CN101673852B - Electrolyte additive and electrolyte and lithium ion battery containing same - Google Patents
Electrolyte additive and electrolyte and lithium ion battery containing same Download PDFInfo
- Publication number
- CN101673852B CN101673852B CN200810141897.4A CN200810141897A CN101673852B CN 101673852 B CN101673852 B CN 101673852B CN 200810141897 A CN200810141897 A CN 200810141897A CN 101673852 B CN101673852 B CN 101673852B
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- additive
- battery
- carbonate
- carbon atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 *c1c(*)c(*)nc(*)c1* Chemical compound *c1c(*)c(*)nc(*)c1* 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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 battery containing the electrolyte additive.
Description
[technical field]
The present invention relates to a kind of electrolysis additive and containing the electrolyte of this additive and lithium ion battery.
[background technology]
Along with the develop rapidly of information technology, portable electric appts is day by day universal, and the demand for high-specific energy battery increases year by year.Lithium ion battery has that operating voltage is high, specific energy is large, lightweight, the advantage such as have extended cycle life, be widely used in the aspects such as video camera, mobile phone, notebook computer, portable surveying instrument, just progressively replace the continuous expanded application field of conventional batteries and the market share.Simultaneously due in recent years to the increase of green energy resource demand, lithium ion battery used for electric vehicle is also more and more by the concern of people.
But the safety risks that lithium ion battery exists is the matter of utmost importance that application is concerned about always.The electrolyte that current lithium ion battery adopts is generally use inflammable organic carbonate system, when battery under abuse state (as thermal shock, overcharge, cross put, short circuit etc.) exothermic reaction may be there is, when the temperature of battery just may on firely even be exploded higher than during predetermined temperature, cause dangerous accident.
In order to improve lithium ion battery security, the most frequently used method adds flame-retardant additive in electrolyte, 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 the stability of electrolyte self simultaneously, avoid battery burning upon an over-temperature condition or blast.More about the research of flame-retardant additive at present, comprise the compounds such as ester class or ethers such as phosphorous, halogen, but these flame-retardant additives or there is larger viscosity, the conductivity of electrolyte is declined, thus greatly reduce efficiency for charge-discharge, the multiplying power discharging property of battery, or have a strong impact on the high temperature performance etc. of battery.
Prior art has by adding the pyridine compounds and their shown in formula II in the electrolyte of secondary cell, and improve the cycle performance of battery, wherein, in formula II, R1-R5 is hydrogen atom or alkyl alkyl.But this electrolyte does not solve the security performance of battery, and rate discharge characteristic and the high temperature storage performance of battery still do not reach ideal situation.
Formula II
[summary of the invention]
The object 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 improving the combination property of battery is provided, this additive can not only improve the security performance of battery, and the rate discharge characteristic of the battery containing this electrolysis additive, cycle performance and high temperature storage performance all improve a lot.The present invention provides electrolyte containing this additive and lithium rechargeable battery simultaneously.
The additive that the invention provides a kind of electrolyte of lithium-ion secondary battery contains the pyridine compounds and their shown in formula I:
Formula I
Wherein, R
1~ R
5independently be selected from separately halogen atom, nitro, cyano group, the ester group containing 1-20 carbon atom or the ester group containing 1-20 carbon atom containing halogen atom, the alkoxyl containing 1-20 carbon atom or the alkoxyl containing 1-20 carbon atom containing halogen atom, the alkyl containing 1-20 carbon atom or contain halogen atom the alkyl containing 1-20 carbon atom, containing 6-30 carbon atom aryl or contain halogen atom contain in the aryl of 6-30 carbon atom any one; R
1~ R
5in have at least one to be selected from halogen atom.
Present invention also offers a kind of electrolyte of lithium rechargeable battery, this electrolyte contains solvent, electrolyte and additive, and wherein, described additive is additive provided by the invention.
