the ferric phosphate lithium cell of the present embodiment is obtained after standing 12 hours.
The mass fraction of ethylene carbonate is 20.0% in the electrolyte, and the mass fraction of the dibutyl carbonate is
30.0%, the mass fraction of fluorine-containing carbonic ester is 10.0%, and the mass fraction of the ionic liquid is 15.0%, the hexafluoro arsenic
The mass fraction of sour lithium is 15.0%, and the mass fraction of the vinyl vinylene carbonate is 5.0%, the silicon of the hexamethyl two
The mass fraction of amine alkane is 5.0%.
It is worth noting that：Carbonats compound includes ethylene carbonate, dibutyl carbonate and fluorine-containing carbonic ester, therefore
The mass fraction of the carbonats compound is 60.0%.
Fluorine-containing carbonic ester chemical structural formula is in the present embodiment：
Wherein Rf：H(CF2CF2)3CH2 -、F(CF2CF2)5CH2CH2 -；
Ionic liquid chemical structural formula is in the present embodiment：
R12：CH3CH2 -, R13：CH3CH2 -, R14：CH3BrCH-, R15：CH3CH2CH2CH2CH2 -,
R16：BrCH2CH2 -, R17：CH3CH2CH2CH2CH2CH2 -；
Comparative example two：
Contrast electrolyte, the electrolyte of comparative example two and the electricity of embodiment two are prepared under conditions of identical with embodiment two
The component for solving liquid is identical, only difference is that the mass fraction that comparative example two is used is 15.0% fluorine-containing carbonic ester (chemistry knot
Structure is same as Example 2), the ethylene carbonate that mass fraction is 20.0%, the dibutyl carbonate that mass fraction is 20.0%, institute
It is 20.0% to state the mass fraction of ionic liquid, and the mass fraction of the hexafluoroarsenate lithium is 15.0%, the vinyl carbonic acid
The mass fraction of vinylene is 5.0%, and the mass fraction of the HMDS is 5.0%..
It is worth noting that：Carbonats compound includes ethylene carbonate, dibutyl carbonate and fluorine-containing carbonic ester, therefore
The mass fraction of the carbonats compound is 55.0%.
By in above electrolyte compounding ferric phosphate lithium cell, monomer capacity is prepared for 25.0AH aluminum hull square batteries, according to
GB T31484-2015, GB T31485-2015 standards carry out battery performance test, and test result is as follows：
As can be seen that using the embodiment of the present application two show under the conditions of -40 DEG C of the ferric phosphate lithium cell that electrolyte is made by
Capability retention is 66.36% after circulating 3000 times according to 3C discharge and recharges system, is circulated according to 3C discharge and recharges system under the conditions of 25 DEG C
Capability retention is 82.40% after 3000 times, capability retention after circulating 3000 times according to 3C discharge and recharges system under the conditions of 60 DEG C
It is 80.5%.And according to 3C discharge and recharge systems under the conditions of -40 DEG C of the ferric phosphate lithium cell that the electrolyte shown in comparative example two is made
Capability retention is 38.51% after circulating 3000 times, and capacity is protected after circulating 3000 times according to 3C discharge and recharges system under the conditions of 25 DEG C
Holdup is 57.20%, and capability retention is 40.08% after circulating 3000 times according to 3C discharge and recharges system under the conditions of 60 DEG C.It can be seen that
The ferric phosphate lithium cell being made of the electrolyte shown in the embodiment of the present application is multiple under the conditions of normal temperature and high and low temperature environment
Remain to keep capability retention higher after the circulation of high power charging-discharging system.
Time of penetration respectively 15h, 53h are shelved in embodiment one, comparative example one, embodiment two, the preparation of comparative example two,
10h and 48h.It can be seen that the electrolyte shown in the embodiment of the present application, by optimizing electrolyte solvent species and percentage by weight,
Change of the parameters such as electrolyte system viscosity, moisture, acidity value, compatibility and electrical conductivity with use environment is adjusted from control
And micro change, wellability and compatibility increase of the electrolyte to ferric phosphate lithium cell both positive and negative polarity pole piece.By the embodiment of the present application
After the electrolyte for showing is injected into battery core housing, the positive/negative plate in electrolysis liquid energy rapid osmotic electric core shell body；
During the positive/negative plate of electrolyte shown in the embodiment of the present application in rapid osmotic electric core shell body, not with just
There is chemical reaction and produce the physical reactions of similar compatibility in the composition on negative plate surface, can well maintain positive/negative plate composition
Stability.
