CN105789701A - Electrolyte and lithium ion battery comprising same - Google Patents
Electrolyte and lithium ion battery comprising same Download PDFInfo
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- CN105789701A CN105789701A CN201610194875.9A CN201610194875A CN105789701A CN 105789701 A CN105789701 A CN 105789701A CN 201610194875 A CN201610194875 A CN 201610194875A CN 105789701 A CN105789701 A CN 105789701A
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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
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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Abstract
The application relates to the field of batteries, in particular to electrolyte and a lithium ion battery comprising the electrolyte. The electrolyte of the present application includes an organic solvent, a lithium salt, and an additive including a hydrogenated thiophene-boron trifluoride complex compound and lithium fluorophosphate. Under the common synergistic effect of the electrolyte during hydrogenation of thiophene-boron trifluoride coordination compounds and lithium fluorophosphate, SEI films capable of preventing the electrolyte from being decomposed are formed on the surfaces of a positive plate and a negative plate of the lithium ion battery, and acidic substances generated in the electrolyte can be neutralized, so that the cycle performance and the storage performance of the lithium ion battery are greatly improved.
Description
Technical field
The application relates to field of batteries, particularly relates to a kind of electrolyte and includes the lithium ion battery of this electrolyte.
Background technology
At present, the positive electrode active materials employed in lithium ion battery mainly have LiMn2O4, cobalt acid lithium, ternary material,
LiFePO 4s etc., under normal conditions, select the charge cutoff voltage of the lithium ion battery of the above-mentioned positive electrode being previously mentioned
Less than 4.2V, but it is as progress and the development in market of science and technology, promotes the energy density of lithium ion battery day by day
Seeming important and urgent, the effective ways of a kind of energy density promoting lithium ion battery are exploitation high-voltage lithium ion batteries.
But, under the high voltage of 4.6V, the electrolyte positive electrode surface oxidation Decomposition at battery of routine, electrolysis can be caused
The oxidation Decomposition of liquid self can promote the deteriorative reaction of positive electrode active materials simultaneously, affects the performance of lithium ion battery further,
Such as storage performance and cycle performance.
For defect and the deficiency of existing battery, special release the application.
Summary of the invention
The primary goal of the invention of the present invention is to propose a kind of electrolyte.
Second goal of the invention of the present invention is to propose a kind of lithium ion battery.
In order to complete the purpose of the present invention, the technical scheme of employing is:
The application relates to a kind of electrolyte, and including organic solvent, lithium salts and additive, described additive includes hydrogenating thiophene
Fen-boron trifluoride coordination compound and fluorophosphate lithium.
Preferably, described hydrogenation thiophene-boron trifluoride coordination compound is in the compound of structural formula as shown in formula I
At least one:
Wherein, R1, R2, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted C1～20Alkane
Base, substituted or unsubstituted C2～20Thiazolinyl, substituted or unsubstituted C6～26Aryl；
Substituent group is selected from halogen, cyano group.
Preferably, described hydrogenation thiophene-boron trifluoride coordination compound is in the compound of structural formula as shown in formula I A
At least one；
Wherein, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted C1～20Alkyl, replacement
Or unsubstituted phenyl；Substituent group is selected from halogen, cyano group.
Preferably, R3, R4It is each independently selected from hydrogen atom, fluorine atom.
Preferably, at least one during described fluorophosphate lithium compound is single lithium fluophosphate and difluorophosphate.
Preferably, the 0.05% of the gross weight that content is electrolyte of described hydrogenation thiophene-boron trifluoride coordination compound
～10%.
Preferably, the 0.001%～2% of the gross weight that content is electrolyte of described fluorophosphate lithium.
Preferably, described organic solvent is selected from ethylene carbonate, Allyl carbonate, butylene, fluoro ethylene carbonate
In ester, Ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4-fourth
At least one in ester, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate and ethyl n-butyrate..
