CN101673852A - Electrolyte additive and electrolyte and lithium ion battery containing same - Google Patents
Electrolyte additive and electrolyte and lithium ion battery containing same Download PDFInfo
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- CN101673852A CN101673852A CN200810141897A CN200810141897A CN101673852A CN 101673852 A CN101673852 A CN 101673852A CN 200810141897 A CN200810141897 A CN 200810141897A CN 200810141897 A CN200810141897 A CN 200810141897A CN 101673852 A CN101673852 A CN 101673852A
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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
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- 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
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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
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Abstract
The invention provides an electrolyte additive. The additive is a pyridine compound with a special structure, and can improve comprehensive performance of the battery containing the electrolyte additive. The additive not only improves the safety performance of the battery, but also improves the high-rate discharge performance, cycle performance and high-temperature storage performance the batterycontaining the electrolyte additive.
Description
[technical field]
The present invention relates to a kind of electrolysis additive and contain the electrolyte and the lithium ion battery of this additive.
[background technology]
Along with fast development of information technology, portable electric appts is universal day by day, increases year by year for the demand of high-specific energy battery.Lithium ion battery has that operating voltage height, specific energy are big, in light weight, advantage such as have extended cycle life, be widely used in aspects such as video camera, mobile phone, notebook computer, portable surveying instrument, just progressively replaced the conventional batteries continuous expanded application field and the market share.Simultaneously because in recent years to the increase of green energy resource demand, the used for electric vehicle lithium ion battery also more and more is subjected to people's attention.
Yet the fail safe hidden danger that lithium ion battery exists is to use the matter of utmost importance of being concerned about always.The electrolyte of lithium ion battery employing at present generally is to use inflammable organic carbonate system, when battery under the abuse state (as thermal shock, overcharge, cross put, short circuit etc.) exothermic reaction may take place, the just on fire even blast of possibility causes dangerous accident when the temperature of battery is higher than predetermined temperature.
In order to improve lithium ion battery security, the most frequently used method is to add flame-retardant additive in electrolyte, the adding of flame-retardant additive can make inflammable organic electrolyte become difficult combustion or non-flammable electrolyte, reduce battery heat release value and self-heating rate, also increase simultaneously the stability of electrolyte self, avoid burning or the blast of battery under overheated condition.At present more about the research of flame-retardant additive, comprise compounds such as ester classes such as phosphorous, halogen or ethers, but these flame-retardant additives or have bigger viscosity, make the conductivity of electrolyte descend, thereby greatly reduce efficiency for charge-discharge, the multiplying power discharging property of battery, or have a strong impact on high temperature performance of battery etc.
Prior art has by adding the pyridine compounds and their shown in the formula II in the electrolyte of secondary cell, improves the cycle performance of battery, and wherein, R1-R5 is hydrogen atom or alkyl alkyl among the formula II.But this electrolyte does not solve the security performance of battery, and the multiplying power discharging characteristic of battery and high temperature storage performance still do not reach ideal situation.
Formula II
[summary of the invention]
The objective of the invention is to overcome the shortcoming that existing additive can not make the combination property of secondary cell be improved, a kind of electrolyte flame-retardant additive that improves the combination property of battery is provided, this additive can not only improve the security performance of battery, and the multiplying power discharging characteristic, cycle performance and the high temperature storage performance that contain the battery of this electrolysis additive all improve a lot.The present invention provides electrolyte and the lithium rechargeable battery that contains this additive simultaneously.
The additive that the invention provides a kind of electrolyte of lithium-ion secondary battery contains the pyridine compounds and their shown in the formula I:
Formula I
Wherein, R
1～R
5Independently be selected from halogen atom, nitro, cyano group separately, contain the ester group of 1-20 carbon atom or contain halogen atom the ester group that contains 1-20 carbon atom, contain the alkoxyl of 1-20 carbon atom or contain halogen atom the alkoxyl that contains 1-20 carbon atom, contain the alkyl of 1-20 carbon atom or contain halogen atom the alkyl that contains 1-20 carbon atom, contain the aryl of 6-30 carbon atom or contain in the aryl that contains 6-30 carbon atom of halogen atom any one; R
1～R
5In have at least one to be selected from halogen atom.
