CN105140561A - Non-aqueous electrolyte of lithium ion battery and lithium ion battery - Google Patents
Non-aqueous electrolyte of lithium ion battery and lithium ion battery Download PDFInfo
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- CN105140561A CN105140561A CN201510397735.7A CN201510397735A CN105140561A CN 105140561 A CN105140561 A CN 105140561A CN 201510397735 A CN201510397735 A CN 201510397735A CN 105140561 A CN105140561 A CN 105140561A
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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
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to non-aqueous electrolyte of a lithium ion battery. The non-aqueous electrolyte comprises a non-aqueous organic solvent, lithium salt and a film forming additive; the film forming additive comprises phosphate ester compound containing triple bonds; the film forming additive also comprises sulfones compound; the sulfones compound comprises cyclic sulfones compound and/or straight chain sulfones compound, wherein R1-R4 are separately selected from hydrogen atom, halogen or alkyl with the carbon atom number of 1-5; and A is alkylidene, with the carbon atom number of 2-6, substituted by hydrogen atom, halogen or alkyl with the carbon atom number of 1-5. The invention further relates to the lithium ion battery. The non-aqueous electrolyte of the lithium ion battery has the beneficial effects of improving low-temperature performance, and further improving the high-temperature performance and the cycle performance of the battery.
Description
Technical field
The present invention relates to lithium-ion battery electrolytes technical field, particularly a kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery.
Background technology
Lithium ion battery is compared with other batteries, have that quality is light, volume is little, operating voltage is high, energy density is high, power output is large, charge efficiency is high, memory-less effect and the advantage such as to have extended cycle life, become the first-selection of 3C (i.e. computer, communication and consumption electronic product) field lithium rechargeable battery at present.The baby battery in 3C field, requires to have that specific energy is high, cycle performance and the good feature of high-temperature behavior.The specific energy density of cobalt acid lithium material Yin Qigao and good cycle performance are the first-selected positive electrodes of 3C field lithium ion battery always, but cobalt acid lithium is its poor stability as the shortcoming of positive electrode and price is high.Nickel ternary cobalt manganese material has suitable energy density and lower price, and has the advantage to high voltage development, but nickel ternary cobalt manganese material exists the shortcoming of high-temperature behavior deficiency as positive electrode.
Electrolyte is the key factor affecting the every chemical property of battery, and especially, the performance of the additive in electrolyte to the properties of battery is even more important.In 3C field, in order to make lithium ion battery have higher energy density, a kind of scheme improves the operating voltage of lithium battery.Along with the raising of lithium battery operating voltage, the decomposition reaction of electrolyte can aggravate, but the problem thereupon brought is the high-temperature behavior of battery and the deterioration of cycle performance; Another kind of scheme improves the capacity of battery.This just requires the positive and negative electrode surface density of battery and improving constantly of compacted density, and the problem thereupon brought is the continuous increase of the impedance of battery.And the scheme that prior art is taked is the combination of above-mentioned two schemes, and there is high-temperature behavior in various degree and cycle performance worsens, impedance is high shortcoming in the lithium battery after the combination of above-mentioned two schemes simultaneously, therefore, lithium battery is made in use to face more distinct issues.
In order to ensure the cycle performance of battery excellence, usually can select in electrolyte to add traditional film for additive, such as vinylene carbonate (VC) or fluorinated ethylene carbonate (FEC).Because this kind of additive is when battery initial charge, can form excellent SEI film at graphite cathode, this SEI film compactness is good, and Heat stability is good obviously can improve the cycle performance, particularly high temperature cyclic performance of battery; But there is the undesirable deficiency of high-temperature storage performance in the film for additive of this quasi-tradition; In addition, number of patent application be 201410534841.0 Chinese patent disclose a kind of novel film for additive, namely containing the phosphate compound of three key, it not only can improve high temperature cyclic performance, obviously can also improve storge quality; But there is the comparatively large and deficiency that cryogenic property is poor of DC internal resistance (DCIR) as film for additive in the above-mentioned phosphate compound containing three key.