Present invention also offers a kind of lithium rechargeable battery, this battery battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in battery container, and electrode group comprises winding 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 containing halogen atom and nitrogen-atoms in its molecule, the chain reaction of hydroxyl free radical when can occur when being heated to act synergistically thus stop burning, the burning of organic electrolyte cannot be carried out or be difficult to carry out, improving the security performance of lithium ion battery.Simultaneously, the nitrogen-atoms of pyridine compounds and their provided by the invention has lone pair electrons pair, compound can be formed with anion, the conductivity of electrolyte can not only be increased, the transport number of lithium ion can also be increased, thus improve the multiplying power discharging property of battery, the cycle performance and the high-temperature shelf property that contain the battery of this compounds electrolyte better simultaneously.
Therefore, adopt additive provided by the invention to make the security performance of battery, multiplying power discharging property, cycle performance and high temperature storage performance all obtain the raising of arriving very greatly, the combination property of battery is improved.
[embodiment]
The object 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 improving the combination property of battery is provided, this additive can not only improve the security performance of battery, and the rate discharge characteristic of the battery containing this electrolysis additive, cycle performance and high temperature storage performance all improve a lot.
The invention provides a kind of additive of electrolyte of lithium-ion secondary battery, the pyridine compounds and their containing shown in formula I:
Formula I
Wherein, R
1~ R
5independently be selected from separately halogen atom, nitro, cyano group, the ester group containing 1-20 carbon atom or the ester group containing 1-20 carbon atom containing halogen atom, the alkoxyl containing 1-20 carbon atom or the alkoxyl containing 1-20 carbon atom containing halogen atom, the alkyl containing 1-20 carbon atom or contain halogen atom the alkyl containing 1-20 carbon atom, containing 6-30 carbon atom aryl or contain halogen atom contain in the aryl of 6-30 carbon 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 molecule, when can occur when being heated to act synergistically thus stop burning, the chain reaction of hydroxyl free radical, makes the burning of organic electrolyte carry out or is difficult to carry out, improving the security performance of lithium ion battery.
Wherein, the alkyl of alkyl preferably containing 1-6 carbon atom, the alkyl further preferably containing 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 refers to the aromatic group containing 6-30 carbon atom comprising at least one phenyl ring, such as, phenyl, naphthyl, indenyl, perylene base or xenyl etc., can have the substituting group that 1 ~ 5 is selected from hydroxyl, halogen, haloalkyl, nitro, cyano group, alkoxyl etc.
With the quality of electrolyte for benchmark, the mass percentage of preferable additives of the present invention is 0.1-30%, more preferably 5-20%.
Invention also provides the electrolyte containing this additive, this electrolyte contains solvent, electrolyte and above-mentioned additive.
With the quality of electrolyte for benchmark, the mass percentage 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), tetraphenylboronic acid lithium (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 Lithium (LiC
4f
9sO
3), fluoro sulfimide lithium (LiN (C
xf
2x+1sO
2) (C
yf
2y+1sO
2) (in formula, x and y is positive integer)) and lithium iodide (LiI) in one or more.The concentration of general lithium salts is 0.5-2.0 mol/L, is preferably 0.7-1.6 mol/L.When the concentration of lithium salts is less than 0.5 mol/L, the conductivity of electrolyte declines because lithium-ion-conducting is not enough.When the concentration of lithium salts is greater than 2.0 mol/L, 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, such as, adopt gamma-butyrolacton (GBL), vinyl carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), vinylene carbonate (VC), methyl ethyl carbonate (EMC), dipropyl carbonate (DPC), methyl propyl carbonate (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, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, DMF, sulfolane, methyl-sulfoxide, dimethyl sulfite and other is fluorine-containing, sulfur-bearing or containing unsaturated bond ring-type organosilane ester in one or more.There is no particular limitation for the ratio of various solvent, arbitrarily can adjust collocation as required, the weight proportion of such as two kinds of solvents is 1:0.9-3.2, and the weight proportion of three kinds of solvents is 1:1-1.5:0.2-1.5, and the weight proportion of four kinds of solvents is 1:1-1.7:0.1-1.2:0.2-0.9.The present invention in order to increase lithium salts solubility in a solvent, preferably 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 what the present invention found common film for additive unexpectedly adds the performance improving the batteries such as the battery capacity of battery after with the addition of above-mentioned fire retardant, multiplying power, circulation further.
With the quality of electrolyte for benchmark, the present invention's preferred SEI film film for additive 0.1-11 % by 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 one or more in carbon dioxide, carbon disulfide, sulfur dioxide, vinylene carbonate (VC), ethylene sulfite (ES), propylene sulfite (PS), lithium carbonate etc.