Preferably, described 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), double trifluoromethanesulfonimide lithium, double (fluorine sulphonyl) imine lithium, double
At least one in Lithium bis (oxalate) borate, difluorine oxalic acid boracic acid lithium, wherein, RF=CnF2n+1, n is the integer of 1～10, is preferably
LiPF6、LiN(SO2RF)2In at least one；
It is furthermore preferred that the concentration that described lithium salts is in the electrolytic solution is 0.5mol L-1～2mol L-1。
The application further relates to a kind of lithium ion battery, including the positive plate containing positive electrode active materials, containing negative electrode active
The negative plate of material, isolating membrane and electrolyte described herein.
The Advantageous Effects that the application can reach is:
In the electrolyte that the application provides, owing to including hydrogenating thiophene-boron trifluoride coordination compound and fluoro phosphorus simultaneously
Acid lithium, therefore, it is possible to improve cycle performance and the storage performance of lithium ion battery.Under the common synergism of the two, lithium from
The positive and negative plate surface of sub-battery is respectively formed the SEI film that can stop electrolyte decomposition, especially forms resistance on negative plate surface
Anti-little and fine and close solid electrolyte interface (SEI) film；Further, since electrolyte contains hydrogenation thiophene-boron trifluoride simultaneously
Coordination compound and fluorophosphate lithium, it is also possible to stablize lithium salts；Additionally it is possible to the acidic materials produced in neutralization electrolyte,
Such as PF5、HF、CO2Deng, effectively reduce the corrosion to SEI film of these acidic materials.Thus can be under the synergism of the two, significantly
Improve the cycle performance of lithium ion battery；Meanwhile, the storage performance of electrolyte is also significantly improved.
Detailed description of the invention
Being described in detail below by the application, the feature of the application and advantage will become more along with these explanations
For clear, clear and definite.
The purpose of the application is to provide a kind of electrolyte, including organic solvent, lithium salts and additive, described additive bag
Include hydrogenation thiophene-boron trifluoride coordination compound and fluorophosphate lithium.
In above-mentioned electrolyte, hydrogenation thiophene-boron trifluoride coordination compound refers to that hydrogenation thiophene mentioned above is organic
The coordination compound that molecule and boron trifluoride are formed, boron trifluoride is anion, and hydrogenation thiophene is cation, whole hydrogenation thiophene
Fen-boron trifluoride coordination compound is electric neutrality.
At least one in the compound of structural formula as shown in formula I of hydrogenation thiophene-boron trifluoride coordination compound:
Wherein, R1, R2, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted C1～20Alkane
Base, substituted or unsubstituted C2～20Thiazolinyl, substituted or unsubstituted C6～26Aryl；
Substituent group is selected from halogen, cyano group.
Wherein, halogen atom is F, Cl, Br, preferably F, Cl；
Wherein, as described below in above-mentioned formula I substituent group.
Carbon number is the alkyl of 1～20, and alkyl can be chain-like alkyl, it is possible to for cycloalkyl, be positioned on the ring of cycloalkyl
Hydrogen can be replaced by alkyl, in described alkyl, the preferred lower limit of carbon number is 2,3,4,5, preferred higher limit is 3,4,5,
6,8,10,12,14,16,18.Preferably, the alkyl selecting carbon number to be 1～10, it is further preferred that select carbon number
Being the chain-like alkyl of 1～6, carbon number is the cycloalkyl of 3～8, it is further preferred that the chain selecting carbon number to be 1～4
Shape alkyl, carbon number is the cycloalkyl of 5～7.As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, different
Propyl group, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, cyclopenta, cyclohexyl.
Carbon number be the thiazolinyl of 2～20 can be cyclic alkenyl radical, it is possible to for chain thiazolinyl.It addition, in thiazolinyl double bond
Number is preferably 1.In described thiazolinyl, the preferred lower limit of carbon number is 3,4,5, and preferred higher limit is 3,4,5,6,8,10,
12,14,16,18.Preferably, the thiazolinyl selecting carbon number to be 2～10, it is further preferred that selecting carbon number is 2～6
Thiazolinyl, it is further preferred that selecting carbon number is the thiazolinyl of 2～5.As the example of thiazolinyl, specifically can enumerate: second
Thiazolinyl, pi-allyl, isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base.To the specifically chosen of alkynyl and thiazolinyl
Identical.