The present invention also provides a kind of electrolyte of lithium rechargeable battery, and this electrolyte contains solvent, electrolyte and additive, and wherein, described additive is an additive provided by the invention.
The present invention also provides a kind of lithium rechargeable battery, this battery comprises battery container, electrode group and electrolyte, and electrode group and electrolyte are sealed in the battery container, and the electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, wherein, described electrolyte is electrolyte provided by the invention.
Pyridine compounds and their provided by the present invention, because of containing halogen atom and nitrogen-atoms in its molecule, stop the chain reaction of hydroxyl free radical when burning thereby when being heated, can act synergistically, make the burning of organic electrolyte can't carry out or be difficult to carrying out, improve the security performance of lithium ion battery.Simultaneously, it is right that the nitrogen-atoms of pyridine compounds and their provided by the invention has lone pair electrons, can form compound with anion, can not only increase the conductivity of electrolyte, can also increase the transport number of lithium ion, thereby improved the multiplying power discharging property of battery, the cycle performance and the high-temperature shelf property of battery that contains this compounds electrolyte simultaneously is better.
Therefore, adopt additive provided by the invention to make security performance, multiplying power discharging property, cycle performance and the high temperature storage performance of battery all obtain very big raising of arriving, the combination property of battery is improved.
[embodiment]
The objective of the invention is to overcome the shortcoming that existing additive can not make the combination property of secondary cell be improved, a kind of electrolyte flame-retardant additive that improves the combination property of battery is provided, this additive can not only improve the security performance of battery, and the multiplying power discharging characteristic, cycle performance and the high temperature storage performance that contain the battery of this electrolysis additive all improve a lot.
The invention provides a kind of additive of electrolyte of lithium-ion secondary battery, contain the pyridine compounds and their shown in the formula I:
Formula I
Wherein, R
1～R
5Independently be selected from halogen atom, nitro, cyano group separately, contain the ester group of 1-20 carbon atom or contain halogen atom the ester group that contains 1-20 carbon atom, contain the alkoxyl of 1-20 carbon atom or contain halogen atom the alkoxyl that contains 1-20 carbon atom, contain the alkyl of 1-20 carbon atom or contain halogen atom the alkyl that contains 1-20 carbon atom, contain the aryl of 6-30 carbon atom or contain in the aryl that contains 6-30 carbon atom of halogen atom any one.The preferred R of the present invention
1～R
5In have at least one to be selected from halogen atom, with the nitrogen-atoms in the molecule, stop the chain reaction of hydroxyl free radical when burning thereby when being heated, can act synergistically, make the burning of organic electrolyte can't carry out or be difficult to carrying out, improve the security performance of lithium ion battery.
Wherein, alkyl preferably contains the alkyl of 1-6 carbon atom, further preferably contains the alkyl of 1-3 carbon atom.Preferable methyl of the present invention, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, cyclopenta, n-hexyl, cyclohexyl etc.Wherein, aryl is meant the aromatic group that contains 6-30 carbon atom that comprises at least one phenyl ring, for example, phenyl, naphthyl, indenyl, perylene base or xenyl etc. can have 1～5 substituting group that is selected from hydroxyl, halogen, haloalkyl, nitro, cyano group, alkoxyl etc.
Quality with electrolyte is a benchmark, and the quality percentage composition of preferable additives of the present invention is 0.1-30%, more preferably 5-20%.
The present invention provides the electrolyte that contains this additive simultaneously, and this electrolyte contains solvent, electrolyte and above-mentioned additive.
Quality with electrolyte is a benchmark, and the quality percentage composition of preferable additives of the present invention is 0.1-30%, more preferably 5-20%.
According to electrolyte provided by the invention, electrolyte can use the electrolyte of any routine well known by persons skilled in the art, can be selected from lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4), di-oxalate lithium borate (LiBOB), trifluoromethyl sulfonic acid lithium (LiCF
3SO
3), perfluoro butyl sulfonic acid lithium (LiC
4F
9SO
3), fluoro sulfimide lithium (LiN (C
xF
2x+1SO
2) (C
yF
2y+1SO
2) (x and y are positive integer in the formula)), and lithium iodide (LiI) in one or more.The concentration of general lithium salts is the 0.5-2.0 mol, is preferably the 0.7-1.6 mol.When the concentration of lithium salts during less than 0.5 mol, the conductivity of electrolyte descends because of lithium-ion-conducting is not enough.When the concentration of lithium salts during greater than 2.0 mol, the animal migration of lithium ion reduces because of the increase of electrolyte viscosity.
