CN105845982B - Electrolyte and lithium ion battery comprising same - Google Patents
Electrolyte and lithium ion battery comprising same Download PDFInfo
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- CN105845982B CN105845982B CN201610194358.1A CN201610194358A CN105845982B CN 105845982 B CN105845982 B CN 105845982B CN 201610194358 A CN201610194358 A CN 201610194358A CN 105845982 B CN105845982 B CN 105845982B
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
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- 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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Abstract
The present application relates to an electrolyte and a lithium ion battery including the same, wherein the electrolyte includes an organic solvent, a lithium salt, and an additive including a hydrogenated thiophene-boron trifluoride complex compound and a sultone compound. The electrolyte simultaneously comprises the hydrogenated thiophene-boron trifluoride coordination compound and the sultone compound, so that the decomposition of the electrolyte on the surface of an electrode can be inhibited under the synergistic effect of the hydrogenated thiophene-boron trifluoride coordination compound and the sultone compound, the corrosion of an acidic substance generated in the electrolyte to a solid electrolyte film can be effectively reduced, and the cycle performance and the storage performance of a lithium ion battery at normal temperature and high temperature can be improved.
Description
Technical field
This application involves field of batteries more particularly to a kind of electrolyte and the lithium ion battery including the electrolyte.
Background technology
At present, the positive electrode active materials employed in lithium ion battery mainly have LiMn2O4, cobalt acid lithium, ternary material,
LiFePO 4 etc. under normal conditions, selects the charge cutoff voltage of the lithium ion battery of the above-mentioned positive electrode being previously mentioned
No more than 4.2V, but with advances in technology and the continuous development in market, the energy density of lithium ion battery is promoted increasingly
Seem important and urgent, a kind of effective ways for the energy density for promoting lithium ion battery are exploitation high-voltage lithium ion batteries.
However, under the high voltage of 4.6V, conventional electrolyte can be caused in the positive electrode surface oxygenolysis of battery, electrolysis
The oxygenolysis of liquid itself can promote the deteriorative reaction of positive electrode active materials simultaneously, further influence the performance of lithium ion battery,
Such as storage performance and cycle performance.
The defects of for existing battery and deficiency, spy release the application.
The content of the invention
The primary goal of the invention of the application is to propose a kind of electrolyte.
The second goal of the invention of the application is to propose a kind of lithium ion battery.
In order to complete the purpose of the present invention, the technical solution used for：
This application involves a kind of electrolyte, and including organic solvent, lithium salts and additive, the additive includes hydrogenation thiophene
Fen-boron trifluoride complex and sultone compounds.
Preferably, the hydrogenation thiophene-boron trifluoride complex is in the compound of structural formula as shown in formula I
It is at least one：
Wherein, R1, R2, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano, substituted or unsubstituted C1~20Alkane
Base, substituted or unsubstituted C2~20Alkenyl, substituted or unsubstituted C6~26Aryl；
Substituent group is selected from halogen, cyano.
Preferably, the hydrogenation thiophene-boron trifluoride complex is in the compound of structural formula as shown in I A of formula
At least one；
Wherein, R3、R4It is each independently selected from hydrogen atom, halogen atom, cyano, substituted or unsubstituted C1~20Alkyl, substitution
Or unsubstituted phenyl；Substituent group is selected from halogen, cyano.
Preferably, R3、R4It is each independently selected from hydrogen atom, fluorine atom.
Preferably, the sultone compounds are in following formula II, V compound represented of formula III, formula IV and formula
At least one：
Wherein, R11、R12、R13、R14It is each independently selected from hydrogen atom, halogen atom, nitro, cyano, carboxyl, sulfonic group, takes
Generation or unsubstituted C1~20Alkyl, substituted or unsubstituted C1~20Alkoxy, substituted or unsubstituted C2~20Alkenyl, substitution or not
Substituted C2~20Alkynyl, substituted or unsubstituted C1~20Alkane sulfonyl, substituted or unsubstituted C2~20Alkene sulfonyl, substitution or not
Substituted C2~20Alkynes sulfonyl；
Substituent group is selected from halogen, cyano, nitro, carboxyl or sulfonic group.
Preferably, R11、R12、R13、R14It is each independently selected from hydrogen atom, substituted or unsubstituted C1~6Linear chain or branch chain
Alkyl, substituted or unsubstituted C1~6Straight or branched alkoxyl；Substituted or unsubstituted C5~7Cycloalkyl, substitution or unsubstituted
C2~6Alkenyl, substituted or unsubstituted C2~6Alkynyl；
Substituent group is selected from halogen, cyano.
Preferably, the content of the hydrogenation thiophene-boron trifluoride complex is the 0.05% of the total weight of electrolyte
~10%；The content of the sultone compounds is the 0.1%~10% of the total weight of electrolyte.
Preferably, the organic solvent is selected from ethylene carbonate, propene carbonate, butylene, fluoro ethylene carbonate
Ester, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, in 1,4- fourths
At least one of ester, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate and ethyl butyrate.