Wherein, the preparation method of electrolyte is: nonaqueous solvents, electrolyte and additive are mixed, and mode and the order of mixing are not limit, and all can not affect 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 battery container, and electrode group comprises winding 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, electrode group comprises winding or stacked positive pole, barrier film and negative pole successively, and barrier film is between positive pole and negative pole.Winding or stacked mode are conventionally known to one of skill in the art.
Wherein, consisting of of positive pole is conventionally known to one of skill in the art, in general, and the positive electrode that positive pole comprises collector and coating and/or fills on a current collector.Collector is conventionally known to one of skill in the art, such as, 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 transition metal, 0.9≤m≤1.1,0≤n≤1.0), Li
1+am
bmn
2-bo
4(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 for-0.1≤a≤0.2,0≤b≤1.0), 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, the kind of positive pole binding agent and content are conventionally known to one of skill in the art.The preferred hydrophobic adhesives of the present invention mixes with hydrophilic adhesive.The ratio of hydrophobic adhesives and hydrophilic adhesive has no particular limits, and can determine according to actual needs, and such as, the part by weight of hydrophilic adhesive and hydrophobic adhesives can be 0.3:1-1:1.Adhesive can use with the aqueous solution or emulsion form, also can use in solid form, preferably use with the aqueous solution or emulsion form, now the concentration of described hydrophilic binder agent solution and the concentration of described hydrophobic adhesives emulsion are had no particular limits, can adjust flexibly this concentration according to the viscosity of slurry coating of positive pole to be prepared and cathode size and the requirement of operability, the concentration of such as described hydrophilic binder agent solution can be 0.5-4wt%, and the concentration of described hydrophobic adhesives emulsion can be 10-80wt%.Described hydrophobic adhesives 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 optionally can also contain conductive agent, and conductive agent is for increasing the conductivity of electrode, and reduce the internal resistance of battery, the kind of conductive agent and content are conventionally known to one of skill in the art.The present invention is preferably selected from one or more in conductive carbon black, acetylene black, nickel powder, copper powder and electrically conductive graphite containing conductive agent, and take positive electrode as benchmark, the content of conductive agent is generally 0-15wt%, is preferably 0-10wt%.
Wherein, negative pole adopts negative pole known in this area, namely containing negative current collector and the negative electrode material layer be coated on this negative current collector.Anticathode material layer of the present invention has no particular limits, and like the prior art, 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 conventional in prior art, such as material with carbon element.Material with carbon element can be non-graphitic carbon, graphite or the charcoal that obtained by high-temperature oxydation by polyyne family macromolecule material, also can use other material with carbon element such as pyrolytic carbon, coke, organic polymer sinter, active carbon etc.Organic polymer sinter can be by phenolic resins, epoxy resin etc. being sintered and the product of gained after carbonizing.
Negative material provided by the invention can also optionally containing conductive agent usually contained in prior art negative material.Because conductive agent is for increasing the conductivity of electrode, reduce the internal resistance of battery, therefore the present invention is preferably containing conductive agent.The content of described conductive agent and kind are conventionally known to one of skill in the art, and such as, take negative material as benchmark, the content of conductive agent is generally 0.1-12 % by weight.Described conductive agent can be selected from one or more in conductive carbon black, nickel powder, copper powder.
Wherein, adhesive can be selected from the binding agent of lithium ion battery routine, as one or more in polyvinyl alcohol, polytetrafluoroethylene, CMC (CMC), butadiene-styrene rubber (SBR).In general, the content of binding agent is the 0.5-8 % by weight of negative electrode active material, is preferably 2-5 % by weight.
The solvent that the present invention is used for positive electrode and negative material can be selected from the conventional solvent used in this area, as 1-METHYLPYRROLIDONE (NMP), N can be selected from, one or more in dinethylformamide (DMF), N, N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF) and water and alcohols.The consumption of solvent enables described slurry be coated on described collector.In general, the consumption of solvent is make the concentration of positive active material in slurries be 40-90 % by weight, is preferably 50-85 % by weight.
The preparation method of positive pole and negative pole can adopt various method known in the field.