According to electrolyte provided by the invention, solvent can use the solvent of any routine well known by persons skilled in the art, for example adopt gamma-butyrolacton (GBL), vinyl carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), vinylene carbonate (VC), methyl ethyl carbonate (EMC), dipropyl carbonate (DPC), carbonic acid first propyl ester (MPC), propylene carbonate (PC), methyl formate (MF), methyl acrylate (MA), methyl butyrate (MB) ethyl acetate (EP), ethylene sulfite (ES), propylene sulfite (PS), methyl sulfide (DMS), diethyl sulfite (DES), oxolane, acid anhydrides, the N-methyl pyrrolidone, the N-methylformamide, the N-methylacetamide, acetonitrile, N, dinethylformamide, sulfolane, methyl-sulfoxide, dimethyl sulfite and other are fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more.There is no particular limitation for the ratio of all kinds of solvents, can arbitrarily adjust collocation as required, for example the weight proportion of two kinds of solvents is 1: 0.9-3.2, the weight proportion of three kinds of solvents are 1: 1-1.5: 0.2-1.5, the weight proportion of four kinds of solvents are 1: 1-1.7: 0.1-1.2: 0.2-0.9.The present invention is in order to increase the solubility of lithium salts in solvent, preferred two or three mixed solvent.
The present invention also can contain other additives simultaneously, the present invention preferably adds SEI film film for additive, and the present invention finds that unexpectedly the adding of common film for additive can further improve the performance of batteries such as the battery capacity of battery after having added above-mentioned fire retardant, multiplying power, circulation.
Quality with electrolyte is a benchmark, the preferred SEI film of the present invention film for additive 0.1-11 weight %, more preferably 1-8%.
Wherein, film for additive is selected from and well known to a person skilled in the art film for additive, can be selected from carbon dioxide, carbon disulfide, sulfur dioxide, vinylene carbonate (VC), ethylene sulfite (ES), propylene sulfite (PS), the lithium carbonate etc. one or more.
Wherein, the preparation method of electrolyte is: nonaqueous solvents, electrolyte and additive are mixed, and the mode of mixing and order are not limit, and all can not influence the performance of electrolyte.
Lithium rechargeable battery provided by the invention, comprise battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in the battery container, and the electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, wherein, described electrolyte is electrolyte provided by the invention.
Wherein, the structure of electrode group is conventionally known to one of skill in the art, and in general, the electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, and barrier film is between positive pole and negative pole.Coiling or stacked mode are conventionally known to one of skill in the art.
Wherein, anodal consisting of is conventionally known to one of skill in the art, and in general, positive pole comprises collector and coating and/or is filled in positive electrode on the collector.Collector is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil, nickel plated steel strip or Punching steel strip.Positive electrode active materials is conventionally known to one of skill in the art, and it comprises positive active material and binding agent, and positive active material can be selected from the positive active material of lithium ion battery routine.As Li
xNi
1-yCoO
2(0.9≤x≤1.1,0≤y≤1.0), Li
mMn
2-nA
nO
2(A is a transition metal, 0.9≤m≤1.1,0≤n≤1.0), Li
1+aM
bMn
2-bO
4(0.1≤a≤0.2,0≤b≤1.0, M is one or more in the elements such as lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, sulphur), LiFe
1-x-yM
xN
yPO
4(0.001≤x, y≤0.1, M, N are one or more in the elements such as magnesium, strontium, aluminium, tin, antimony, vanadium, yttrium, titanium).