Preferably, the lithium salts is selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro grass
Acid phosphoric acid lithium, LiN (SO2RF)2、LiN(SO2F)(SO2RF), it is double trifluoromethanesulfonimide lithiums, double (fluorine sulphonyl) imine lithiums, double
At least one of Lithium bis (oxalate) borate, difluorine oxalic acid boracic acid lithium, wherein, RFFor-CnF2n+1, n is 1~10 integer, is preferably
LiPF6And/or LiN (SO2RF)2；
It is furthermore preferred that the concentration of the lithium salts in the electrolytic solution is 0.5molL-1~2molL-1。
The application further relates to a kind of lithium ion battery, including the positive plate containing positive electrode active materials, contains negative electrode active
The electrolyte of the negative plate of material, isolation film and the application.
The attainable advantageous effects of the application include as follows：
Simultaneously including hydrogenation thiophene-boron trifluoride complex and sultone compounds in the electrolyte of the application
When, under the common synergistic effect of the two, decomposition of the electrolyte in electrode surface can be inhibited, effectively reduce being generated in electrolyte
Corrosion of the acidic materials to solid electrolyte plasma membrane, improve the cycle performance and height of lithium ion battery at ambient and elevated temperatures
Storage performance under temperature, such as lithium ion battery are respectively provided with excellent cyclicity under 4.6V high voltages and at 25 DEG C and 45 DEG C
Can, there is excellent storage performance at 85 DEG C.
Specific embodiment
It is described in detail below by the application, will become more with these explanations with advantage the characteristics of the application
To be clear, clear and definite.
The application's is designed to provide a kind of electrolyte, including organic solvent, lithium salts and additive, the additive bag
Include hydrogenation thiophene-boron trifluoride complex and sultone compounds.
In above-mentioned electrolyte, in thiophene-boron trifluoride complex is hydrogenated, boron trifluoride is in anion, is hydrogenated
For thiophene in cation, it is in electroneutral entirely to hydrogenate thiophene-boron trifluoride complex.
In above-mentioned electrolyte, sultones can be saturation sultones or unsaturated sulfonic acid lactone.
It hydrogenates thiophene-boron trifluoride complex and is selected from least one of compound of structural formula as shown in formula I：
Wherein, R1, R2, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano, substituted or unsubstituted C1~20Alkane
Base, substituted or unsubstituted C2~20Alkenyl, substituted or unsubstituted C6~26Aryl,；
Substituent group is selected from halogen, cyano.
Halogen in the application is selected from F, Cl, Br, and preferably F, Cl.
In above-mentioned formula I, substituent group is as described below.
Carbon number is 1~20 alkyl, and alkyl can be chain-like alkyl or cycloalkyl, on the ring of cycloalkyl
Hydrogen can be substituted by alkyl, in the alkyl the preferred lower limiting value of carbon number be 2,3,4,5, preferred upper limit value be 3,4,5,
6,8,10,12,14,16,18.Preferably, select carbon number for 1~10 alkyl, it is further preferred that selection carbon number
For 1~6 chain-like alkyl, carbon number is 3~8 cycloalkyl, it is further preferred that select carbon number for 1~4 chain
Shape alkyl, carbon number are 5~7 cycloalkyl.As the example of alkyl, can specifically enumerate：It is methyl, ethyl, n-propyl, different
Propyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl, isopentyl, neopentyl, cyclopenta, cyclohexyl.
Carbon number is 2~20 alkenyl, can be cyclic alkenyl radical or chain alkenyl.In addition, in alkenyl double bond
Number is preferably 1.The preferred lower limiting value of carbon number is 3,4,5 in the alkenyl, and preferred upper limit value is 3,4,5,6,8,10,
12,14,16,18.Preferably, select carbon number for 2~10 alkenyl, it is further preferred that selecting carbon number as 2~6
Alkenyl, it is further preferred that select carbon number for 2~5 alkenyl.As the example of alkenyl, can specifically enumerate：Second
Alkenyl, pi-allyl, isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base.
Carbon number be 6~26 aryl, such as phenyl, benzene alkyl, at least contain there are one phenyl aryl such as xenyl,
Condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and condensed-nuclei aromatics base can also be substituted by alkyl or alkenyl.Preferably, select
Select carbon number be 6~16 aryl, it is further preferred that select carbon number for 6~14 aryl, still more preferably
Ground, select carbon number for 6~9 aryl.As the example of aryl, can specifically enumerate：Phenyl, benzyl, xenyl, to first
Phenyl, o-tolyl, tolyl.
When alkenyl that alkyl that the carbon number being previously mentioned is 1~20, carbon number are 2~20, carbon number be 6~
26 aryl, after being substituted by halogen atom, formed accordingly successively halogenated alkyl, carbon number that carbon number is 1~20 be 2~
20 halogenated alkenyl, the halogenated aryl that carbon number is 6~26, wherein halogen atom is F, Cl, Br, is preferably F, Cl.In institute's shape
Into halo groups in, halogen atom substitutes part hydrogen atom or whole hydrogen atom, and the number of halogen atom can be 1,2
It is a, 3 or 4.
Preferably, select carbon number for 1~10 halogenated alkyl, carbon number be 2~10 halogenated alkenyl, carbon atom
Number is 6~16 halogenated aryl；It is further preferred that select halogenated chain-like alkyl, carbon number 3 of the carbon number for 1~6
The halogenated aryl that halogenated alkenyl that~8 halogenated cycloalkyl, carbon number are 2~6, carbon number are 6~14；It is further excellent
Selection of land, select carbon number for 1~4 halogenated chain-like alkyl, carbon number be 5~7 halogenated cycloalkyl, carbon number 2
~5 halogenated alkenyl, the halogenated aryl that carbon atom is 6~10.