Carbon number is the aryl of 6～26, such as phenyl, benzene alkyl, at least contain a phenyl aryl such as xenyl,
Condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and condensed-nuclei aromatics base also can be replaced by alkyl or thiazolinyl.Preferably, choosing
Select the aryl that carbon number is 6～16, it is further preferred that the aryl selecting carbon number to be 6～14, the most preferably
Ground, the aryl selecting carbon number to be 6～9.As the example of aryl, specifically can enumerate: phenyl, benzyl, xenyl, to first
Phenyl, o-tolyl, a tolyl.
When the thiazolinyl that the alkyl that the carbon number being previously mentioned is 1～20, carbon number are 2～20, carbon number be 6～
After the aryl of 26 is replaced by halogen atom, the most accordingly formed carbon number be 1～20 haloalkyl, carbon number be 2～
The haloalkenyl group of 20, carbon number are the halogenated aryl of 6～26；Wherein halogen atom is F, Cl, Br, preferably F, Cl.In institute's shape
In the halo group become, halogen atom to part hydrogen atom or all hydrogen atom replace, the number of halogen atom can be 1,2
Individual, 3 or 4.
Preferably, select carbon number be 1～10 haloalkyl, carbon number be 2～10 haloalkenyl group, carbon atom
Number is the halogenated aryl of 6～16；It is further preferred that the halo chain-like alkyl selecting carbon number to be 1～6, carbon number are 3
～the halogenated aryl that haloalkenyl group that the halogenated cycloalkyl of 8, carbon number are 2～6, carbon number are 6～14；The most excellent
Selection of land, select carbon number be 1～4 halo chain-like alkyl, carbon number be 5～7 halogenated cycloalkyl, carbon number be 2
～the halogenated aryl that the haloalkenyl group of 5, carbon atom are 6～10.
As the example of halo group, specifically can enumerate: trifluoromethyl (-CF3), 2-fluoro ethyl, 3-fluorine n-pro-pyl, 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-hexenyl, adjacent fluorophenyl, to fluorophenyl, a fluorophenyl, 4-trifluoromethylphenyl, 2,6-difluoromethyl phenyl, the fluoro-1-of 2-
Naphthyl.In above-mentioned concrete example, F can be replaced by Cl and/or Br.
Preferably, above-mentioned formula I substituent group is selected from: R1, R2, R3, R4Be each independently selected from hydrogen atom, halogen atom, cyano group,
Substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C1～12Thiazolinyl, substituted 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 coordination compound is selected from as shown in formula I A
At least one in the compound of structural formula；
Wherein, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted C1～20Alkyl, replacement
Or unsubstituted phenyl；Substituent group is selected from halogen, cyano group.
As a kind of improvement of the application electrolyte, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano group, replacement
Or unsubstituted C1～12Alkyl；Substituent group is selected from halogen, cyano group；
As a kind of improvement of the application electrolyte, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano group, replacement
Or unsubstituted C1～6Alkyl；Substituent group is selected from halogen, cyano group.
As a kind of improvement of the application electrolyte, R3, R4It is each independently selected from hydrogen atom, fluorine atom.
As the example of hydrogenation thiophene-boron trifluoride coordination compound, specific as follows shown:
As a kind of improvement of the application electrolyte, hydrogenation thiophene-boron trifluoride coordination compound is also selected from:
In this application, the hydrogenation thiophene-boron trifluoride coordination compound being previously mentioned can be according to the synthesis of existing routine
Method synthesizes, such as, refer to patent: CN200780033378.X.
In above-mentioned electrolyte, fluorophosphate lithium compound is at least one in single lithium fluophosphate and difluorophosphate.
Wherein, the chemical formula of single lithium fluophosphate is Li2PO3F, the chemical formula of difluorophosphate are LiPO2F2。
In this application, the fluorophosphate lithium being previously mentioned can synthesize according to the synthetic method of existing routine, such as
Refer to document: Japan Patent JP2008-140767.