Wherein, anodal kind and content with binding agent is conventionally known to one of skill in the art.The preferred hydrophobicity adhesive of the present invention mixes with hydrophilic adhesive.The ratio of hydrophobicity adhesive and hydrophilic adhesive has no particular limits, and can determine according to actual needs, and for example, the part by weight of hydrophilic adhesive and hydrophobicity adhesive can be 0.3: 1-1: 1.Adhesive can use with the aqueous solution or emulsion form, also can use with solid form, preferably use with the aqueous solution or emulsion form, have no particular limits the concentration of described hydrophilic adhesive solution and the concentration of described hydrophobicity adhesive agent emulsion this moment, the viscosity that can be coated with according to the slurry of positive pole that will prepare and cathode size and the requirement of operability are adjusted flexibly to this concentration, the concentration of for example described hydrophilic adhesive solution can be 0.5-4wt%, and the concentration of described hydrophobicity adhesive agent emulsion can be 10-80wt%.Described hydrophobicity adhesive can be polytetrafluoroethylene, butadiene-styrene rubber or their mixture.Described hydrophilic adhesive can be hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol or their mixture.The content of described adhesive is the 0.01-8wt% of positive active material, is preferably 1-5wt%.
Wherein, positive electrode can also optionally contain conductive agent, and conductive agent is used to increase the conductivity of electrode, reduces the internal resistance of battery, and the kind of conductive agent and content are conventionally known to one of skill in the art.The present invention preferably contains conductive agent and is selected from conductive carbon black, acetylene black, nickel powder, copper powder and the electrically conductive graphite one or more, is benchmark with the positive electrode, and the content of conductive agent is generally 0-15wt%, is preferably 0-10wt%.
Wherein, negative pole adopts known negative pole in this area, promptly contains negative current collector and the negative electrode material layer that is coated on this negative current collector.Anticathode material layer of the present invention has no particular limits, and is the same with prior art, and negative electrode material layer generally includes the conductive agent that negative electrode active material, binding agent and selectivity contain.Negative electrode active material can adopt various negative electrode active materials commonly used in the prior art, for example material with carbon element.Material with carbon element can be non-graphitized charcoal, graphite or the charcoal that obtained by high-temperature oxydation by polyyne family macromolecule material, also can use other material with carbon element for example pyrolytic carbon, coke, organic polymer sinter, active carbon etc.The organic polymer sinter can be by the product with gained after sintering such as phenolic resins, epoxy resin and the charing.
Negative material provided by the invention can also optionally contain the common conductive agent that contains in the prior art negative material.Because conductive agent is used to increase the conductivity of electrode, reduce the internal resistance of battery, so the present invention preferably contains conductive agent.The content of described conductive agent and kind are conventionally known to one of skill in the art, for example, are benchmark with the negative material, and the content of conductive agent is generally 0.1-12 weight %.Described conductive agent can be selected from one or more in conductive carbon black, nickel powder, the copper powder.
Wherein, adhesive can be selected from the binding agent of lithium ion battery routine, as in polyvinyl alcohol, polytetrafluoroethylene, CMC (CMC), the butadiene-styrene rubber (SBR) one or more.In general, the content of binding agent is the 0.5-8 weight % of negative electrode active material, is preferably 2-5 weight %.
The solvent that the present invention is used for positive electrode and negative material can be selected from the conventional solvent that uses in this area, as being selected from N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N, one or more in N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can be coated on the described collector described slurry and gets final product.In general, the consumption of solvent is that to make the concentration of positive active material in the slurries be 40-90 weight %, is preferably 50-85 weight %.
Preparation method anodal and negative pole can adopt the whole bag of tricks known in the field.
According to lithium rechargeable battery provided by the invention, membrane layer is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy, and is sealed in the battery container with positive pole, negative pole and electrolyte.Described membrane layer can be selected from and well known to a person skilled in the art various membrane layers used in the lithium rechargeable battery, and for example polyolefin micro porous polyolefin membrane, modified polypropene felt, polyethylene felt, glass mat, ultra-fine fibre glass paper vinylon felt or nylon felt and wettability microporous polyolefin film are through welding or the bonding composite membrane that forms.
According to lithium ion battery provided by the invention, the preparation method of this battery comprises and will between positive pole and the negative pole barrier film be set, and constitutes the electrode group, this electrode group is contained in the battery container, injects electrolyte, then that battery container is airtight, wherein, described electrolyte is electrolyte provided by the invention.Except described electrolyte prepared according to method provided by the invention, other step was conventionally known to one of skill in the art.
The present invention is described further for the following examples, but can not be interpreted as it is qualification to protection range of the present invention.By the description of these instantiations, those skilled in the art can more be expressly understood the advantage of compositions of additives of the present invention.