As the example of halo groups, can specifically enumerate：Trifluoromethyl (- CF3), 2- fluoro ethyls, 3- fluorine n-propyl, 2-
Fluorine isopropyl, 4- fluorine normal-butyl, 3- fluorine sec-butyl, 5- fluorine n-pentyl, 4- fluorine isopentyl, 1- are fluoride-based, 3- fluorine pi-allyl, 6-
Fluoro- 4- hexenyls, o-fluorophenyl, p-fluorophenyl, fluorophenyl, 4- trifluoromethylphenyls, 2,6- difluoromethyls phenyl, the fluoro- 1- of 2-
Naphthalene.In above-mentioned specific example, F can be substituted by Cl and/or Br.
As a kind of improvement of the application electrolyte, above-mentioned I substituent group of formula is selected from：R1, R2, R3, R4It is each independently selected from
Hydrogen atom, halogen atom, cyano, substituted or unsubstituted C1~12Alkyl, substituted or unsubstituted C1~12Alkenyl, substitution or unsubstituted
C6~22Aryl.
As a kind of improvement of the application electrolyte, R1, R2, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyanogen
Base, substituted or unsubstituted C1~6Alkyl, substituted or unsubstituted phenyl.
As a kind of improvement of the application electrolyte, hydrogenation thiophene-boron trifluoride complex is selected from as shown in I A of formula
At least one of compound of structural formula；
Wherein, R3、R4It is each independently selected from hydrogen atom, halogen atom, cyano, substituted or unsubstituted C1~20Alkyl substitutes
Or unsubstituted phenyl；Substituent group is selected from halogen, cyano.
As a kind of improvement of the application electrolyte, R3、R4It is each independently selected from hydrogen atom, halogen atom, cyano, substitution
Or unsubstituted C1~12Alkyl；Substituent group is selected from halogen, cyano；
As a kind of improvement of the application electrolyte, R3、R4It is each independently selected from hydrogen atom, halogen atom, cyano, substitution
Or unsubstituted C1~6Alkyl；Substituent group is selected from halogen, cyano.
As a kind of improvement of the application electrolyte, R3、R4It is each independently selected from hydrogen atom, fluorine atom.
It is specific as follows shown as the example of hydrogenation thiophene-boron trifluoride complex：
As a kind of improvement of the application electrolyte, hydrogenation thiophene-boron trifluoride complex is also selected from：
In this application, the hydrogenation thiophene-boron trifluoride complex being previously mentioned can be according to existing conventional synthesis
Method is synthesized, such as can refer to document：CN200780033378.X.
Sultone compounds in the application are in following formula II, V compound represented of formula III, formula IV and formula
At least one：
In above-mentioned formula II, formula III, formula IV and formula V, R11、R12、R13、R14Be each independently selected from hydrogen atom, halogen atom,
Nitro, cyano, carboxyl, sulfonic group, substituted or unsubstituted C1~20Alkyl, substituted or unsubstituted C1~20Alkoxy, substitution or
Unsubstituted C2~20Alkenyl, substituted or unsubstituted C2~20Alkynyl, substituted or unsubstituted C1~20Alkane sulfonyl, substitution do not take
The C in generation2~20Alkene sulfonyl, substituted or unsubstituted C2~20Alkynes sulfonyl；
Wherein, substituent group is selected from halogen, cyano, nitro, carboxyl or sulfonic group；Halogen is F, Cl, Br, preferably F, Cl.
As a kind of improvement of the application electrolyte, R11、R12、R13、R14Be each independently selected from hydrogen atom, substitution or not
Substituted C1~6Straight or branched alkyl, substituted or unsubstituted C1~6Straight or branched alkoxyl；Substituted or unsubstituted C5~7
Cycloalkyl, substituted or unsubstituted C2~6Alkenyl, substituted or unsubstituted C2~6Alkynyl；Substituent group is selected from halogen, cyano.
As a kind of improvement of the application electrolyte, R11、R12、R13、R14Be each independently selected from hydrogen atom, substitution or not
Substituted C1~3Straight or branched alkyl, substituted or unsubstituted C1~3Straight or branched alkoxyl；Substituted or unsubstituted C5~6
Cycloalkyl, substituted or unsubstituted C2~4Alkenyl, substituted or unsubstituted C2~4Alkynyl；Substituent group is selected from halogen, cyano.
In above-mentioned formula II, formula III, formula IV and formula V, substituent group is as described below.
Carbon number is 1~20 alkyl, can be chain-like alkyl or cycloalkyl, positioned at the ring hydrogen of cycloalkyl
It can be substituted by alkyl.The preferred lower limiting value of carbon number is 2,3,4,5 in the alkyl, and preferred upper limit value is 3,4,5,6,8,
10,12,14,16,18.Preferably, select carbon number for 1~10 alkyl, it is further preferred that selecting carbon number as 1
~6 chain-like alkyl, carbon number be 3~8 cycloalkyl, it is further preferred that select carbon number for 1~4 chain
Alkyl, carbon number are 5~7 cycloalkyl.As the example of alkyl, can specifically enumerate：Methyl, ethyl, n-propyl, isopropyl
Base, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl, isopentyl, cyclopenta, cyclohexyl.