Further, stating carbonats compound also includes fluorine-containing carbonic ester, and the structural formula of the fluorine-containing carbonic ester is：
Wherein, Rh is H or alkyl；Rf is H (CF2CF2)n1CH2 -, F (CF2CF2)n2CH2CH2 -Or CF3CF2CF2O(CF
(CF3)CF2O)n3CF(CF3)CH2 -；
Wherein, n1、n2It is positive integer；n3It is nonnegative integer.
Embodiment one：
Taking mass fraction respectively is：Propene carbonate, dibutyl carbonate, ionic liquid, in humidity is less than 8ppm environment
Mechanical agitation is well mixed, and solution temperature is controlled at 25 ± 2 DEG C, is configured to electrolyte solvent；Again to addition hexafluoro phosphorus in solvent
Sour lithium, after it is completely dissolved, is uniformly mixed to addition vinylene carbonate, triphenyl phosphite is continued in electrolyte
Afterwards, the electrolyte of the ferric phosphate lithium cell of the present embodiment is obtained after standing 12 hours.
The mass fraction of the electrolyte propene carbonate is 30.0%, and the mass fraction of the dibutyl carbonate is
35.0%, the mass fraction of the ionic liquid is 15.0%, and the mass fraction of the lithium hexafluoro phosphate is 10.0%, the carbon
The mass fraction of sour vinylene is 4.0%, and the mass fraction of the triphenyl phosphite is 6.0%.
Embodiment two：
Ethylene carbonate, dibutyl carbonate, fluorine-containing carbonic ester, ionic liquid are taken respectively, in humidity is less than 8ppm environment
Mechanical agitation is well mixed, and solution temperature is controlled at 25 ± 2 DEG C, is configured to electrolyte solvent；Again to adding hexafluoro in electrolyte
Arsenic acid lithium, after it is completely dissolved, in electrolyte, vinyl vinylene carbonate is added in continuation and HMDS is stirred
Mix after being well mixed, the electrolyte of the ferric phosphate lithium cell of the present embodiment is obtained after standing 12 hours.
The mass fraction of ethylene carbonate is 20.0% in the electrolyte, and the mass fraction of the dibutyl carbonate is
30.0%, the mass fraction of fluorine-containing carbonic ester is 10.0%, and the mass fraction of the ionic liquid is 15.0%, the hexafluoro arsenic
The mass fraction of sour lithium is 15.0%, and the mass fraction of the vinyl vinylene carbonate is 5.0%, the silicon of the hexamethyl two
The mass fraction of amine alkane is 5.0%.
Fluorine-containing carbonic ester chemical structural formula is in embodiment two：
Wherein Rf：H(CF2CF2)3CH2 -、F(CF2CF2)5CH2CH2 -；
It can be seen that the electrolyte of embodiment one and electrolyte and reality that the difference of the electrolyte of embodiment two is embodiment two
The electrolyte of example one is applied compared to adding fluorine-containing carbonic ester.
By in above electrolyte compounding ferric phosphate lithium cell, monomer capacity is prepared for 25.0AH aluminum hull square batteries, according to
GB T31484-2015, GB T31485-2015 standards carry out battery performance test, and test result is as follows：
As can be seen that using the embodiment of the present application one show under the conditions of -40 DEG C of the ferric phosphate lithium cell that electrolyte is made by
Capability retention is 60.8% after circulating 3000 times according to 3C discharge and recharges system, is circulated according to 3C discharge and recharges system under the conditions of 25 DEG C
Capability retention is 81.20% after 3000 times, capability retention after circulating 3000 times according to 3C discharge and recharges system under the conditions of 60 DEG C
It is 81.38%.Shown under the conditions of -40 DEG C of the ferric phosphate lithium cell that electrolyte is made according to 3C charge and discharges using the embodiment of the present application two
Capability retention is 66.36% after electric system circulates 3000 times, after circulating 3000 times according to 3C discharge and recharges system under the conditions of 25 DEG C
Capability retention is 82.40%, and it is 80.5% that capacity is protected after circulating 3000 times according to 3C discharge and recharges system under the conditions of 60 DEG C.It can be seen that
The LiFePO4 electricity that two electrolyte for going out (containing fluorine-containing carbonic ester in i.e. described electrolyte) are made is shown using the embodiment of the present application
Pond after the circulation of multiple high power charging-discharging system at low ambient conditions by still having capability retention higher.