Embodiment 1:
1, the preparation of electrolyte
60 gram vinyl carbonic esters (EC), 30 gram Methylethyl carbonic esters (EMC) and 60 gram diethyl carbonate (DMC) are mixed into mixed solvent; In this mixed solvent, add 19.54 gram LiPF
6Electrolyte. the concentration of LiPF6 is 1ML in this electrolyte
-1, to wherein adding film for additive vinylene carbonate (VC) 2.54 gram (1.5wt%) and flame-retardant additives 3,5-dichloropyridine 8.6 grams (5%) are stirred to all solids material and all dissolve, and make organic electrolyte then.
3, the 5-dichloropyridine
2, Zheng Ji preparation
90 gram polyvinylidene fluoride are dissolved in 1350 gram N-N-methyl-2-2-pyrrolidone N-(NMP) solvents make adhesive solution, in gained solution, add 2820 gram LiCoO then
2With 90 gram acetylene blacks, fully mix and make anode sizing agent, this anode sizing agent is uniformly applied on 20 microns the aluminium foil, through 125 ℃ of dryings 1 hour, obtain about 450 * 44 * 0.125 millimeter positive plate after rolling, cutting, contain 8.10 gram LiCoO on the positive plate
2
3, the preparation of negative pole
30 gram CMC CMC and 75 gram butadiene-styrene rubber (SBR) latex are dissolved in the 1875 gram water, make adhesive solution, 1395 gram graphite are joined in this adhesive solution, mix and make the graphite cathode slurry, this cathode size is coated on equably on the Copper Foil of 12 micron thickness and through 125 ℃ of dryings 1 hour, obtain about 448 * 44 * 0.125 millimeter negative plate after rolling, cutting, contain 4.55 gram graphite on the negative plate.
4, the preparation of battery
The polypropylene diaphragm of above-mentioned positive and negative plate and 20 micron thickness is wound into the electrode group of rectangular lithium ion battery, and this electrode is assembled in 5 millimeters * 34 millimeters * 50 millimeters the rectangular cell aluminum hull, subsequently the prepared electrolyte in front is injected in the battery case for 3.2 milliliters, sealing, make 053450A type lithium rechargeable battery, design capacity is 900 Milliampere Hours.
Embodiment 2:
Prepare electrolyte according to the method identical with embodiment 1, different is that described flame-retardant additive is a 3-bromo-5-methoxypyridine, and the amount of 3-bromo-5-methoxypyridine is 17.2 grams (10%)
3-bromo-5-methoxypyridine
Embodiment 3:
Prepare electrolyte according to the method identical with embodiment 1, different is that described flame-retardant additive is a 2-chloro-5-PMC, and the amount of 2-chloro-5-PMC is 34.4 grams (20%)
2-chloro-5-PMC
Embodiment 4:
Prepare electrolyte according to the method identical with embodiment 1, different is that described flame-retardant additive is a 3-chloro-2,4,5, the 6-ptfe pyridine, and 3-chloro-2,4,5, the amount of 6-ptfe pyridine is 51.6 grams (30%).
3-chloro-2,4,5, the 6-ptfe pyridine
Embodiment 5:
Prepare electrolyte according to the method identical with embodiment 1, different is that described flame-retardant additive is 2-phenyl-5-bromopyridine, and the amount of 2-phenyl-5-bromopyridine is 8.6 grams (5%).
2-phenyl-5-bromopyridine
Embodiment 6:
Prepare electrolyte according to the method identical with embodiment 1, the amount of different is described flame-retardant additive is 60.2 grams (35%).
Embodiment 7:
Prepare electrolyte according to the method identical with embodiment 1, different is not add film for additive vinylene carbonate (VC).
Comparative example 1:
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is that described flame-retardant additive is 1, the 3-dichloro-benzenes, and 1, the 3-dichloro-benzenes is 8.6 grams (5%).
1, the 3-dichloro-benzenes
Comparative example 2:
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is that described flame-retardant additive is a triethyl phosphate, and triethyl phosphate is 17.2 grams (10%).
Comparative example 3:
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is that additive is that film for additive vinylene carbonate (VC) 2.54 gram (1.5wt%) and 2-methyl-5-ethylpyridine 8.6 restrains (5%).