Carbon number is 2~20 unsaturated alkyl, can be alkenyl or alkynyl.Of unsaturated bond in unsaturated alkyl
Number is preferably 1, that is to say, that double bond is denumerable for 1 in alkenyl, and the number of three keys in alkynyl is alternatively 1.It is described
The preferred lower limiting value of carbon number is 3,4,5 in unsaturated alkyl, and preferred upper limit value is 3,4,5,6,8,10,12,14,16,
18.Preferably, select carbon number for 2~10 alkenyl, carbon number be 2~10 alkynyl, it is further preferred that selection carbon
The alkynyl that alkenyl that atomicity is 2~6, carbon number are 2~6, it is further preferred that select carbon number for 2~5 alkene
Base, the alkynyl that carbon number is 2~5.
As the example of unsaturated alkyl, can specifically enumerate：Vinyl, pi-allyl, isopropenyl, pentenyl, hexamethylene
Alkenyl, cycloheptenyl, cyclo-octene base, propinyl, 2-propynyl, 2- butynyls, 3- butynyls, 3- methyl-1s-propinyl, 2- first
Base -3- propinyls, pentynyl, 1- hexin bases, 3- methyl-1s-butynyl, 3,3- dimethyl -1- butynyls, heptynyl, octyne
Base.
Can be that carbon number is 1~20 when containing oxygen atom in the alkyl that the foregoing carbon number being previously mentioned is 1~20
Alkoxy or carbon number be 2~20 saturated fat ether.Preferably, alkoxy, carbon of the carbon number for 1~10 are selected
Atomicity is 1~10 saturated fat ether, it is further preferred that selecting alkoxy, carbon number of the carbon number for 1~6
For 1~6 saturated fat ether, it is further preferred that select carbon number for 1~4 alkoxy, carbon number be 1~4
Saturated fat ether.As the example of oxygen-containing group, can specifically enumerate：Methoxyl group, ethyoxyl, positive propoxy, isopropyl oxygen
Base, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, cyclopentyloxy, cyclohexyloxy, methoxy,
Ethoxyethyl group, isopropoxy normal-butyl.
After the alkyl that the carbon number being previously mentioned is 1~20 is substituted by halogen atom, the corresponding carbon number that formed is 1
~20 halogenated alkyl, wherein halogen atom are F, Cl, Br.In the halo groups formed, halogen atom to part hydrogen atom or
Person's whole hydrogen atom is substituted, for example, the number of halogen atom can be 1,2,3 or 4.
Preferably, select carbon number for 1~10 halogenated alkyl, it is further preferred that selecting carbon number as 1~6
Halogenated chain-like alkyl, carbon number be 3~8 halogenated cycloalkyl, it is further preferred that selecting carbon number as 1~4
Halogenated chain-like alkyl, the halogenated cycloalkyl that carbon number is 5~7.As the example of halogenated alkyl, can specifically enumerate：Trifluoro
Methyl (- CF3), 2- fluoro ethyls, 3- fluorine n-propyl, 2- fluorine isopropyl, 4- fluorine normal-butyl, 3- fluorine sec-butyl, 5- fluorine n-pentyl, 4-
Fluorine isopentyl, the fluoro- 3- methylcyclohexyls of 1- fluorine cyclopenta, 1-, wherein F can be substituted by Cl and/or Br.
After the alkyl that the carbon number being previously mentioned is 1~20 is substituted by cyano, it is corresponding formed carbon number for 2~
21 alkane cyano, wherein cyano can substitute the part hydrogen atom in abovementioned alkyl or whole hydrogen atoms, of cyano
Number is preferably 1.
Preferably, select carbon number for 2~10 alkane cyano, it is further preferred that selecting carbon number as 2~6
Chain alkane cyano, carbon number be 4~8 cycloalkanes cyano, it is further preferred that select carbon number for 3~5 chain alkane
Cyano, the cycloalkanes cyano that carbon number is 4~7.As the example of the group containing cyano, can specifically enumerate：Cyanogen methyl, 2-
Cyano ethyl, 3- cyano n-propyl, 2- cyanoisopropyls, 4- cyano normal-butyl, 4- cyano isopentyl, 6- cyano n-hexyl, 3-
Cyan cyclopentyl, 4- cyanogen methylcyclohexyls.
It is corresponding to be formed after the alkyl that the carbon number being previously mentioned is 1~20 is substituted by nitro, carboxyl or sulfonic group
Nitro alkyl, carboxyalkyl, sulfonic group alkyl, wherein nitro, carboxyl or sulfonic group are to part hydrogen atom or whole hydrogen atoms
Substituted, for example, the number of substitution can be 1,2,3 or 4.After alkyl is substituted by above-mentioned group, it can be formed as follows
Group：Nitre methyl, 2- nitro-ethyls, 3- nitros n-propyl, 2- nitros isopropyl, 4- nitros normal-butyl, 4- nitros isopentyl, 6-
Nitro n-hexyl, 3- nitros cyclopenta, 4- nitre methylcyclohexyls etc., in the example enumerated, nitro can be by carboxyl or sulfonic group
Substituted.
As a kind of improvement of the application electrolyte, shown in the example table 1 specific as follows of sultones：
Table 1
In above-mentioned electrolyte, the content of hydrogenation thiophene-boron trifluoride complex is the total weight of electrolyte
0.05%~10%, it is preferably the 0.1%~4% of the total weight of electrolyte；The content of sultone compounds is electrolyte
The 0.1%~10% of total weight is preferably the 1%~5% of the total weight of electrolyte.