Number of patent application be 201380029910 patent application a kind of secondary cell is disclosed, described secondary cell comprises can occlusion release the positive pole of lithium and comprise the electrolyte of non-aqueous solution electrolysis solvent, wherein said just having the positive electrode active materials run at the current potential of more than 4.5V relative to lithium, and wherein said non-aqueous solution electrolysis solvent comprises the sulphones represented by pre-fixed pattern and the fluorinated ether compound represented by pre-fixed pattern.Namely, aforementioned patents disclose and adopt sulphones and fluorinated ether compound simultaneously, to improve the cycle characteristics of lithium battery and to reduce gas generation, by " just having the positive electrode active materials run at the current potential of more than 4.5V relative to lithium ", the energy density of lithium battery is improved in addition.The raising of the energy density of above-mentioned patent is not by its Additive.Although above-mentioned patent to a certain degree can improve the energy density of lithium battery, still there is the problem that battery impedance is high.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of high-temperature behavior good and the non-aqueous electrolyte for lithium ion cell that impedance is low, provide a kind of lithium ion battery comprising above-mentioned non-aqueous electrolyte for lithium ion cell further.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
A kind of non-aqueous electrolyte for lithium ion cell, comprise non-aqueous organic solvent, lithium salts and film for additive, described film for additive comprises the phosphate compounds containing three key, described film for additive also comprises sulfone compound, described sulfone compound comprises cyclic sulfones compounds and/or straight chain sulfone compound, the structural formula of described cyclic sulfones compounds as shown in the formula:
The structural formula of described straight chain sulfone compound as shown in the formula:
Wherein, R
1-R
4separately be selected from hydrogen atom, halogen or carbon number be 1 ?5 alkyl, A to be carbon number be 2 ?6 by hydrogen atom, halogen or carbon number be 1 ?3 the alkylidene that replaces of alkyl.
The present invention also provides a kind of lithium ion battery, the barrier film comprising positive pole, negative pole and be placed between positive pole and negative pole, also comprises above-mentioned non-aqueous electrolyte for lithium ion cell.
Beneficial effect of the present invention is:
(1) form thin, the uniform composition of thickness and the good diaphragm of compactness at positive pole, reduce impedance and also improve conductivity, thus improve the cryogenic property of non-aqueous electrolyte for lithium ion cell;
(2) obtain on the basis of good high-temperature behavior and cycle performance adding the phosphate compound containing unsaturated three key, improve the decomposition reaction of electrolyte at positive pole further, thus improve high-temperature behavior and the cycle performance of battery further.
Embodiment
By describing technology contents of the present invention in detail, being realized object and effect, be explained below in conjunction with execution mode.
The design of most critical of the present invention is: added by cyclic sulfones compounds in the nonaqueous electrolytic solution of the phosphate compound containing unsaturated three key, while not affecting high-temperature behavior and cycle performance, obviously can fall internal resistance, and then improve the cryogenic property of battery.
The invention provides a kind of non-aqueous electrolyte for lithium ion cell, comprise non-aqueous organic solvent, lithium salts and film for additive, described film for additive comprises the phosphate compounds containing three key, described film for additive also comprises sulfone compound, described sulfone compound comprises cyclic sulfones compounds and/or straight chain sulfone compound, the structural formula of described cyclic sulfones compounds as shown in the formula:
The structural formula of described straight chain sulfone compound as shown in the formula:
Wherein, R
1-R
4separately be selected from hydrogen atom, halogen or carbon number be 1 ?5 alkyl, A to be carbon number be 2 ?6 by hydrogen atom, halogen or carbon number be 1 ?3 the alkylidene that replaces of alkyl.
Know-why of the present invention is:
Phosphate compound containing unsaturated three key can form stable passivating film in negative terminal surface, can stop the decomposition of electrolyte largely.In addition; phosphate compound containing unsaturated three key also can form diaphragm at positive electrode surface; electrolyte can be stoped further in the oxidized decomposition of positive electrode surface; suppress the stripping of cathode metal ion simultaneously; especially, when charging voltage is equal to or greater than 4.35V, its effect is more obvious, can significantly improve high-temperature behavior and the cycle performance of lithium battery; but the interpolation of above-mentioned phosphate compound also causes internal resistance to increase simultaneously, thus the problem of deteriorated low temperature performance.