2-methyl-5-ethylpyridine
Performance test:
1, electrolyte flash-point
The employing agar diffusion method of remaining silent is measured the flash-point of embodiment 1-7 and comparative example 1-3 prepared electrolyte, and used instrument is the SBS-06 type flash point tester that the tall and sturdy Science and Technology Ltd. in east, Jilin Province produces.Each sample measurement is averaged for three times, and the result who records is as shown in table 1.
2, the test of self-extinguishing time
Reference literature J.Electrochem.Soc., 2002,149 (5), A622-A626.With the mineral wool is that raw material is made the glass cotton balls that diameter is 0.3-0.5cm, claims that its weight is m
1, then the glass cotton balls is placed in the electrolyte to be measured and fully soaks, take out and be weighed as m
2, the difference of the quality of glass cotton balls is the quality of cotton balls institute Electolyte-absorptive before and after soaking.This glass cotton balls is placed in front end to be converted on the thin wire of " O " type and with the gas igniter it to be lighted a fire, the record igniter is removed the time T that extinguish automatically to flame afterwards the back, and this time is called as self-extinguishing time SET (Self-extinguishing time).Obvious because cotton balls size and infiltration degree etc. can make cotton balls institute Electolyte-absorptive quality difference, thus cause self-extinguishing time to compare.And if be standard with the self-extinguishing time T ' of unit mass electrolyte, can compare the fire resistance of different electrolytes fire retardant.The computing formula of T ' is as follows:
T’＝T/(m
2-m
1)
All self-extinguishing times all are meant the self-extinguishing time T ' of unit mass electrolyte among the present invention.Each sample in measurement is averaged for three times, and the result who records is as shown in table 1.
Table 1
| Flash-point (℃) | Self-extinguishing time (s/g) | |
| Embodiment 1 | ??41 | ??24 |
| Embodiment 2 | ??42 | ??21 |
| Embodiment 3 | ??44 | ??19 |
| Embodiment 4 | ??46 | ??15 |
| Embodiment 5 | ??41 | ??27 |
| Embodiment 6 | ??45 | ??20 |
| Embodiment 7 | ??41 | ??26 |
| Comparative example 1 | ??35 | ??45 |
| Comparative example 2 | ??40 | ??33 |
| Comparative example 3 | ??34 | ??42 |
From table 1 test result as can be known, electrolyte embodiment 1-7 flash-point of the present invention is higher than the electrolyte of comparative example 1-3; Self-extinguishing time is lower than the electrolyte of comparative example 1-3, thereby electrolyte of the present invention as can be seen has very high fail safe, and the security performance that contains the battery of this electrolyte can be greatly improved.
2, battery overcharges experiment
The lithium ion battery of the foregoing description 1-7 and Comparative Examples 1-3 gained is respectively got 50,, be limited to 4.2V in the charging, battery is crossed with 1C be charged to 5V then, detect the state of battery with 1C constant-current constant-voltage charging 2.5 hours.
The result is as shown in table 2, and wherein test back battery swell (expansion rate＞20%), leakage do not occur, smolders, on fire, fracture phenomena is qualified.
Table 2
| Battery | Test result |
| Embodiment 1 | All qualified |
| Experimental example 2 | All qualified |
| Experimental example 3 | All qualified |
| Experimental example 4 | All qualified |
| Experimental example 5 | All qualified |
| Experimental example 6 | All qualified |
| Experimental example 7 | All qualified |
| Comparative example 1 | 6/10 is qualified, 2/10 swell, and 2/10 smolders |
| Comparative example 2 | 8/10 is complete, 1/10 swell, and 1/10 smolders |
| Comparative example 3 | 5/10 is qualified, 3/10 swell, and 2/10 smolders |
From the test result of table 2 as can be known, battery embodiment 1-7 of the present invention cross with 1C in full electricity back be charged to do not occur swell under the 5V situation, smolder, the phenomenon of on fire, blast, security performance is good; And a plurality of battery swells, some battery even the phenomenon that taken place to smolder have all appearred in the battery of the electrolyte of the pyridine additive that replaces with the battery of the Comparative Examples 1-2 of the electrolyte of other flame-retardant additives with alkyl under the situation of overcharging equally, the fail safe of battery is relatively poor, obviously has potential safety hazard.