If the content that thiophene-boron trifluoride complex is hydrogenated in electrolyte is excessive, can be in positive and negative plate surface shape
Into thicker and fine and close passivating film, the conductive performance of lithium ion is reduced, so as to deteriorate lithium ion battery at ambient and elevated temperatures
Cycle performance and high-temperature storage performance；And the content of sultone compounds is excessive, can also be formed very on negative plate surface
Passivating film that is thick and stablizing, again such that the impedance of negative plate greatly increases, reduces the conductive performance of lithium ion, so as to dislike
Change lithium ion battery cycle performance at ambient and elevated temperatures and high-temperature storage performance.
In above-mentioned electrolyte, the organic solvent can be non-aqueous organic solvent, and the organic solvent is that carbon number is 1
~8 and containing at least one ester group compound.
As the example of organic solvent, can enumerate：Ethylene carbonate, propene carbonate, butylene, fluoro carbonic acid second
Enester, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- fourths
At least one of lactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate, ethyl butyrate.
In above-mentioned electrolyte, lithium salts can be organic lithium salt or inorganic lithium salt, specifically, can contain in lithium salts
At least one of fluorine element, boron element, P elements.Preferably, lithium salts is selected from lithium hexafluoro phosphate (LiPF6), LiBF4
(LiBF4), lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), tetrafluoro oxalic acid lithium phosphate (LiTFOP), LiN (SO2RF)2、
LiN(SO2F)(SO2RF), double trifluoromethanesulfonimide lithium LiN (CF3SO2)2(being abbreviated as LiTFSI), double (fluorine sulphonyl) imines
Lithium Li (N (SO2F)2) (being abbreviated as LiFSI), di-oxalate lithium borate LiB (C2O4)2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium
LiBF2(C2O4At least one of) (being abbreviated as LiDFOB), wherein, substituent RF=-CnF2n+1Saturation perfluoroalkyl, n 1
~10 integer, and 2n+1 is more than zero integer.Particularly preferably LiPF6And/or LiN (SO2RF)2。
Preferably, the concentration of lithium salts in the electrolytic solution is 0.5M~2M (M=molL-1)。
In this application, the preparation method of electrolyte selects conventional method, such as by organic solvent, lithium salts and can add
Agent is added to be uniformly mixed.
The another object of the application is the provision of lithium ion battery, and lithium ion battery includes electrolyte, lives containing anode
Positive plate, the negative plate and isolation film containing negative electrode active material of property material.
In above-mentioned lithium ion battery, positive plate further includes binding agent and conductive agent, will include positive electrode active materials, glues
The anode sizing agent of agent and conductive agent is tied coated on plus plate current-collecting body, positive plate is obtained after anode sizing agent drying.It likewise, will
The negative electrode slurry for including negative electrode active material, binding agent and conductive agent is coated on negative current collector, treats that negative electrode slurry is dried
After obtain negative plate.
Preferably, positive electrode active materials are selected from cobalt acid lithium LiCoO2, cobalt nickel lithium manganate ternary material, LiFePO 4, manganese
Sour lithium (LiMnO2At least one of), such as the mixture of cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material can be used as positive-active material
Material.As the example of cobalt nickel lithium manganate ternary material, can specifically enumerate：LiNi1/3Co1/3Mn1/3O2、
LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2。
Preferably, negative electrode active material is carbon material and/or silicon materials.
In above-mentioned lithium ion battery, the specific species of lithium battery diaphragm is not exposed to specific limitation, can be existing
Any diaphragm material used in lithium ion battery, such as polyethylene, polypropylene, Kynoar and their MULTILAYER COMPOSITE
Film, but it is not limited only to these.
Embodiment
The application is further described below by way of specific example.But these examples are only exemplary, not to this
The protection domain of application forms any restrictions.
In following embodiments, comparative example and test example, reagent, material and the instrument used be not such as special
Explanation, be conventional reagent, conventional material and conventional instrument, it is commercially available, wherein involved reagent can also lead to
Conventional synthesis process synthesis is crossed to obtain.
In following embodiments, comparative example and test example, used reagent is as follows：
Additive：
Hydrogenate thiophene-boron trifluoride complex：1~compound of compound 3；
Sultone compounds：The sultones 12 (1,3- propene sultone, abbreviation PST) mentioned in foregoing table 1.
Lithium salts：Lithium hexafluoro phosphate (LiPF6)。
Organic solvent：Ethylene carbonate (EC), methyl ethyl carbonate (EMC).
Positive electrode active materials：Cobalt nickel lithium manganate ternary material：LiNi1/3Co1/3Mn1/3O2LiNi0.5Co0.2Mn0.3O2、
LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2Deng.
Isolation film：Using PE porous polymer films as isolation film.
Embodiment 1：The preparation of lithium ion battery (following abbreviation batteries) 1~29
Battery 1~29 is prepared by the following method：
(1) prepared by negative plate
Negative electrode active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber, thickener sodium carboxymethylcellulose are pressed
It is graphite according to weight ratio：Acetylene black：Butadiene-styrene rubber：Sodium carboxymethylcellulose=95:2:2:1 is mixed, and adds in deionized water
Afterwards, it is thoroughly mixed, forms uniform negative electrode slurry；By this slurry coated on negative current collector copper foil, then dry, is cold
Pressure, obtains negative plate.