In above-mentioned electrolyte, the gross weight that content is electrolyte of hydrogenation thiophene-boron trifluoride coordination compound
0.05%～10%, preferably the 0.1%～4% of the gross weight of electrolyte, the content of fluorophosphate lithium is the gross weight of electrolyte
The 0.001%～2% of amount, preferred content is the 0.01%～1% of the gross weight of electrolyte.
If in the electrolytic solution, hydrogenation thiophene-boron trifluoride coordination compound content is excessive, then can cause at positive and negative plate
Surface forms thicker SEI film, reduces the conductive performance of lithium ion, deteriorates lithium ion battery cyclicity at ambient and elevated temperatures
Energy and high rate performance；And the content of fluorophosphate lithium is excessive, then can affect the electrical conductivity of electrolyte, reduce the conductivity of lithium ion
Can, deteriorate lithium ion battery cycle performance at ambient and elevated temperatures and storage performance.
If in the electrolytic solution, hydrogenation thiophene-boron trifluoride coordination compound content is too small, it is impossible to be effectively improved lithium-ion electric
Pond cycle performance at ambient and elevated temperatures, cycle performance the most under high pressure；And the content of fluorophosphate lithium is too small, with
Sample can not play the effect of stable lithium salts, and the performance of battery is not had effect.
In above-mentioned electrolyte, organic solvent can be non-aqueous organic solvent, organic solvent preferably carbon number is 1～8,
And the compound containing at least one ester group.
As the example of organic solvent, can enumerate: ethylene carbonate, Allyl carbonate, butylene, fluoro ethylene
Alkene ester, Ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4-fourth
Lactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate, ethyl n-butyrate..
In above-mentioned electrolyte, lithium salts can be organic lithium salt, it is possible to for inorganic lithium salt, specifically, can contain in lithium salts
At least one in fluorine element, boron element, P elements.Preferably, lithium salts is selected from lithium hexafluoro phosphate (LiPF6), LiBF4
(LiBF4), lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), LiTFOP (tetrafluoro oxalic acid lithium phosphate), 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(C2O4) at least one in (being abbreviated as LiDFOB), wherein, substituent RF=CnF2n+1Saturated perfluoroalkyl, n is 1
～the integer of 10, and the integer that 2n+1 is more than zero.Particularly preferably LiPF6And/or LiN (SO2RF)2.Described lithium salts is at electrolyte
In concentration be 0.5M～2M (M=mol L-1)。
In this application, the preparation method of electrolyte selects conventional method, such as can be by organic solvent, lithium salts with add
Add agent mix homogeneously.
The another object of the application there are provided lithium ion battery, and lithium ion battery includes electrolyte, lives containing positive pole
The property positive plate of material, the negative plate containing negative active core-shell material and isolating membrane.
In above-mentioned lithium ion battery, positive plate also includes binding agent and conductive agent, will include positive electrode active materials, glue
The anode sizing agent of knot agent and conductive agent is coated on plus plate current-collecting body, treats that anode sizing agent obtains positive plate after drying.Same, will
The cathode size including negative active core-shell material, binding agent and conductive agent is coated on negative current collector, treats that cathode size is dried
Rear acquisition negative plate.
Preferably, positive electrode active materials is selected from cobalt acid lithium LiCoO2, cobalt nickel lithium manganate ternary material, LiFePO 4, manganese
Acid lithium (LiMnO2The mixture of at least one in), such as cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material can be as positive-active material
Material.As the example of cobalt nickel lithium manganate ternary material, specifically can enumerate: LiNi1/3Co1/3Mn1/3O2、
LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2。
Preferably, negative active core-shell material is material with carbon element and/or silicon materials.
In above-mentioned lithium ion battery, the concrete kind of lithium battery diaphragm is not exposed to concrete restriction, 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 1
The application is further described below by way of instantiation.But these examples are the most exemplary, not to this
The protection domain of application constitutes any restriction.
In following embodiment, comparative example and test example, reagent, material and the instrument used is as the most special
Explanation, be conventional reagent, conventional material and conventional instrument, the most commercially available, wherein involved reagent also can lead to
Cross conventional synthesis process synthesis to obtain.