4, multiplying power discharging volume test
Lithium ion battery (30 batteries of every kind of condition are got its mean value) 1C (900mA) constant voltage charge of the foregoing description 1-7 and comparative example 1-3 gained was shelved 10 minutes to 4.2V, be discharged to 3.0V with 5C (4500mA) then; Respectively with 4C (3600mA), 3C (2700mA), 2C (1800mA), 1C (900mA), 0.5C (450mA), 0.2C (180mA) constant-current discharge to by voltage 3.0V.Write down discharge capacity, compare the discharging efficiency that obtains the different multiplying discharge with the 0.2C capacity.The result is as shown in table 3:
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | |
| ??5C | ??72.4 | ??69.1 | ??65.8 | ??63.1 | ??61.4 | ??60.1 | ??59.8 | ??50.2 | ??51.7 | ??51.3 |
| ??4C | ??84.5 | ??82.3 | ??77.9 | ??74.5 | ??73.5 | ??71.6 | ??70.4 | ??63.1 | ??65.9 | ??65.4 |
| ??3C | ??89.3 | ??87.9 | ??82.5 | ??81.4 | ??80.9 | ??78.8 | ??77.1 | ??70.3 | ??74.3 | ??74.1 |
| ??2C | ??93.5 | ??92.6 | ??89.7 | ??88.9 | ??88.2 | ??86.5 | ??85.8 | ??84.9 | ??85.6 | ??85.2 |
| ??1C | ??98.1 | ??97.5 | ??95.6 | ??94.7 | ??94.4 | ??94.3 | ??93.6 | ??91.8 | ??93.4 | ??92.0 |
| ??0.5C | ??99.8 | ??99.3 | ??98.8 | ??98.2 | ??97.8 | ??97.5 | ??96.9 | ??96.2 | ??96.5 | ??96.3 |
| ??0.2C | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 |
As can be seen from Table 3, the multiplying power discharging characteristic of battery embodiment 1-7 of the present invention is better than the battery multiplying power discharging characteristic of Comparative Examples 1-3, even especially experimental example 1-2 battery is with the 5C heavy-current discharge, when its discharge capacity still can maintain 0.2C more than 65%, and the discharge capacity sustainment rate of the battery of comparative example 1-3 under different multiplying is all low slightly, and therefore battery of the present invention has good multiplying power discharging characteristic.
5, cycle performance test
The lithium ion battery of the foregoing description 1-7 and comparative example 1-3 gained is carried out the cycle performance test.Method of testing is: with battery with the 1C constant-current constant-voltage charging to 4.2V, shelved 5 minutes, be discharged to 3.0V with 1C, the gained capacity is designated as initial capacity.Repeat above step 500 time, obtain the capacity that 500 circulation backs of battery 1C is discharged to 3.0V, be designated as residual capacity.Capacity surplus ratio after the computation cycles.The result is as shown in table 4.
Table 4
As known from Table 4, battery experimental example 1-7 of the present invention is obviously higher than the circulation surplus ratio of the battery of Comparative Examples 1-3 at the capacity surplus ratio of circulation after 500 times, and the capacity surplus ratio can remain on more than 80%, the cycle performance of battery be improved significantly.
6, high-temperature storage stability test
The battery of embodiment 1-7 and comparative example 1-3 is carried out high-temperature storage stability can be tested.Method of testing is as follows: the battery after will changing into uses the 1C constant current charge to 4.2V, with the 4.2V constant voltage charge, and charging initial current 100mA, charging cut-off current 20mA.Be discharged to 3.0V with 1C then, measure the initial capacity that obtains battery discharge.And then with the 1C constant current charge to 4.2V; With the 4.2V constant voltage charge, charging initial current 100mA, charging cut-off current 20mA.After charging is finished, cooled off 30 minutes, measure cell thickness, internal resistance, voltage; The baking box that battery is put into 85 ℃ was deposited 48 hours; Take out battery and put normal temperature after 60 minutes, measure cell thickness, internal resistance, voltage; Battery is discharged to 3.0V with 1C, measures the storage capacity that obtains battery discharge.Use the 1C constant current charge to 4.2V on battery again; Be discharged to 3.0V with 1C then, above-mentioned charge and discharge process 3 times is repeatedly measured last discharge process, the recovery capacity of the battery discharge that obtains.And then with battery with the 1C constant current charge to 4.2V; Take off battery normal temperature and place after 60 minutes, the recovery internal resistance of test battery, recovery thickness.Press following formula calculated capacity recovery rate and internal resistance rate of change:
Capacity restoration rate=recovery capacity/initial capacity * 100%
Internal resistance rate of change=recovery internal resistance increase/initial internal resistance * 100%
Gained the results are shown in Table 5:
Table 5
As can be seen from Table 5, the battery of experimental example 1-7 is compared with the battery of comparative example 1-3 under 85 ℃ high temperature, has all better suppressed the rising of the internal resistance of cell and thickness, has improved the capacity restoration rate of battery simultaneously.Illustrate that containing battery high-temperature storge quality of the present invention is significantly improved.