For the problems referred to above, the present invention, on the basis of adding the phosphate compound containing unsaturated three key, adds sulfone compound.Because the oxidizing potential of sulfone compound is lower, can form at positive pole the diaphragm that a layer thickness is thinner, uniform composition, compactness are good.
The main component of the diaphragm that sulfone compound is formed after positive pole reaction is sulfonic alkyl lithium or sulfonic alkyl compounds; by the setting of the structural formula of sulfone compound of the present invention; the sulfonic alkyl compounds molecular weight generated is little, for chain and stable in properties; copolymerization or secondary response etc. can not occur between them simultaneously, and (copolymerization or secondary response make the molecule quantitative change of product large and the thickness of diaphragm can be made to increase; thus increase impedance), thus ensure that the diaphragm formed has that thickness is thin, uniform composition and the good character of compactness.
The compactness of diaphragm effectively can improve the decomposition reaction of electrolyte at positive pole well, stops the stripping of cathode metal ion; The thickness of diaphragm and the character of uniform composition, effectively can reduce impedance; The simultaneously thin and diaphragm of uniform composition be beneficial to improve lithium ion in charge and discharge process in said protection film by property, and then improve lithium ion conductivity; And the raising of the reduction of impedance and lithium ion conductivity all effectively can improve the cryogenic property (comprising DC impedance and AC impedance) of electrolyte.
The reduction of impedance is except the impact of the thickness and uniformity that are subject to diaphragm, also closely bound up with the composition of diaphragm.The main component of diaphragm is sulfonic alkyl lithium or sulfonic alkyl compounds, C-S; C-S chemical bond is than C-C chemical bond more easy fracture under high potential, and oxidation Decomposition current potential is lower, this kind of change is the reason that possible cause the positive pole diaphragm impedance of formation lower.
If the film for additive of sulfonic alkyl compounds as positive pole is directly added in electrolyte, other decomposition reactions may be there are in sulfonic alkyl compounds, and can not effectively form protective layer at positive pole, cause electrolyte to decompose in high temperature environments comparatively seriously thus worsen high temperature cyclic performance and the storge quality of battery; .
Described diaphragm by improving the decomposition reaction of electrolyte at positive pole, can also improve the stability of electrolyte in electrochemistry, thus improving high-temperature behavior and the cycle performance of battery further;
Therefore nonaqueous electrolytic solution of the present invention has the beneficial effect making lithium ion battery obtain excellent cycle performance, excellent cryogenic property and high-temperature behavior.
It should be noted that; the effect of phosphate compound added containing unsaturated three key is not only high-temperature behavior in order to improve battery and cycle performance; its sulfone compound more of the present invention provides good reaction environment in the reaction of positive pole, thus obtains the diaphragm with better character.
In addition, sulfone compound can be independent cyclic sulfones compounds, and can be also independent chain sulfone compounds, can also be the mixture of cyclic sulfones compounds and chain sulfone compounds.
When adding separately cyclic sulfones compounds, the excellent low-impedance protection film of one deck can be formed at positive pole, effectively improving the cryogenic property of battery.
When adding separately chain sulfone compounds, can reduce the viscosity of nonaqueous electrolytic solution, the ionic conduction performance of nonaqueous electrolytic solution improves thereupon, thus improves the performance of battery.When to add the mixture of cyclic sulfones compounds and chain sulfone compounds simultaneously, both may produce synergy, at the diaphragm even compact that positive pole is formed, effectively suppress digestion of metallic ion, improve the performance of battery.
In the structural formula of cyclic sulfones compounds of the present invention, A to be carbon number be 2 ?6 by hydrogen atom, halogen or carbon number be 1 ?3 the alkylidene that replaces of alkyl, namely the nuclear carbon atomicity of cyclic sulfones compounds is 3-6.