In following embodiment, comparative example and test example, used reagent is as follows:
Additive:
Hydrogenation thiophene-boron trifluoride coordination compound: compound 1～compound 3；
Fluorophosphate lithium: the difluorophosphate being previously mentioned.
Lithium salts: lithium hexafluoro phosphate (LiPF6)。
Organic solvent: ethylene carbonate (EC), Ethyl methyl carbonate (EMC).
Positive electrode active materials: cobalt nickel lithium manganate ternary material (LiNi1/3Co1/3Mn1/3O2)。
Isolating membrane: using PE porous polymer film as isolating membrane.
The preparation of lithium ion battery (following be all called for short battery) 1～28
Battery 1～28 is prepared the most by the following method:
(1) prepared by negative plate
Negative electrode active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber, thickening agent sodium carboxymethyl cellulose are pressed
It is graphite according to weight ratio: acetylene black: butadiene-styrene rubber: sodium carboxymethyl cellulose=95:2:2:1 mixes, adds deionized water
After, it is thoroughly mixed, forms uniform cathode size；This slurry is coated on negative current collector Copper Foil, then dry, 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
Ratio is lithium-nickel-manganese-cobalt ternary material: acetylene black: polyvinylidene fluoride=96:2:2 mixes, and adds Solvents N-methyl pyrrolidine
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, obtain positive plate.
(3) prepared by electrolyte
Electrolyte 1～28 is prepared the most by the following method:
< in the argon gas atmosphere glove box of 10ppm, it is that EC:EMC=3:7 is carried out by EC, EMC according to weight ratio in water content
After mixing, obtain mixed solvent, then the lithium salts LiPF that will be fully dried6It is dissolved in above-mentioned mixed solvent, adds the most wherein
Enter to hydrogenate thiophene-boron trifluoride coordination compound and difluorophosphate, after stirring, it is thus achieved that electrolyte, wherein LiPF6Dense
Degree is 1mol/L.
(4) preparation of battery
Battery 1～28 prepares the most by the following method:
Positive plate, isolating membrane, negative plate are folded in order, makes isolating membrane be between positive/negative plate to play the work of isolation
With, then winding obtains naked battery core；Naked battery core is placed in outer package paper tinsel, the above-mentioned electrolyte prepared is injected into after drying
Battery in, be then passed through Vacuum Package, stand, be melted into, the operation such as shaping, it is thus achieved that battery.
Above-mentioned prepare battery during, used in electrolyte selected in each battery, each electrolyte
The hydrogenation kind of thiophene-boron trifluoride coordination compound and content thereof and the content of fluorophosphate lithium, as shown in table 1 below.
In table 1 below, the content of hydrogenation thiophene-boron trifluoride coordination compound and the content of fluorophosphate lithium are
The calculated percetage by weight of gross weight based on electrolyte.
Table 1
Comparative example: lithium ion battery (following be all called for short battery) 1#～17#Preparation
Battery 1#～17#It is prepared the most by the following method:
Repeat the preparation of battery 1 in embodiment 1, wherein in the preparation of electrolyte, change hydrogenation thiophene-boron trifluoride and join
The position kind of compound, content, and/or change the content of difluorophosphate, remaining condition is the most constant.
Above-mentioned prepare battery during, used in electrolyte selected in each battery, each electrolyte
The hydrogenation kind of thiophene-boron trifluoride coordination compound and content thereof and the content of difluorophosphate, as shown in table 2 below.
In table 2 below, the hydrogenation thiophene-content of boron trifluoride coordination compound and the content of difluorophosphate are
The calculated percetage by weight of gross weight based on electrolyte.
Table 2
Note: in table 2, "-" represents and is not added with any kind of material.