According to lithium rechargeable battery provided by the invention, membrane layer is arranged between positive pole and negative pole, has electrical insulation capability and liquid retainability energy, and seals in the cell housing together with electrolyte with positive pole, negative pole.Described membrane layer can be selected from and well known to a person skilled in the art various membrane layers used in lithium rechargeable battery, and such as 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 bonding composite membrane.
According to lithium ion battery provided by the invention, the preparation method of this battery comprises and arranges barrier film by between positive pole and negative pole, forms electrode group, this electrode group is held in the cell housing, injects electrolyte, then that battery container is airtight, wherein, described electrolyte is electrolyte provided by the invention.Except described electrolyte is according to except method preparation provided by the invention, other step is 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 limiting the scope of the present invention.By the description of these instantiations, those skilled in the art more clearly can understand the advantage of compositions of additives of the present invention.
Embodiment 1:
1, the preparation of electrolyte
60 grams of vinylcarbonates (EC), 30 grams of methyl ethyl carbonate (EMC) and 60 grams of diethyl carbonate (DMC) are mixed into mixed solvent; 19.54 grams of LiPF are added in this mixed solvent
6electrolyte. in this electrolyte, the concentration of LiPF6 is 1ML
-1then film for additive vinylene carbonate (VC) 2.54 grams (1.5wt%) and flame-retardant additive 3 is added wherein, 5-dichloropyridine 8.6 grams (5%), is stirred to all solids material and all dissolves, obtained organic electrolyte.
3,5-dichloropyridine
2, the preparation of positive pole
90 grams of polyvinylidene fluoride are dissolved in obtained adhesive solution in 1350 grams of METHYLPYRROLIDONE (NMP) solvents, then in gained solution, add 2820 grams of LiCoO
2with 90 grams of acetylene blacks, fully mix obtained anode sizing agent, this anode sizing agent is uniformly applied on the aluminium foil of 20 microns, through 125 DEG C of dryings 1 hour, calendering, cut after obtain the positive plate of about 450 × 44 × 0.125 millimeter, containing 8.10 grams of LiCoO on positive plate
2.
3, the preparation of negative pole
30 grams of CMC CMC and 75 gram butadiene-styrene rubber (SBR) latex are dissolved in 1875 grams of water, obtained adhesive solution, 1395 grams of graphite are joined in this adhesive solution, mix obtained graphite cathode slurry, on the Copper Foil this cathode size being coated on equably 12 micron thickness and through 125 DEG C of dryings 1 hour, calendering, cut after obtain the negative plate of about 448 × 44 × 0.125 millimeter, containing 4.55 grams of graphite on 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 assembling is entered in the rectangular cell aluminum hull of 5 millimeters × 34 millimeters × 50 millimeters, subsequently obtained electrolyte 3.2 milliliters is injected in battery case above, sealing, make 053450A type lithium rechargeable battery, design capacity is 900 Milliampere Hours.
Embodiment 2:
Preparing electrolyte according to the method identical with embodiment 1, is the bromo-5-methoxypyridine of 3-unlike described flame-retardant additive, and the amount of the bromo-5-methoxypyridine of 3-is 17.2 grams (10%)
The bromo-5-methoxypyridine of 3-
Embodiment 3:
Preparing electrolyte according to the method identical with embodiment 1, is CCMP unlike described flame-retardant additive, and the amount of CCMP is 34.4 grams (20%)
CCMP
Embodiment 4:
Preparing electrolyte according to the method identical with embodiment 1, is chloro-2,4,5, the 6-ptfe pyridines of 3-unlike described flame-retardant additive, and the amount of chloro-2,4,5, the 6-ptfe pyridines of 3-is 51.6 grams (30%).
Chloro-2,4,5, the 6-ptfe pyridines of 3-
Embodiment 5:
Preparing electrolyte according to the method identical with embodiment 1, is 2-phenyl-5-bromopyridine unlike described flame-retardant additive, 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 unlike described flame-retardant additive is 60.2 grams (35%).
Embodiment 7:
Electrolyte is prepared, unlike not adding film for additive vinylene carbonate (VC) according to the method identical with embodiment 1.