(2) prepared by positive plate
By positive electrode active materials lithium-nickel-manganese-cobalt ternary material, conductive agent acetylene black, binding agent polyvinylidene fluoride by weight
Than for lithium-nickel-manganese-cobalt ternary material：Acetylene black：Polyvinylidene fluoride=96:2:2 are mixed, and add in Solvents N-methyl pyrrolidines
Ketone after being thoroughly mixed, forms uniform anode sizing agent；This slurry is coated on plus plate current-collecting body aluminium foil, then dry,
Cold pressing, obtains positive plate.
(3) prepared by electrolyte
Electrolyte 1~29 is prepared by the following method：
In water content<In the argon gas atmosphere glove box of 10ppm, by EC, EMC according to weight ratio be EC：EMC=3：7 carry out
After mixing, mixed solvent, then the lithium salts LiPF that will fully dry are obtained6Above-mentioned in the mixed solvent is dissolved in, is then added thereto
Enter to hydrogenate thiophene-boron trifluoride complex and sultone compounds, after stirring evenly, obtain electrolyte, wherein LiPF6
Concentration be 1mol/L.
(4) preparation of battery
Battery 1~29 is prepared by the following method：
Positive plate, isolation film, negative plate are folded in order, isolation film is made to be between positive/negative plate the work for playing isolation
With then winding obtains naked battery core；Naked battery core is placed in outer packing paper tinsel, after the above-mentioned electrolyte prepared is injected into drying
Battery in, then by processes such as Vacuum Package, standing, chemical conversion, shapings, obtain battery.
It is above-mentioned prepare battery during, it is used in selected electrolyte, each electrolyte in each battery
The species of thiophene-boron trifluoride complex and its species and its content of content and sultone compounds are hydrogenated, it is as follows
It states shown in table 2.
In table 2 below, thiophene-content of boron trifluoride complex and the content of sultone compounds are hydrogenated
It is the weight percent that the total weight based on electrolyte is calculated.
Table 2
Comparative example：Lithium ion battery (following abbreviation batteries) 1#~17#Preparation
Battery 1#~17#Prepared by the following method：
The preparation of battery 1 in embodiment 1 is repeated, wherein in the preparation of electrolyte, changes hydrogenation thiophene-boron trifluoride and matches somebody with somebody
The position species of compound, content and/or the species, the content that change sultone compounds, remaining condition are constant.
It is above-mentioned prepare battery during, it is used in selected electrolyte, each electrolyte in each battery
The species of thiophene-boron trifluoride complex and its species and its content of content and sultone compounds are hydrogenated, it is as follows
It states shown in table 3.
In Table 3 below, thiophene-content of boron trifluoride complex and the content of sultone compounds are hydrogenated
It is the weight percent that the total weight based on electrolyte is calculated.
Table 3
Note：In table 3, "-" expression is not added with any kind of substance.
Test case
(1) the high-temperature storage performance test of battery
With the high-temperature storage performance of the volume change characterization battery before and after battery storage.
The battery being prepared in embodiment and comparative example carries out following tests：
At 25 DEG C, 4.6V first charges to battery with the constant current of 0.5C, further with 4.6V constant-potential charges
It is 0.025C to electric current, then battery is measured to the initial volume of battery in deionized water with drainage, by battery at this time
Initial volume as the volume before battery storage, then battery is placed at 85 DEG C and stores 6h, after to be stored, test electricity
Then the volume change of battery is calculated in the volume of pond after storage at high temperatures by following formula.In addition, test result such as following table
Shown in 4.
The volume change (%) of battery=[volume before volume/battery storage after battery high-temperature storage] × 100%
(2) the normal-temperature circulating performance test of battery
The battery being prepared in embodiment and comparative example carries out following tests：
At 25 DEG C, 4.6V first charges to battery with the constant current of 1C, further with 4.6V constant-potential charges extremely
Electric current is 0.025C, and then with the constant current of 1C by battery discharge to 3.0V, this is a charge and discharge cycles process, this
Discharge capacity is the discharge capacity of the 1st Xun Huan.Battery carries out multiple cycle charge discharge electrical testing in a manner described, and detection obtains the
The discharge capacity of 100 Xun Huans, and pass through the circulation volume conservation rate that battery is calculated in following formula.In addition, test result is as follows
Shown in table 4.
Capacity retention ratio (%) after the cycle of battery 100 times=[discharge capacity/1st time cycle of the 100th cycle is put
Capacitance] × 100%
(3) the high temperature cyclic performance test of battery
The battery being prepared in embodiment and comparative example carries out following tests：
At 45 DEG C, 4.6V is first charged to lithium rechargeable battery with the constant current of 1C, it is further constant with 4.6V
Voltage charges to electric current as 0.025C, and then with the constant current of 1C by battery discharge to 3.0V, this is a charge and discharge cycles
Process, this discharge capacity are the discharge capacity of the 1st Xun Huan.Battery carries out multiple cycle charge discharge electrical measurement in a manner described
Examination, detection obtains the discharge capacity of the 100th Xun Huan, and passes through the capacity retention ratio that following formula is calculated after the cycling of battery.
In addition, test result is as shown in Table 4 below.