Test case
(1) storage performance test
The battery prepared in embodiment and comparative example all carries out following test:
At 25 DEG C, with 0.5C constant current charge to 4.6V, then with the constant voltage of 4.6V, battery is charged to electric current
Less than 0.05C, with the constant current of 0.5C to battery discharge to 3.0V；Again with 0.5C constant current charge to 4.6V, then with
The constant voltage of 4.6V charges to electric current and is less than 0.05C battery, and then battery is placed at 60 DEG C storage 30 days, knot to be stored
Shu Hou, with the constant current of 0.5C to battery discharge to 3.0V；Again with 0.5C constant current charge to 4.6V, then with the perseverance of 4.6V
Determine voltage and battery charged to electric current less than 0.05C, with the constant current of 0.5C to battery discharge to 3.0V, be so repeated 3 times,
Take last discharge capacity as recovering capacity.It addition, test result is as shown in Table 3 below.
The storage of battery can recover capacity rate (%)=[battery high-temperature storage after recovered capacity/battery storage before
Capacity] × 100%
(2) the normal-temperature circulating performance test of battery
The battery prepared in embodiment and comparative example all carries out following test:
At 25 DEG C, first with the constant current of 1C, battery is charged to 4.6V, further with 4.6V constant-potential charge extremely
Electric current is 0.025C, 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 circulation.Battery carries out repeatedly cycle charge discharge electrical testing in a manner described, and detection obtains the
The discharge capacity of 100 circulations, and the circulation volume conservation rate of battery is calculated by following formula.It addition, test result is as follows
Shown in table 3.
Capability retention (%) after 100 circulations of battery=[putting of the discharge capacity/1st time circulation of the 100th circulation
Capacitance] × 100%
(3) the high temperature cyclic performance test of battery
The battery prepared in embodiment and comparative example all carries out following test:
At 45 DEG C, first with the constant current of 1C, battery is charged to 4.6V, further with 4.6V constant-potential charge extremely
Electric current is 0.025C, 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 circulation.Battery carries out repeatedly cycle charge discharge electrical testing in a manner described, and detection obtains the
The discharge capacity of 100 circulations, and the capability retention after the circulation of battery is calculated by following formula.It addition, test result
As shown in Table 3 below.
Capability retention (%) after 100 circulations of battery=[putting of the discharge capacity/1st time circulation of the 100th circulation
Capacitance] × 100%
Table 3
Related data from above-mentioned table 3, analyzes as follows:
(1) 60 DEG C of storage performance test result analysis
By to battery 2#, battery 3#And battery 4 and battery 1#Test obtain as a result, it is possible to learn, when in electrolyte with
When Shi Hanyou difluorophosphoric acid lithium compound and hydrogenation thiophene-boron trifluoride coordination compound, more only add hydrogenation thiophene-borontrifluoride
Boron coordination compound or only interpolation difluorophosphate or the situation without additive, good rate capability.
The test result contrast of the battery obtained by battery 1-8, it is known that the amount of fixing difluorophosphate is 0.5%
Time, along with the addition of hydrogenation thiophene-boron trifluoride coordination compound increases, battery high rate performance first improves and reduces afterwards；
The test result contrast of the battery obtained by battery 4 and battery 9-12, it is known that fixing hydrogenation thiophene-three
When the amount of boron fluoride coordination compound is 2%, along with the addition of difluorophosphate coordination compound increases, battery high rate performance
First improve and reduce afterwards；
Same, battery 13～28 high rate performance is analyzed, there is analysis result same as described above.
(2) test result analysis of cycle performance
Capability retention after the circulation obtained by battery 1～28 and battery 1#Capability retention after the circulation obtained can
To find out, containing hydrogenation thiophene-boron trifluoride coordination compound and fluorophosphate lithium compound in electrolyte, battery has higher
Capability retention, battery have under high temperature and room temperature excellence cycle performance.
By battery 1#～9#Capability retention after the circulation obtained, it is known that electrolyte 1#In do not add any adding
Add agent so that organic solvent can produce more side reaction in pole piece, and the capability retention causing battery is low.
At battery 2#With battery 3#In, respectively in respective electrolyte add hydrogenation thiophene-boron trifluoride ligand compound
Thing, difluorophosphoric acid lithium compound, due to hydrogenation thiophene-the SEI film that formed of boron trifluoride coordination compound can't be effective
Ground stops the side reaction between active substance and electrolyte, or difluorophosphate can not effectively stablize lithium salts, so that battery
Cycle performance substantially can not get improve.