When the nuclear carbon atomicity of cyclic sulfones compounds is less than 3 (such as 3); its diaphragm generated after positive pole reaction easily decomposes; thus do not reach and effectively fall low-impedance object; when the nuclear carbon atomicity of cyclic sulfones compounds is greater than 6; the molecular weight of the product of its diaphragm generated after positive pole reaction is excessive; thus the thickness of diaphragm is excessive, it is unsatisfactory therefore to fall low-impedance effect.
From foregoing description, the beneficial effect of non-aqueous electrolyte for lithium ion cell of the present invention is:
(1) form thin, the uniform composition of thickness and the good diaphragm of compactness at positive pole, reduce impedance and also improve conductivity, thus improve the cryogenic property of non-aqueous electrolyte for lithium ion cell;
(2) obtain on the basis of good high-temperature behavior and cycle performance adding the phosphate compound containing unsaturated three key, improve the decomposition reaction of electrolyte at positive pole further, thus improve high-temperature behavior and the cycle performance of battery further.
Further, the structural formula of described cyclic sulfones compounds be following structural formula 1, structural formula 2 one or both,
Wherein, R
5-R
19separately be selected from the alkyl that hydrogen atom, halogen or carbon number are 3 ~ 5.
Seen from the above description, the nuclear carbon atomicity of described cyclic sulfones compounds is 4-6, has molecular weight moderate, ensures that the diaphragm of its generation after positive pole reaction not easily decomposes and thickness is thin, thus effectively reduces impedance.
Further, described sulfone compound is one or more in sulfolane, ring penta sulfone and dimethyl sulfone.
Seen from the above description, sulfone compound can be simple sulfolane, ring penta sulfone or dimethyl sulfone structure.
Further, the content of described cyclic sulfones compounds and/or straight chain sulfone compound is the 0.1%-10% of electrolyte total weight.
Seen from the above description, when the content of sulfone compound is less than 0.1%, sulfone compound cannot effectively play a role; When the content of sulfone compound is greater than 10%, the diaphragm that sulfone compound is formed at positive pole is thicker, and impedance is comparatively large, causes the deterioration of cryogenic property; Preferably, the content of sulfone compound is the 1%-5% of electrolyte total weight, and this is to obtain higher chemical stability in the electrolytic solution, gives full play to the performance of electrolyte; ; Preferably; the content of cyclic sulfones compounds is the 1-3% of electrolyte total weight; the synergy that the content of chain sulfone compounds is both 1-2% of electrolyte total weight; the diaphragm thickness formed at positive pole is comparatively even; and compactness is good; effectively can reduce impedance, and improve the performance of battery.
Further, described sulfone compound accounts for the ratio that the total weight of electrolyte and described phosphate compounds account for the total weight of electrolyte and is more than or equal to 0.2.When the content of sulfone compound is lower, the diaphragm formed at positive pole and easily being dissolved, to reduction impedance with improve battery performance and do not have due effect.But generally speaking ratio is unsuitable too high, what if phosphate compounds may be described too high contains quantity not sufficient, causes at it fine and close not at the SEI film of negative pole formation, causes high-temperature behavior not enough.
Further, described non-aqueous organic solvent is selected from one or more in ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate.
Further, described lithium salts is selected from one or more in lithium hexafluoro phosphate, lithium perchlorate, LiBF4, two fluorine Lithium bis (oxalate) borate, two (trimethyl fluoride sulfonyl) imine lithium and two fluorine sulfimide lithium salts.
The structural formula of described phosphate compounds can as shown in structural formula 5:
wherein, R
20-R
22separately be selected from the alkyl that carbon number is 1-4, and R
20-R
22in at least one is unsaturated alkyl containing three key.
The content of described phosphate compounds is the 0.1%-5% of electrolyte total weight, is preferably 0.2%-1.5%.
The present invention also provides a kind of lithium ion battery, the barrier film comprising positive pole, negative pole and be placed between positive pole and negative pole, also comprises above-mentioned non-aqueous electrolyte for lithium ion cell.
Further, described positive pole is selected from LiCoO
2, LiNiO
2, LiMn
2o
4, LiCo
1-ym
yo
2, LiNi
1-ym
yo
2, LiMn
2-ym
yo
4and LiNi
xco
ymn
zm
1-x-y-zo
2in one or more, wherein, M be selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti one or more, and 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
Further, the charge cutoff voltage of described lithium ion battery is more than or equal to 4.35V.