The application selects ionic liquid as the part of electrolyte, and cooperates with work with the additive performance in electrolyte
With, electrolyte quality quality, stability and feature can be improved, ferric phosphate lithium cell batch uniformity, low can be effectively improved
Contradiction between warm type and high rate performance and cycle life.One of the reason for usual ferric phosphate lithium cell batch uniformity difference is exactly
The stability of electrolyte is bad, because electrolyte is after long-term storage, the lithium salts in electrolyte, additive etc. produces micro- into branch
Layering, causes electrolyte local concentration heterogeneity；Chemical property difference is that ferric phosphate lithium cell most significantly lacks under cryogenic conditions
One of fall into, most important reason be exactly electrolyte under cryogenic, electrical conductivity reduction, solvent becomes sticky etc., cause lithium from
Son can not be migrated normally, and then cause battery capacity dramatic decrease, cycle life reduction.Using the electricity shown in the embodiment of the present application
Even if solution liquid is under -40 DEG C of low temperature environments, after the rate of capacity performance first is higher than circulation under 80.0%, 3C discharge and recharge systems 3000 times
Capability retention can be higher than 60.0%.
Further, the additive includes：Film for additive and stability additive.
Further, the film for additive includes：One kind or two in vinylene carbonate, vinyl vinylene carbonate
Kind.
During lithium ion battery first charge-discharge, electrolyte chemically reacts in electrode material surface, forms one
Layer passivation layer is covered in electrode material surface, and this passivation layer is a kind of interfacial film with solid electrolyte characteristic, is electronics
Insulator, be but the excellence conductor of lithium ion, lithium ion can freely be embedded in and deviate from the passivation layer.The embodiment of the present application
Using vinylene carbonate, vinyl vinylene carbonate one or two can be negative in lithium ion battery as film for additive
There is polymerisation and generate poly- alkyl lithium carbonates film in pole pole piece, can effectively suppress negative electrode active material molten with active material
Agent and the reduction of salt anionic and peeled off from collection liquid surface.
Meanwhile, one or two in vinylene carbonate, vinyl vinylene carbonate promote as film for additive
The formation of negative terminal surface SEI films, while the functional group in SEI films produces to METHYLPYRROLIDONE derivative quaternary ammonium salt
Suction-operated, is adsorbed in SEI films surface and is formed protective layer, and then effectively prevents electrolyte and negative pole work under hot conditions
The chemical reaction of property material；
Further, the stability additive includes：HMDS, seven methyl disilazanes, phosphorous triphenyl phosphate
One or more in ester.
The moisture and hydrofluoric acid of trace in electrolyte, can act on forming fluoride and precipitating and be deposited on cathode pole piece with lithium salts
Surface, has important effect to the formation of SEI films.But the too high levels of moisture and hydrofluoric acid in electrolyte, can not only make
Lithium salts is decomposed, but also can destroy the SEI films of formation.The embodiment of the present application uses HMDS, the silicon amine of seven methyl two
One or more in alkane, triphenyl phosphite are hydrionic complexing agent, can eliminate or reduce the moisture dissociated in electrolyte
And hydrofluoric acid, so as to improve the stability and cycle life of lithium ion battery.
The application second aspect shows a kind of compound method of the long-life ferric phosphate lithium cell electrolyte of wide temperature range, such as schemes
Shown in 1, methods described includes：
S101 weighs carbonates chemical combination and ionic liquid respectively, and mechanical agitation mixing is equal in humidity is less than 8ppm environment
It is even, obtain electrolyte solvent；
To lithium salts is added in the electrolyte solvent, at room temperature, lithium salts dissolving is subsequently adding addition to S102 by stirring
After agent stirs, 12h is stood, obtain electrolyte.
From above technical scheme, the embodiment of the present application shows a kind of long-life ferric phosphate lithium cell electrolysis of wide temperature range
Liquid and compound method：The electrolyte includes：Lithium salts, carbonats compound, additive and ionic liquid；Wherein；The carbon
The mass fraction of acid esters compound is：60.0%~65.0%；The mass fraction of the additive is 5.0%~10.0%；
The mass fraction of the ionic liquid is：10.0%~15.0%；The application by optimize electrolyte contained substance species and
The mass fraction of every kind of material, from control adjustment electrolyte system viscosity, moisture, acidity value, compatibility and electrical conductivity etc.