Comparative example 1:
Preparing electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, is 1,3-dichloro-benzenes unlike described flame-retardant additive, and 1,3-dichloro-benzenes is 8.6 grams (5%).
1,3-dichloro-benzenes
Comparative example 2:
Preparing electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, is triethyl phosphate unlike described flame-retardant additive, and triethyl phosphate is 17.2 grams (10%).
Comparative example 3:
Preparing electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, is film for additive vinylene carbonate (VC) 2.54 grams (1.5wt%) and 2-methyl-5-ethylpyridine 8.6 grams (5%) unlike additive.
2-methyl-5-ethylpyridine
Performance test:
1, electrolyte flash-point
Adopt agar diffusion method of remaining silent to measure the flash-point of embodiment 1-7 and the electrolyte prepared by comparative example 1-3, 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 recorded is as shown in table 1.
2, the test of self-extinguishing time
Reference literature J.Electrochem.Soc., 2002,149 (5), A622-A626.Take mineral wool as the glass cotton balls that raw material makes that diameter is 0.3-0.5cm, claim its weight to be m
1, then glass cotton balls is placed in electrolyte to be measured and fully soaks, take out and be weighed as m
2, before and after soaking, the difference of the quality of glass cotton balls is the quality of cotton balls institute Electolyte-absorptive.This glass cotton balls to be placed on thin wire that front end is converted into " O " type and to be lighted a fire by gas igniter, record igniter is afterwards to the time T of flame automatic distinguishing after removing, and this time is called as self-extinguishing time SET (Self-extinguishing time).Obviously because cotton balls size and infiltration degree etc. can make cotton balls institute Electolyte-absorptive quality different, thus self-extinguishing time is caused to compare.And if with the self-extinguishing time T ' of unit mass electrolyte for standard, the fire resistance of different electrolytes fire retardant can be compared.The computing formula of T ' is as follows:
T’＝T/(m
2-m
1)
Self-extinguishing times all in the present invention all refers to the self-extinguishing time T ' of unit mass electrolyte.Each sample is measured three times and is averaged, and the result recorded is as shown in table 1.
Table 1
| Flash-point (DEG C) | 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, electrolyte embodiment 1-7 flash-point of the present invention is higher than the electrolyte of comparative example 1-3; Self-extinguishing time lower than the electrolyte of comparative example 1-3, thus can find out that electrolyte of the present invention has very high fail safe, and the security performance of the battery containing this electrolyte can be greatly improved.
2, battery overcharge experiment
The lithium ion battery of above-described embodiment 1-7 and comparative example 1-3 gained is respectively got 50, and with 1C constant-current constant-voltage charging 2.5 hours, charging upper limit was 4.2V, then battery was crossed with 1C and was charged to 5V, detect the state of battery.
Result is as shown in table 2, and wherein after test, battery does not occur swell (expansion rate >20%), leakage, 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, and 2/10 swell, 2/10 smolders |
| Comparative example 2 | 8/10 is complete, and 1/10 swell, 1/10 smolders |
| Comparative example 3 | 5/10 is qualified, and 3/10 swell, 2/10 smolders |
From the test result of table 2, cell embodiments 1-7 of the present invention after full electricity with 1C cross be charged to 5V situation under there is not swell, smolder, the phenomenon of on fire, blast, security performance is good; And with the battery of the comparative example 1-2 of the electrolyte of other flame-retardant additives and the electrolyte of pyridine additive that replaces with alkyl all there is multiple battery swell in battery, some battery even there occurs smoke event in same overcharge situation, the fail safe of battery is poor, obviously there is potential safety hazard.
4, multiplying power discharging volume test
By lithium ion battery (often kind of condition 30 batteries of above-described embodiment 1-7 and comparative example 1-3 gained, get its mean value) 1C (900mA) constant voltage charge is to 4.2V, shelve 10 minutes, be then discharged to 3.0V with 5C (4500mA); Respectively with 4C (3600mA), 3C (2700mA), 2C (1800mA), 1C (900mA), 0.5C (450mA), 0.2C (180mA) constant-current discharge to by voltage 3.0V.Record discharge capacity, obtain the discharging efficiency that different multiplying discharges compared with 0.2C capacity.Result is as shown in table 3:
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 | Comparative example 2 | Comparative example 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 rate discharge characteristic of cell embodiments 1-7 of the present invention is better than the battery rate discharge characteristic of comparative example 1-3, even if especially experimental example 1-2 battery is with 5C heavy-current discharge, its discharge capacity still can maintain during 0.2C more than 65%, and the discharge capacity sustainment rate of the battery of comparative example 1-3 under different multiplying is all slightly low, therefore battery of the present invention has good rate discharge characteristic.