Embodiment 1
The preparation method of the present embodiment lithium ion battery, comprises positive pole preparation process, negative pole preparation process, electrolyte preparation process, barrier film preparation process and battery number of assembling steps.
Described positive pole preparation process is: by the quality of 96.8:2.0:1.2 than blended anode active material LiNi
0.5co
0.2mn
0.3o
2, conductive carbon black and binding agent polyvinylidene fluoride, be dispersed in METHYLPYRROLIDONE, obtain anode sizing agent, anode sizing agent is uniformly coated on the two sides of aluminium foil, through drying, rolling and vacuumize, and burn-on after aluminum lead-out wire with supersonic welder and obtain positive plate, the thickness of pole plate is between 120-150 μm.
Described negative pole preparation process is: by the quality of 96:1:1.2:1.8 than admixed graphite, conductive carbon black, binding agent butadiene-styrene rubber and carboxymethyl cellulose, dispersion in deionized water, obtain cathode size, cathode size is coated on the two sides of Copper Foil, through drying, rolling and vacuumize, and burn-on after nickel making outlet with supersonic welder and obtain negative plate, the thickness of pole plate is between 120-150 μm.
Described electrolyte preparation process is: ethylene carbonate, methyl ethyl carbonate and diethyl carbonate are mixed for EC:EMC:DEC=3:3:4 (volume ratio) by volume, add the lithium hexafluoro phosphate that concentration is 1.0mol/L after mixing, add the sulfolane of tricresyl phosphate propynyl ester based on the 1wt% of electrolyte total weight and 1wt%.
Described barrier film preparation process is: adopt polypropylene, polyethylene and polypropylene three layers of barrier film, thickness is 20 μm.
Battery number of assembling steps is: between positive plate and negative plate, place three layers of barrier film that thickness is 20 μm, then the sandwich structure that positive plate, negative plate and barrier film form is reeled, square aluminum metal-back is put into after being flattened by coiling body again, the lead-out wire of both positive and negative polarity is welded on the relevant position of cover plate respectively, and with laser-beam welding machine, cover plate and metal-back are welded as a whole, obtain the battery core treating fluid injection; The electrolyte of above-mentioned preparation is injected battery core by liquid injection hole, and the amount of electrolyte will ensure the space be full of in battery core.
The routine of then carrying out initial charge according to the following steps changes into: 0.05C constant current charge 3min, 0.2C constant current charge 5min, 0.5C constant current charge 25min, shelves 1hr, shaping, after-teeming liquid, sealing, then further with the electric current constant current charge of 0.2C to 4.2V, after normal temperature shelf 24hr, 0.2C constant-current constant-voltage charging to 4.2V, then with the electric current constant-current discharge of 0.2C to 3.0V.
1) high temperature cyclic performance test: at 45 DEG C, the battery 1C constant current constant voltage after changing into is charged to 4.35V, then uses 1C constant-current discharge to 3.0V.The conservation rate of the 500th circulation volume is calculated after charge/discharge 500 circulations.Computing formula is as follows:
500th circulation volume conservation rate (%)=(the 500th cyclic discharge capacity/first time cyclic discharge capacity) × 100%;
2) normal-temperature circulating performance test: at 25 DEG C, the battery 1C constant current constant voltage after changing into is charged to 4.35V, then uses 1C constant-current discharge to 3.0V.The conservation rate of the 500th circulation volume is calculated after charge/discharge 500 circulations.Computing formula is as follows:
500th circulation volume conservation rate (%)=(the 500th cyclic discharge capacity/first time cyclic discharge capacity) × 100%;
3) high-temperature storage performance: the battery after changing into is charged to 4.35V with 1C constant current constant voltage at normal temperatures, measures battery initial discharge capacity, after then storing 30 days at 60 DEG C, is discharged to 3.0V with 1C, measures the maintenance capacity of battery and recovers capacity.Computing formula is as follows:
Battery capacity conservation rate (%)=maintenance capacity/initial capacity × 100%;
Capacity resuming rate (%)=recovery capacity/initial capacity × 100%.