Due at battery 4#, battery 5#With battery 7#In, hydrogenation thiophene-boron trifluoride coordination compound and/or difluorophosphoric acid
The weight percentage of lithium compound very little, due to hydrogenation thiophene-the SEI film that formed of boron trifluoride coordination compound can not
Have the feature of compactness and stability concurrently, it is impossible to effectively stop the side reaction between active substance and electrolyte, or difluoro phosphorus
Acid lithium can not effectively stablize lithium salts, makes battery cycle performance under high temperature and room temperature can not get effectively improving.
At battery 6#, battery 8#, battery 9#In, hydrogenation thiophene-boron trifluoride coordination compound and/or difluorophosphoric acid lithiumation
Compound content is too much, and too much hydrogenation thiophene-boron trifluoride coordination compound and difluorophosphoric acid lithium compound remain in electrolyte
In, hydrogenation thiophene-boron trifluoride coordination compound may proceed to react in pole piece, causes interface impedance to become big；Difluorophosphoric acid
Lithium can cause the hydraulic performance declines such as the electrical conductivity of electrolyte, thus deteriorates battery cycle performance under high temperature and room temperature.
In battery 1～8, the content of difluorophosphoric acid lithium compound is 0.5%, adds the hydrogen that content is 0.05%～10%
Change thiophene-boron trifluoride coordination compound, SEI film densification, stable can be formed, stop between active substance and electrolyte
Side reaction, makes battery have higher capability retention after circulating under high temperature and room temperature.
In battery 4 and battery 9～12, the content of hydrogenation thiophene-boron trifluoride coordination compound is 2%, and addition contains
Amount is the difluorophosphoric acid lithium compound of 0.1%～2%, can form SEI film densification, stable, stop active substance and electrolysis
Side reaction between liquid, makes battery have higher capability retention after circulating under high temperature and room temperature.Same, to battery 15
～28 circulation after capability retention be analyzed, there is analysis result same as described above.
It can be seen that work as containing hydrogenated thiophene-boron trifluoride coordination compound and fluorine while of in electrolyte in from the above
During for lithium phosphate compound, improving the capability retention after battery circulates under high temperature and room temperature, battery is under high temperature and room temperature
There is the cycle performance of excellence.
In sum: in the electrolytic solution, when hydrogenation thiophene-boron trifluoride coordination compound content too small or excessive with
And when fluorophosphate lithium compound content is too small or excessive, fine and close, stable, the preferable SEI of interface performance all can not be formed
Film, it is impossible to effectively stablize lithium salts, thus the battery of good cycle under high temperature and room temperature cannot be obtained simultaneously.When electrolyte contains
There are hydrogenation thiophene-boron trifluoride coordination compound and the fluorophosphate lithium compound of 0.001%～2% of 0.05%～10%,
Especially contain hydrogenation thiophene-boron trifluoride coordination compound and the difluorophosphoric acid lithiumation of 0.1%～1% of 0.1%～4.0%
Compound, battery cycle performance under high temperature and room temperature is the most excellent.
Embodiment 2
Preparing electrolyte according to the method for embodiment 1, difference is that additive hydrogenates thiophene-boron trifluoride ligand compound
Thing, the structural formula of fluorophosphate lithium and content are as shown in table 4:
In table 4 below, hydrogenation thiophene-boron trifluoride coordination compound, the content of fluorophosphate lithium are based on electrolyte
The calculated percetage by weight of gross weight.
Table 4
The electrolyte 29～44 prepared is prepared lithium ion battery according to method in above-described embodiment, prepares
60 DEG C of storage performance test results of lithium ion battery and cycle performance are similar to the aforementioned embodiment.
The announcement of book according to the above description, above-mentioned embodiment can also be carried out by the application those skilled in the art
Suitable change and amendment.Therefore, the application is not limited to detailed description of the invention disclosed and described above, to the application's
Some modifications and changes should also be as falling in the protection domain of claims hereof.