5, cycle performance test
The lithium ion battery of above-described embodiment 1-7 and comparative example 1-3 gained is carried out cycle performance test.Method of testing is: by battery with 1C constant-current constant-voltage charging to 4.2V, shelve 5 minutes, be discharged to 3.0V with 1C, gained capacity is designated as initial capacity.Repeat above step 500 time, after obtaining battery 500 circulations, 1C is discharged to the capacity of 3.0V, is designated as residual capacity.Capacity surplus ratio after computation cycles.Result is as shown in table 4.
Table 4
As known from Table 4, the capacity surplus ratio of Cell Experimentation An of the present invention example 1-7 after circulation 500 times is obviously higher than the circulation surplus ratio of the battery of comparative example 1-3, and capacity surplus ratio can remain on more than 80%, the cycle performance of battery be improved significantly.
6, high-temperature storage stability test
Carry out high-temperature storage stability to the battery of embodiment 1-7 and comparative example 1-3 can test.Method of testing is as follows: after the battery 1C constant current charge to 4.2V after changing into, with 4.2V constant voltage charge, charging initial current 100mA, charge cutoff electric current 20mA.Then be discharged to 3.0V with 1C, measure the initial capacity obtaining battery discharge.And then with 1C constant current charge to 4.2V; With 4.2V constant voltage charge, charging initial current 100mA, charge cutoff electric current 20mA.After charging complete, cool 30 minutes, measure cell thickness, internal resistance, voltage; Baking box battery being put into 85 DEG C deposits 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 obtaining battery discharge.Again by battery with 1C constant current charge to 4.2V; Then be discharged to 3.0V with 1C, above-mentioned charge and discharge process 3 times repeatedly, measures last discharge process, the recovery capacity of the battery discharge obtained.And then by battery with 1C constant current charge to 4.2V; Take off after battery normal temperature places 60 minutes, the recovery internal resistance of test battery, recover thickness.By following formulae discovery capacity restoration 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%
Acquired results is in table 5:
Table 5
As can be seen from Table 5, the battery of experimental example 1-7 compared with the battery of comparative example 1-3, all better inhibits the rising of the internal resistance of cell and thickness under the high temperature of 85 DEG C, improves 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 the security performance of battery, high rate performance, cycle performance and high-temperature storage performance are all greatly improved, the combination property of battery is improved.
Claims (10)
1. the pyridine compounds and their shown in formula I as the application of the electrolysis additive of lithium rechargeable battery,
Wherein, R
1~ R
5independently be selected from separately halogen atom, nitro, cyano group, the ester group containing 1-20 carbon atom or the ester group containing 1-20 carbon atom containing halogen atom, the alkoxyl containing 1-20 carbon atom or the alkoxyl containing 1-20 carbon atom containing halogen atom, the alkyl containing 1-20 carbon atom or contain halogen atom the alkyl containing 1-20 carbon atom, containing 6-30 carbon atom aryl or contain halogen atom contain in the aryl of 6-30 carbon atom any one; Described R
1~ R
5in have at least one to be selected from halogen atom.
2. the pyridine compounds and their shown in formula I according to claim 1 is as the application of the electrolysis additive of lithium rechargeable battery, it is characterized in that, described halogen atom is selected from chlorine atom, fluorine atom, bromine atoms.
3. the pyridine compounds and their shown in formula I according to claim 1 is as the application of the electrolysis additive of lithium rechargeable battery, it is characterized in that, with the quality of electrolyte for benchmark, the mass percentage of described additive is 0.1-30%.
4. the pyridine compounds and their shown in the formula I according to claim 1 or 3, as the application of the electrolysis additive of lithium rechargeable battery, is characterized in that, with the quality of electrolyte for benchmark, the mass percentage of described additive is 5-20%.