4) low temperature performance test: at 25 DEG C, the battery 1C constant current constant voltage after changing into is charged to 4.35V, then uses 1C constant-current discharge to 3.0V, record discharge capacity.Then 1C constant current constant voltage is full of, after the environment being placed in-20 DEG C shelves 12h, 1C constant-current discharge to 3.0V, record discharge capacity.
Low temperature discharging efficiency value=1C discharge capacity (-20 DEG C)/1C discharge capacity (25 DEG C) of-20 DEG C.
5) normal low temperature direct impedance (DCIR) performance test: at 25 DEG C, the battery 1C after changing into is charged to half electricity condition, uses 0.1C respectively, 0.2C, 0.5C, 1C and 2C charge and discharge ten seconds, record discharge and recharge cut-ff voltage respectively; At the battery of half electricity condition is placed in-10 DEG C, use 0.1C respectively, 0.2C and 0.5C charge and discharge ten seconds, record discharge and recharge cut-ff voltage respectively.Then, with the charging and discharging currents of different multiplying for abscissa (unit: A), with the cut-ff voltage corresponding to charging and discharging currents for ordinate, linear relationship chart (unit: mV) is done.
The slope value of the linear graph of charging DCIR value=different charging current and corresponding cut-ff voltage.
The slope value of the linear graph of electric discharge DCIR value=different discharging current and corresponding cut-ff voltage.
Embodiment 1-16
In embodiment 1-16, except additive composition, content (based on electrolyte total weight) are by except table 1 Suo Shi, other is all identical with embodiment 1.Table 1 is that each composition of electrolyte is containing scale.
Table 1
| Embodiment | Tricresyl phosphate propynyl ester | Sulfolane | Ring penta sulfone | Dimethyl sulfone |
| Embodiment 1 | 0.1％ | 0.1％ | ||
| Embodiment 2 | 0.5％ | 1％ | ||
| Embodiment 3 | 3％ | 10％ | ||
| Embodiment 4 | 5％ | 30％ | ||
| Embodiment 5 | 0.1％ | 0.1％ | ||
| Embodiment 6 | 0.5％ | 1％ | ||
| Embodiment 7 | 3％ | 10％ | ||
| Embodiment 8 | 5％ | 30％ |
| Embodiment 9 | 0.1％ | 0.1％ | ||
| Embodiment 10 | 0.5％ | 1％ | ||
| Embodiment 11 | 3％ | 10％ | ||
| Embodiment 12 | 5％ | 30％ | ||
| Embodiment 13 | 1％ | 1％ | 1％ | |
| Embodiment 14 | 1％ | 3％ | 3％ | |
| Embodiment 15 | 1％ | 1％ | 1％ | |
| Embodiment 16 | 1％ | 3％ | 3％ |
Comparative example 1-4
In comparative example 1-4, except additive composition and content (based on electrolyte total weight) are by except adding table 2 Suo Shi, other is all identical with embodiment 1.Table 2 is each constituent content table of electrolysis additive.
Table 2
The performance comparison of embodiment 1-16 and comparative example 1-4
Table 3 is the performance comparison table of embodiment 1-16 and comparative example 1-4.
Table 3
Contrasted by embodiment 1-16 and comparative example 1-4, can find that tricresyl phosphate propynyl ester and sulfone compound are when adding separately use, impedance performance is all comparatively large, and cryogenic property is poor, but high-temperature behavior all shows more excellent; When both combine interpolation use, impedance obtains improvement to a certain degree, and DCIR reduces, and the discharging efficiency under low temperature obtains obvious lifting, and high-temperature behavior and cycle performance are not also worsened; That is, after these two kinds of high temperature modification additive combinations use, while guarantee high-temperature behavior and cycle performance, DCIR and cryogenic property can be effectively improved, obtain excellent battery performance.
In sum, non-aqueous electrolyte for lithium ion cell provided by the invention has raising cryogenic property; And improve the high-temperature behavior of battery and the beneficial effect of cycle performance further.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every equivalents utilizing description of the present invention to do, or be directly or indirectly used in relevant technical field, be all in like manner included in scope of patent protection of the present invention.