Parameter micro change with the change of use environment.Wellability and compatibility of the electrolyte to ferric phosphate lithium cell both positive and negative polarity pole piece
Increase.Using under -40 DEG C of environmental conditions of ferric phosphate lithium cell that the electrolyte shown in the embodiment of the present application is made, capacity is sent out first
Rate is waved higher than 80.0%, and capability retention is higher than 60.0% after circulating 3000 times according to 3C discharge and recharges system；Under the conditions of 25 DEG C
Capability retention is higher than 80.0% after circulating 3000 times according to 3C discharge and recharges system；Followed according to 3C discharge and recharge systems under the conditions of 60 DEG C
Capability retention is higher than 80.0% after ring 3000 times.The ferric phosphate lithium cell being made of the electrolyte shown in the embodiment of the present application
By remaining to keep capacity higher to keep after the circulation of multiple high power charging-discharging system under the conditions of normal temperature and high and low temperature environment
Rate.Meanwhile, the application selects ionic liquid as the part of electrolyte, and cooperates with work with the additive performance in electrolyte
With, electrolyte quality quality, stability and feature can be improved, ferric phosphate lithium cell batch uniformity, low can be effectively improved
Contradiction between warm nature and high rate performance and cycle life.
Claims (9)
1. the long-life ferric phosphate lithium cell electrolyte of a kind of wide temperature range, it is characterised in that：The electrolyte is constituted：Lithium salts,
Carbonats compound, additive and ionic liquid；
The mass fraction of the carbonats compound is：60.0%~65.0%；
The mass fraction of the ionic liquid is：10.0%~15.0%；
The mass fraction of the additive is：5%~10%
The mass fraction of the lithium salts is：10%~25%.
2. electrolyte as claimed in claim 1, it is characterised in that the additive includes：Film for additive and stability add
Plus agent.
3. electrolyte as claimed in claim 2, it is characterised in that the film for additive includes：Vinylene carbonate, ethene
One or two in base vinylene carbonate.
4. electrolyte as claimed in claim 2, it is characterised in that the stability additive includes：HMDS,
One or more in seven methyl disilazanes, triphenyl phosphite.
5. electrolyte as claimed in claim 1, it is characterised in that the carbonats compound includes ethylene carbonate, carbon
Acid propylene ester, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dibutyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, carbon
One or more in sour second butyl ester.
6. electrolyte as claimed in claim 5, it is characterised in that the carbonats compound also includes fluorine-containing carbonic ester,
The structural formula of the fluorine-containing carbonic ester is：
Wherein, Rh is H or alkyl；Rf is H (CF2CF2)n1CH2 -, F (CF2CF2)n2CH2CH2 -Or CF3CF2CF2O(CF(CF3)
CF2O)n3CF(CF3)CH2 -；
Wherein, n1、n2It is positive integer；n3It is nonnegative integer.
7. electrolyte as claimed in claim 1, it is characterised in that the anion chemical constitution of the ionic liquid is：
8. electrolyte as claimed in claim 1, it is characterised in that the cation of the ionic liquid includes：Quaternary ammonium ion, piperazine
One or more in pyridine ion, pyrrolidinium ion, quaternary phosphines ion, pyrazolium ion, imidazol ion；
The structure of wherein described quaternary ammonium ion is：
The structure of the piperidines ion is：
The structure of the pyrrolidinium ion is：
The structure of the quaternary phosphine ion is：
The structural formula of the pyrazolium ion is：
The structural formula of the imidazol ion is：
Wherein, the carbon number of R1~R4 and R18~R21 is 1~8 alkyl or substitution alkyl；
R5, R6, R12, R13, R26 and R31 are respectively the alkyl that carbon number is 1~6；
R7~R11, R14~R17, R22~R25, R27~R30 are the alkyl that hydrogen atom, halogen atom or carbon number are 1~6
Or substitution alkyl.
9. the compound method of the long-life ferric phosphate lithium cell electrolyte of a kind of wide temperature range, it is adaptable to as claim 1-9 is any
Electrolyte described in, it is characterised in that methods described includes：
Carbonates chemical combination and ionic liquid are weighed, mechanical agitation is well mixed in humidity is less than 8ppm environment, is electrolysed
Matter solvent；
To lithium salts is added in the electrolyte solvent, at room temperature, lithium salts dissolving is subsequently adding additive and stirred by stirring
After CL, 12h is stood, obtain electrolyte.
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