Therefore, adopt flame-retardant additive provided by the invention that security performance, high rate performance, cycle performance and the high-temperature storage performance of battery all are greatly improved, the combination property of battery is improved.
Claims (10)
1, a kind of electrolysis additive of lithium rechargeable battery is characterized in that, described additive contains the pyridine compounds and their shown in the formula I:
Formula I
Wherein, R
1～R
5Independently be selected from halogen atom, nitro, cyano group separately, contain the ester group of 1-20 carbon atom or contain halogen atom the ester group that contains 1-20 carbon atom, contain the alkoxyl of 1-20 carbon atom or contain halogen atom the alkoxyl that contains 1-20 carbon atom, contain the alkyl of 1-20 carbon atom or contain halogen atom the alkyl that contains 1-20 carbon atom, contain the aryl of 6-30 carbon atom or contain in the aryl that contains 6-30 carbon atom of halogen atom any one; Described R
1～R
5In have at least one to be selected from halogen atom.
2, additive according to claim 1 is characterized in that, described halogen atom is selected from chlorine atom, fluorine atom, bromine atoms.
3, additive according to claim 1 is characterized in that, is benchmark with the quality of electrolyte, and the quality percentage composition of described additive is 0.1-30%.
4, according to claim 1 or 3 described additives, it is characterized in that, is benchmark with the quality of electrolyte, and the quality percentage composition of described additive is 5-20%.
5, a kind of electrolyte of lithium rechargeable battery, this electrolyte contains solvent, electrolyte and additive, it is characterized in that, and described additive comprises any described additive of claim 1-4.
6, electrolyte according to claim 5, it is characterized in that, described solvent is selected from gamma-butyrolacton, vinylene carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, dipropyl carbonate, vinyl carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, methyl formate, methyl acrylate, methyl butyrate, ethyl acetate, acid anhydrides, the N-methyl pyrrolidone, the N-methylformamide, the N-methylacetamide, acetonitrile, N, dinethylformamide, sulfolane, methyl-sulfoxide, the ethene sulfite, the propylene sulfite, methyl sulfide, the diethyl sulfite, dimethyl sulfite, oxolane, fluorine-containing ring-type organic ester, sulphur-containing cyclic organic ester and contain in the unsaturated bond ring-type organic ester one or more.
7, electrolyte according to claim 5 is characterized in that, described electrolyte is selected from LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiSiF
6, LiB (C
6H
5)
4, LiCl, LiBr, LiAlCl
4, LiBOB, LiCF
3SO
3, LiC
4F
9SO
3, LiN (C
xF
2x+1SO
2) (C
yF
2y+1SO
2) and LiI in one or more, wherein, x and y are positive integer in the formula.
8, electrolyte according to claim 5, it is characterized in that, described additive also comprises film for additive, and described film for additive is selected from one or more in carbon dioxide, carbon disulfide, sulfur dioxide, vinylene carbonate, ethylene sulfite, propylene sulfite, the lithium carbonate.
9, electrolyte according to claim 8 is characterized in that, is benchmark with the quality of electrolyte, and the weight percentage of described film for additive is 0.1-11 weight %.
10, a kind of lithium rechargeable battery, this battery comprises battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in the battery container, the electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, it is characterized in that described electrolyte is any described electrolyte among the claim 5-9.
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