Claims (10)
1. a non-aqueous electrolyte for lithium ion cell, comprise non-aqueous organic solvent, lithium salts and film for additive, described film for additive comprises the phosphate compounds containing three key, it is characterized in that, described film for additive also comprises sulfone compound, described sulfone compound comprises cyclic sulfones compounds and/or straight chain sulfone compound, the structural formula of described cyclic sulfones compounds as shown in the formula:
The structural formula of described straight chain sulfone compound as shown in the formula:
Wherein, R
1-R
4separately be selected from hydrogen atom, halogen or carbon number be 1 ?5 alkyl, A to be carbon number be 2 ?6 by hydrogen atom, halogen or carbon number be 1 ?3 the alkylidene that replaces of alkyl.
2. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, the structural formula of described cyclic sulfones compounds is one or both in following structural formula 1, structural formula 2
Wherein, R
5-R
19separately be selected from the alkyl that hydrogen atom, halogen or carbon number are 1 ~ 5.
3. non-aqueous electrolyte for lithium ion cell according to claim 1, it is characterized in that, described sulfone compound is sulfolane, 3-methyl sulfolane, 3,3, one or more in 4,4-tetrachloro sulfolane, ring penta sulfone and dimethyl sulfone, Methylethyl sulfone, diethyl sulfone.
4. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, the content of described cyclic sulfones compounds and/or straight chain sulfone compound is the 0.1%-10% of electrolyte total weight.
5. non-aqueous electrolyte for lithium ion cell according to claim 1, is characterized in that, described sulfone compound accounts for the ratio that the total weight of electrolyte and described phosphate compounds account for the total weight of electrolyte and is more than or equal to 0.2.
6. non-aqueous electrolyte for lithium ion cell according to claim 1, it is characterized in that, described non-aqueous organic solvent be selected from ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate one or more.
7. non-aqueous electrolyte for lithium ion cell according to claim 1, it is characterized in that, described lithium salts be selected from lithium hexafluoro phosphate, lithium perchlorate, LiBF4, two fluorine Lithium bis (oxalate) borate, two (trimethyl fluoride sulfonyl) imine lithium and two fluorine sulfimide lithium salts one or more.
8. a lithium ion battery, the barrier film comprising positive pole, negative pole and be placed between positive pole and negative pole, is characterized in that, also comprises the non-aqueous electrolyte for lithium ion cell described in any one of claim 1-5.
9. lithium ion battery according to claim 8, is characterized in that, described positive pole is selected from LiCoO
2, LiNiO
2, LiMn
2o
4, LiCo
1-ym
yo
2, LiNi
1-ym
yo
2, LiMn
2-ym
yo
4and LiNi
xco
ymn
zm
1-x-y-zo
2in one or more, wherein, M be selected from Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti one or more, and 0≤y≤1,0≤x≤1,0≤z≤1, x+y+z≤1.
10. lithium ion battery according to claim 8, is characterized in that, the charge cutoff voltage of described lithium ion battery is more than or equal to 4.35V.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510397735.7A CN105140561A (en) | 2015-07-08 | 2015-07-08 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| PCT/CN2015/089164 WO2017004885A1 (en) | 2015-07-08 | 2015-09-08 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN201910517222.3A CN110233292B (en) | 2015-07-08 | 2016-07-08 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN201610538401.1A CN106340672A (en) | 2015-07-08 | 2016-07-08 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| PCT/CN2016/113008 WO2018006563A1 (en) | 2015-07-08 | 2016-12-29 | Non-aqueous electrolyte solution for lithium-ion battery and lithium-ion battery |
Applications Claiming Priority (1)
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| CN113937252A (en) * | 2021-10-11 | 2022-01-14 | 西北工业大学 | Laser-assisted construction method for anode interface layer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110233292B (en) | 2021-02-12 |
| CN110233292A (en) | 2019-09-13 |
| WO2017004885A1 (en) | 2017-01-12 |
| WO2018006563A1 (en) | 2018-01-11 |
| CN106340672A (en) | 2017-01-18 |
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