5. an electrolyte for lithium rechargeable battery, this electrolyte contains solvent, electrolyte and additive, it is characterized in that, described additive comprises the additive described in claim 1-4 any one.
6. electrolyte according to claim 5, it is characterized in that, described solvent is selected from gamma-butyrolacton, vinylene carbonate, methyl ethyl carbonate, methyl propyl carbonate, dipropyl carbonate, vinyl carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, methyl formate, methyl acrylate, methyl butyrate, ethyl acetate, acid anhydrides, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, N, dinethylformamide, sulfolane, methyl-sulfoxide, ethene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, dimethyl sulfite, oxolane, fluorine-containing ring-type organic ester, sulphur-containing cyclic organic ester and containing one or more in unsaturated bond ring-type organic ester.
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, in formula, x and y is positive integer.
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, lithium carbonate.
9. electrolyte according to claim 8, is characterized in that, with the quality of electrolyte for benchmark, the weight percentage of described film for additive is 0.1-11 % by weight.
10. a lithium rechargeable battery, this battery battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in battery container, electrode group comprises winding or stacked positive pole, barrier film and negative pole successively, it is characterized in that, described electrolyte is the electrolyte in claim 5-9 described in any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810141897.4A CN101673852B (en) | 2008-09-11 | 2008-09-11 | Electrolyte additive and electrolyte and lithium ion battery containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810141897.4A CN101673852B (en) | 2008-09-11 | 2008-09-11 | Electrolyte additive and electrolyte and lithium ion battery containing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101673852A CN101673852A (en) | 2010-03-17 |
| CN101673852B true CN101673852B (en) | 2015-01-14 |
Family
ID=42020930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810141897.4A Active CN101673852B (en) | 2008-09-11 | 2008-09-11 | Electrolyte additive and electrolyte and lithium ion battery containing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101673852B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104518239A (en) * | 2013-09-26 | 2015-04-15 | 中国科学院过程工程研究所 | Lithium ion battery amide-type additive having film-forming and stabilizing functions and electrolyte containing same |
| CN103746151A (en) * | 2013-12-07 | 2014-04-23 | 新余英泰能科技有限公司 | Method capable of enabling electronic cigarette battery to pass needling detection |
| WO2016159108A1 (en) * | 2015-03-31 | 2016-10-06 | 旭化成株式会社 | Nonaqueous electrolyte and nonaqueous secondary battery |
| CN109216783B (en) * | 2017-06-29 | 2020-09-15 | 比亚迪股份有限公司 | Film-forming additive composition for lithium ion battery, non-aqueous electrolyte and lithium ion battery |
| CN107658503A (en) * | 2017-10-23 | 2018-02-02 | 华南师范大学 | A kind of lithium secondary cell electrolyte and lithium secondary battery |
| CN109962289B (en) * | 2017-12-22 | 2022-03-11 | 财团法人工业技术研究院 | Electrolyte composition and metal ion battery comprising same |
| CN109687022B (en) * | 2018-12-25 | 2020-12-01 | 杉杉新材料（衢州）有限公司 | Electrolyte containing fluorine solvent and pyridine additive and lithium ion battery using electrolyte |
| CN109950622A (en) * | 2019-04-01 | 2019-06-28 | 杉杉新材料（衢州）有限公司 | A kind of manganate lithium ion battery nonaqueous electrolytic solution and lithium ion battery |
| WO2021174421A1 (en) * | 2020-03-03 | 2021-09-10 | 宁德新能源科技有限公司 | Electrolyte solution and electrochemical device using electrolyte solution |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3000272B2 (en) * | 1997-07-30 | 2000-01-17 | 東部韓農化學株式會社 | Method for producing carbonaceous powder for negative electrode active material of lithium ion secondary battery |
| CN1385918A (en) * | 2002-05-22 | 2002-12-18 | 哈尔滨光宇电源集团股份有限公司 | Novel electrolyte for lithium ion cell |
| CN1741313A (en) * | 2004-08-26 | 2006-03-01 | 黄穗阳 | High-energy and low-cost lithium polymer battery |