Claims (10)
1. an electrolyte, it is characterised in that include organic solvent, lithium salts and additive, described additive include hydrogenate thiophene-
Boron trifluoride coordination compound and fluorophosphate lithium.
Electrolyte the most according to claim 1, it is characterised in that described hydrogenation thiophene-boron trifluoride coordination compound choosing
At least one in the compound of structural formula shown in formula I freely:
Wherein, R1, R2, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted C1～20Alkyl, take
Generation or unsubstituted C2～20Thiazolinyl, substituted or unsubstituted C6～26Aryl；
Substituent group is selected from halogen, cyano group.
Electrolyte the most according to claim 1, it is characterised in that described hydrogenation thiophene-boron trifluoride coordination compound choosing
At least one in the compound of structural formula shown in Formulas I A freely；
Wherein, R3, R4It is each independently selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted C1～20Alkyl, replacement or not
Substituted phenyl；Substituent group is selected from halogen, cyano group.
Electrolyte the most according to claim 1, it is characterised in that R3, R4It is each independently selected from hydrogen atom, fluorine atom.
Electrolyte the most according to claim 1, it is characterised in that described fluorophosphate lithium compound be single lithium fluophosphate and
At least one in difluorophosphate.
Electrolyte the most according to claim 1, it is characterised in that described hydrogenation thiophene-boron trifluoride coordination compound
Content is the 0.05%～10% of the gross weight of electrolyte.
Electrolyte the most according to claim 1, it is characterised in that the gross weight that content is electrolyte of described fluorophosphate lithium
The 0.001%～2% of amount.
Electrolyte the most according to claim 1, it is characterised in that described organic solvent is selected from ethylene carbonate, carbonic acid third
Alkene ester, butylene, fluorinated ethylene carbonate, Ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbon
Acid 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 in ethyl n-butyrate..
Electrolyte the most according to claim 1, it is characterised in that
Described lithium salts be selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro oxalic acid lithium phosphate,
LiN(SO2RF)2、LiN(SO2F)(SO2RF), double trifluoromethanesulfonimide lithium, double (fluorine sulphonyl) imine lithium, double oxalic acid boric acid
At least one in lithium, difluorine oxalic acid boracic acid lithium, wherein, RF=CnF2n+1, n is the integer of 1～10, preferably LiPF6、LiN
(SO2RF)2In at least one；
It is furthermore preferred that the concentration that described lithium salts is in the electrolytic solution is 0.5mol L-1～2mol L-1。
10. a lithium ion battery, it is characterised in that include the positive plate containing positive electrode active materials, containing negative electrode active material
The electrolyte according to any one of negative plate, isolating membrane and claim 1～9 expected.
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| CN113045593A (en) * | 2019-12-26 | 2021-06-29 | 北京卫蓝新能源科技有限公司 | Boron-containing organic matter and preparation method and application thereof |
| CN113725485A (en) * | 2021-07-22 | 2021-11-30 | 合肥国轩高科动力能源有限公司 | High-voltage lithium ion battery electrolyte and lithium ion battery |
| WO2022127194A1 (en) | 2020-12-17 | 2022-06-23 | 北京卫蓝新能源科技有限公司 | Sulfur-based boron trifluoride salt electrolyte containing unsaturated heterocycle, preparation method therefor and use thereof |
| WO2022160099A1 (en) * | 2021-01-26 | 2022-08-04 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device, and electronic device |
| WO2023184154A1 (en) * | 2022-03-29 | 2023-10-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and secondary battery thereof, battery module, battery pack and electric device |
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Effective date of registration: 20191219 Address after: 213300 No. 1000 North Avenue, Kunlun Street, Liyang City, Changzhou City, Jiangsu Province Patentee after: CONTEMPORARY AMPEREX TECHNOLOGY Ltd. (JIANGSU) Address before: 352100, Xingang Road, Ningde Town, Jiaocheng District, Fujian, 1 Patentee before: Contemporary Amperex Technology Co.,Ltd. |