Capacity retention ratio (%) after the cycle of battery 100 times=[discharge capacity/1st time cycle of the 100th cycle is put
Capacitance] × 100%
Table 4
Related data from above-mentioned table 4, is analyzed as follows：
(1) test result analysis of high-temperature storage performance
By the volume change that battery 1~30 obtains and battery 1#It can be seen that in the comparison of obtained volume change
Addition hydrogenation thiophene-boron trifluoride complex and sultone compounds in the electrolytic solution, enable to battery have compared with
Low volume change.
By battery 1#~8#Obtained volume change is it is known that electrolyte 1#In without adding in any additive so that
Anode has very strong oxidisability under high-voltage state, understands the organic solvent in oxidation electrolyte, is easy to cause battery producing gas,
The volume change for making battery is excessively high.
Due in battery 4#, battery 5#With battery 7#In, hydrogenate thiophene-boron trifluoride complex and/or sultones
The characteristics of weight percentage of compound is very little, and the passivating film formed cannot have both compactness and stability can not also have
Effect ground prevents the side reaction between active material and electrolyte, makes the volume change after battery storage excessively high.
In battery 1~8, the content of sultone compounds is 2%, and addition content is 0.05%~10% nitrogen-containing hetero
Ring-boron trifluoride complex can form composite passivation film that is fine and close, stablizing, prevent between active material and electrolyte
Side reaction, make battery after storage at high temperatures have relatively low volume change, and with hydrogenation thiophene-boron trifluoride coordinationization
The increase of object content is closed, after battery stores 6h at 85 DEG C, there is relatively low volume change.
In battery 9~14, the content of hydrogenation thiophene-boron trifluoride complex is 2%, and it is 0.5% to add in content
~10% sultone compounds can form composite passivation film that is fine and close, stablizing, prevent between active material and electrolyte
Side reaction, make battery that there is relatively low volume change, and the increasing of the content with sultone compounds after storage at high temperatures
Add, after battery stores 6h at 85 DEG C, there is relatively low volume change.Likewise, the volume of 15~30 gained of battery is become
Rate is analyzed, and has analysis result same as described above.
(2) test result analysis of cycle performance
Capacity retention ratio and battery 1 after the cycling obtained by battery 1~30#Capacity retention ratio after obtained cycling can
To find out, have higher containing hydrogenation thiophene-boron trifluoride complex and sultone compounds, battery in electrolyte
Capacity retention ratio, battery have excellent cycle performance under high temperature and room temperature.
By battery 1#~17#Capacity retention ratio after obtained cycling is it is known that electrolyte 1#In not any add without adding in
Add agent so that organic solvent can generate more side reaction in pole piece, and the capacity retention ratio for causing battery is low.
In battery 2#With battery 3#In, addition hydrogenates thiophene-boron trifluoride ligand compound in respective electrolyte respectively
Object, sultone compounds can't effectively prevent the pair between active material and electrolyte by the passivating film formed
Reaction, so that the cycle performance of battery cannot improve substantially.
Due in battery 4#, battery 5#With battery 7#In, hydrogenate thiophene-boron trifluoride complex and/or sultones
The characteristics of weight percentage of compound is very little, and the composite passivation film formed cannot have both compactness and stability, can not
The side reaction between active material and electrolyte is effectively prevented, makes cycle performance of the battery under high temperature and room temperature that cannot have
The improvement of effect.
In battery 6#With battery 8#In, hydrogenate thiophene-boron trifluoride complex or sultone compounds content mistake
More, excessive hydrogenation thiophene-boron trifluoride complex and sultone compounds residual in the electrolytic solution, continue in pole piece
Surface is reacted, and interface impedance is caused to become larger, and deteriorates cycle performance of the battery under high temperature and room temperature.
In battery 1~8, the content of sultone compounds is 2%, adds in content as 0.05%~10% hydrogenation thiophene
Fen-boron trifluoride complex can form composite passivation film that is fine and close, stablizing, prevent between active material and electrolyte
Side reaction, make battery cycled under high temperature and room temperature after have higher capacity retention ratio.
In battery 4 and battery 9~14, the content of hydrogenation thiophene-boron trifluoride complex is 2%, and addition contains
Measure the sultone compounds for 0.5%~10%, composite passivation film that is fine and close, stablizing can be formed, prevent active material with
Side reaction between electrolyte makes battery have higher capacity retention ratio after being cycled under high temperature and room temperature.Likewise, to electricity
Capacity retention ratio after pond 15~30 is cycled is analyzed, and has analysis result same as described above.
In from the above thiophene-boron trifluoride complex and sulfonic acid are hydrogenated as can be seen that working as in electrolyte simultaneously
During lactone compound, the capacity retention ratio after battery cycles under high temperature and room temperature is improved, battery has under high temperature and room temperature
Excellent cycle performance.
In summary：In the electrolytic solution, when hydrogenation thiophene-boron trifluoride complex content it is too small or excessive,
When sultone compounds content is too small or excessive, it cannot all form that fine and close, stablizing, interface performance is preferably composite passivated
Film can not obtain the battery of the good cycle under high temperature and room temperature simultaneously.When electrolyte contains 0.05%~10% hydrogenation
Thiophene-boron trifluoride complex and 0.5%~10% sultone compounds, especially containing 0.1%~4.0%
Hydrogenate thiophene-boron trifluoride complex and 1%~4% sultone compounds, battery following under high temperature and room temperature
Ring performance and high-temperature storage performance are all more excellent.
Embodiment 2
Method according to embodiment 1 prepares electrolyte, and difference lies in additives to hydrogenate thiophene-boron trifluoride ligand compound
Object, the structural formula of sultone compounds and content are as shown in table 5：
Wherein, the structural formula of sultone compounds sultones as shown in table 1, hydrogenation thiophene-boron trifluoride are matched somebody with somebody
Position compound, the content of sultone compounds are the weight percent that the total weight based on electrolyte is calculated.
Table 5
The electrolyte 31~46 being prepared is prepared into lithium ion battery according to method in above-described embodiment, is prepared
The high-temperature storage performance of lithium ion battery, normal-temperature circulating performance, high temperature cyclic performance are similar to the aforementioned embodiment.
The announcement of book according to the above description, the application those skilled in the art can also carry out the above embodiment
Appropriate change and modification.Therefore, the application is not limited to specific embodiment disclosed and described above, to the application's
Some modifications and changes should also be as falling into the protection domain of claims hereof.
Claims (10)
1. a kind of electrolyte, which is characterized in that including organic solvent, lithium salts and additive, the additive include hydrogenation thiophene-
Boron trifluoride complex and sultone compounds；The content of the hydrogenation thiophene-boron trifluoride complex is electricity
Solve the 0.05%~10% of the total weight of liquid；The content of the sultone compounds is the 0.1%~10% of the total weight of electrolyte；
Hydrogenation thiophene-boron trifluoride the complex is selected from least one of compound of structural formula as shown in formula I：
Wherein, R1, R2, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano, substituted or unsubstituted C1~20Alkyl takes
Generation or unsubstituted C2~20Alkenyl, substituted or unsubstituted C6~26Aryl；Substituent group is selected from halogen, cyano.
2. electrolyte according to claim 1, which is characterized in that the hydrogenation thiophene-boron trifluoride complex choosing
At least one of compound of structural formula shown in Formulas I A freely；
Wherein, R3, R4It is each independently selected from the substituted or unsubstituted C of hydrogen atom, halogen atom, cyano1~20Alkyl, substitution or not
Substituted phenyl；Substituent group is selected from halogen, cyano.
3. electrolyte according to claim 2, which is characterized in that R3、R4It is each independently selected from hydrogen atom, fluorine atom.
4. electrolyte according to claim 1, which is characterized in that the sultone compounds be selected from following formula II,
At least one of V compound represented of formula III, formula IV and formula：
Wherein, R11、R12、R13、R14Be each independently selected from hydrogen atom, halogen atom, nitro, cyano, carboxyl, sulfonic group, substitution or
Unsubstituted C1~20Alkyl, substituted or unsubstituted C1~20Alkoxy, substituted or unsubstituted C2~20Alkenyl, substitution or unsubstituted
C2~20Alkynyl, substituted or unsubstituted C1~20Alkane sulfonyl, substituted or unsubstituted C2~20Alkene sulfonyl, substitution do not take
The C in generation2~20Alkynes sulfonyl；Substituent group is selected from halogen, cyano, nitro, carboxyl or sulfonic group.
5. electrolyte according to claim 4, which is characterized in that R11、R12、R13、R14Be each independently selected from hydrogen atom,
Substituted or unsubstituted C1~6Straight or branched alkyl, substituted or unsubstituted C1~6Straight or branched alkoxyl；Substitution does not take
The C in generation5~7Cycloalkyl, substituted or unsubstituted C2~6Alkenyl, substituted or unsubstituted C2~6Alkynyl；Substituent group is selected from halogen, cyanogen
Base.
6. the electrolyte according to claim 1, which is characterized in that the organic solvent is selected from ethylene carbonate, carbonic acid third
Enester, butylene, fluorinated ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbon
Sour first propyl ester, ethyl propyl carbonic acid ester, 1,4- butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate with
And at least one of ethyl butyrate.
7. electrolyte according to claim 1, which is characterized in that the lithium salts is selected from lithium hexafluoro phosphate, tetrafluoro boric acid
Lithium, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro oxalic acid lithium phosphate, LiN (SO2RF)2、LiN(SO2F)(SO2RF), double (fluorine sulphonyl) it is sub-
At least one of amine lithium, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, wherein, RF = -CnF2n+1, n be 1~10 it is whole
Number.
8. electrolyte according to claim 7, which is characterized in that the lithium salts is selected from LiPF6、LiN(SO2RF)2In
It is at least one.
9. electrolyte according to claim 7, which is characterized in that the concentration of the lithium salts in the electrolytic solution is 0.5
mol·L−1~2 molL−1。
10. a kind of lithium ion battery, which is characterized in that including the positive plate containing positive electrode active materials, contain negative electrode active material
Negative plate, isolation film and the electrolyte according to any one of claims 1 to 9 of material.
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| CN108682888A (en) * | 2018-04-08 | 2018-10-19 | 湖南航盛新能源材料有限公司 | Electrolyte containing Low ESR sultones and preparation method thereof and power battery |
| CN110676511A (en) * | 2019-09-02 | 2020-01-10 | 孚能科技(赣州)股份有限公司 | Lithium ion battery electrolyte and lithium ion secondary battery |
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