| CN101172646A (en) * | 2007-11-05 | 2008-05-07 | 桂林工学院 | Method of producing spinel structured lithium titanate |
| CN101188312A (en) * | 2007-10-12 | 2008-05-28 | 广州市鹏辉电池有限公司 | Non water solvent electrolysis additive and its battery |
| CN101202359A (en) * | 2006-12-14 | 2008-06-18 | 上海比亚迪有限公司 | Additive composition and electrolytic solution and lithium ion secondary battery containing the same |
-
2008
- 2008-09-11 CN CN200810141897.4A patent/CN101673852B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3000272B2 (en) * | 1997-07-30 | 2000-01-17 | 東部韓農化學株式會社 | Method for producing carbonaceous powder for negative electrode active material of lithium ion secondary battery |
| CN1385918A (en) * | 2002-05-22 | 2002-12-18 | 哈尔滨光宇电源集团股份有限公司 | Novel electrolyte for lithium ion cell |
| CN1741313A (en) * | 2004-08-26 | 2006-03-01 | 黄穗阳 | High-energy and low-cost lithium polymer battery |
| CN101202359A (en) * | 2006-12-14 | 2008-06-18 | 上海比亚迪有限公司 | Additive composition and electrolytic solution and lithium ion secondary battery containing the same |
| CN101188312A (en) * | 2007-10-12 | 2008-05-28 | 广州市鹏辉电池有限公司 | Non water solvent electrolysis additive and its battery |
| CN101172646A (en) * | 2007-11-05 | 2008-05-07 | 桂林工学院 | Method of producing spinel structured lithium titanate |
Non-Patent Citations (1)
| Title |
|---|
| Newkome, George R. et al..Complexes of palladium(II), platinum(II), copper(II), cobalt(II), and zinc(II) chlorides with 6,6"-dimethyl-2,2"-dipyridyl.《J. Inorg. Nucl. Chem.》.1981,第43卷(第7期),1529-31. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101673852A (en) | 2010-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101673852B (en) | Electrolyte additive and electrolyte and lithium ion battery containing same | |
| CN101207197B (en) | Lithium ion battery anode material and lithium ion battery and anode containing the material | |
| CN101783422B (en) | Additive and electrolyte containing the same and lithium-ion battery | |
| CN100517855C (en) | Electrolytic solution, lithium ion battery containing the same and their preparation method | |
| US20080254361A1 (en) | Non-Aqueous Electrolyte for Battery and Non-Aqueous Electrolyte Secondary Battery Comprising the Same | |
| CN108352504A (en) | Electrode for secondary battery and lithium secondary battery comprising the electrode | |
| CN103633363B (en) | A kind of lithium ion battery and preparation method thereof | |
| CN108987808B (en) | High-voltage lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN101494305A (en) | Lithium ion battery electrolyte and battery and battery set containing the same | |
| CN102487151B (en) | Lithium ion secondary battery | |
| CN102035039A (en) | High-safety lithium ion battery | |
| WO2012120846A1 (en) | Nonaqueous electrolyte additive, nonaqueous electrolyte, and nonaqueous electrolyte secondary battery | |
| CN105655641B (en) | A kind of electrolyte and its lithium ion battery | |
| CN108808087A (en) | A kind of electrolyte containing phosphorimide lithium and the battery using the electrolyte | |
| CN110085906A (en) | Nonaqueous electrolytic solution, the lithium ion battery containing the nonaqueous electrolytic solution | |
| KR20160007261A (en) | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same | |
| JP2010015719A (en) | Nonaqueous electrolyte for battery, and nonaqueous electrolyte secondary battery equipped with it | |
| JP5738010B2 (en) | Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery | |
| JP5093992B2 (en) | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery provided with the same | |
| CN101630758A (en) | Lithium-ion secondary battery and preparation method thereof | |
| CN101197436A (en) | Positive plate of lithium ion secondary battery, and battery including the same | |
| CN109037776A (en) | Electrolyte and battery comprising same | |
| JP4785735B2 (en) | Nonaqueous electrolyte for battery and nonaqueous electrolyte battery provided with the same | |
| CN101599556A (en) | A kind of electrolysis additive and contain the electrolyte and the lithium ion battery of this additive | |
| CN101593851B (en) | Additive composition, electrolyte containing same and lithium ion secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |