CN101599556A - A kind of electrolysis additive and contain the electrolyte and the lithium ion battery of this additive - Google Patents
A kind of electrolysis additive and contain the electrolyte and the lithium ion battery of this additive Download PDFInfo
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- CN101599556A CN101599556A CNA2008100678071A CN200810067807A CN101599556A CN 101599556 A CN101599556 A CN 101599556A CN A2008100678071 A CNA2008100678071 A CN A2008100678071A CN 200810067807 A CN200810067807 A CN 200810067807A CN 101599556 A CN101599556 A CN 101599556A
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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
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Abstract
The invention provides a kind of electrolysis additive, described additive comprises naphthalene derivatives, this additive not only makes battery have good anti-over-charging ability, improved the security performance of battery, and the high temperature cyclic performance and the multiplying power discharging property that contain the battery of this electrolysis additive all improve a lot.
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]
Lithium ion battery is a kind of novel chemical power source, and energy density is big, operating voltage is high, the life-span is long, the characteristics of no environment public hazards because of it has, and is widely used in the portable type electronic products such as mobile phone.Therefore combination property such as its fail safe is had relatively high expectations.
In the use of lithium ion battery, because the fault of charging control circuit is easy to occur overcharging, cause the irreversible reduction of battery cathode lithium ion, reduced the charge and discharge cycles efficient of battery; And when charging voltage reaches the decomposition voltage of electrolyte, also can cause the decomposition of electrolyte, produce gas at anode, make battery in press liter, inner product heat and loss of stability has a strong impact on the cycle life and the fail safe of battery, even can cause the complete failure of battery.Therefore, to seek suitable effective additives for overcharge protection very important for lithium ion battery.
In the prior art, the additives for overcharge protection of lithium ion battery mainly contains the over-charge protective additive method of the protection using integrated circuit method and the chemical method of physical method.The integrated circuit method is reliable, quick, be widely used, but complex structure must have outer packing plastic, and cost an arm and a leg.Existing over-charge protective additive comprises the additive based on polymerization reaction such as biphenyl, cyclohexyl benzene, but biphenyl, cyclohexyl benzene can increase the internal resistance of battery when using, battery performance is reduced; With the additive based on the reduction-oxidation reciprocal reaction such as halide, metallocene and the derivative thereof of lithium, the derivative of benzene, these several additive over-charge protective effects are obvious, but ineffective under high charge current, can reduce circulation and other performance of battery simultaneously.
[summary of the invention]
When the objective of the invention is to overcome existing additive the security performance of lithium rechargeable battery be improved, the shortcoming that other combination properties reduce, a kind of electrolysis additive that improves the combination property of battery is provided, this additive not only makes battery have good anti-over-charging ability, improved the security performance of battery, and the high temperature cyclic performance and the multiplying power discharging property that contain the battery of this electrolysis additive all are greatly improved.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 naphthalene derivatives shown in the formula I
Formula I
Wherein, R
1, R
2Be selected from the alkyl that contains 1-20 carbon atom independently of one another or contain the haloalkyl of 1-20 carbon atom; R
3～R
9Be selected from hydrogen, halogen atom independently of one another, contain 1-20 carbon atom alkyl, contain the haloalkyl of 1-20 carbon atom or contain in the amido of 1-20 carbon atom any one.
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.
The oxidizing potential of naphthalene derivatives is more than 4.2V, when voltage reaches the oxidizing potential of self, redox reaction can take place, cathode potential is locked near the oxidizing potential of itself, thereby reach the purpose that prevents battery overcharge, improved the fail safe of battery.Because the nitrogen in the molecule contains lone pair electrons, can form compound with anion, has not only improved the conductivity of electrolyte, can also increase the transport number of lithium ion, thereby make the multiplying power discharging of battery and high temperature cyclic performance be significantly improved.
Adopt the additive of electrolyte of lithium-ion secondary battery provided by the invention, can improve the security performance of battery, over-charging especially, the electrolyte that contains this additive makes battery after being full of electricity, 2.5h overcharges test with the 1C charging, and not swell of battery is not on fire does not explode; Can improve the multiplying power discharging property of battery, the electrolyte that contains additive of the present invention is significantly increased the heavy-current discharge capacity of battery; Can also improve the high temperature cyclic performance of battery.
Therefore, adopt additive provided by the invention to make security performance, multiplying power discharging property and the high temperature cyclic 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 existing additive reduces the battery combination property when improving the lithium rechargeable battery security performance shortcoming, a kind of electrolysis additive that improves the battery combination property is provided, this additive not only makes battery have good anti-over-charging ability, improved the security performance of battery, and the high temperature cyclic performance and the multiplying power discharging property that contain the battery of this electrolysis additive all are greatly improved.
The additive of described electrolyte of lithium-ion secondary battery contains the naphthalene derivatives shown in the formula I
Formula I
Wherein, R
1, R
2Be selected from the alkyl that contains 1-20 carbon atom independently of one another or contain the haloalkyl of 1-20 carbon atom; R
3～R
9Be selected from hydrogen, halogen atom independently of one another, contain 1-20 carbon atom alkyl, contain the haloalkyl of 1-20 carbon atom or contain in the amido of 1-20 carbon atom any one.Wherein, R
1, R
2The alkyl that preferably contains the straight chain of 1-20 carbon atom respectively more preferably contains the alkyl of the straight chain of 1-6 carbon atom, works as R
1, R
2Identical and when containing the alkyl of straight chain of 1-3 carbon atom the effect of this additive performance better.
The oxidizing potential of naphthalene derivatives is more than 4.2V, when voltage reaches the oxidizing potential of self, redox reaction can take place, cathode potential is locked near the oxidizing potential of itself, thereby reach the purpose that prevents battery overcharge, improved the fail safe of battery.Because the nitrogen in the molecule contains lone pair electrons, can form compound with anion, has not only improved the conductivity of electrolyte, can also increase the transport number of lithium ion, thereby make the multiplying power discharging of battery and high temperature cyclic performance be significantly improved.
Quality with electrolyte is a benchmark, and the quality percentage composition of described additive is 0.1-40 weight %, be preferably 0.5%-10 weight %.
The present invention provides the electrolyte that contains this additive simultaneously, and this electrolyte contains solvent, electrolyte and above-mentioned additive.
According to electrolyte provided by the invention, described content of additive be described electrolyte total amount 0.1-40 weight %, be preferably 0.5%-10 weight %.
According to electrolyte provided by the invention, described 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, described 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, and described additive is the additive of the performance of the known raising battery of art technology, as SEI film film for additive, flame-retardant additive etc.
The present invention preferably adds SEI film film for additive, is benchmark with the quality of electrolyte, described SEI film film for additive 0.1-11 weight %, preferred 1-8%.
Described 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.
The structure of described electrode group is conventionally known to one of skill in the art, and in general, described 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.
Consisting of of described positive pole 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.Described 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.Described positive electrode active materials is conventionally known to one of skill in the art, and it comprises positive active material and binding agent, and described 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).
Described anodal kind and content with binding agent is conventionally known to one of skill in the art.Preferred hydrophobicity adhesive mixes with hydrophilic adhesive.The ratio of described 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.Described 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%.
Described 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 described 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%.
Described 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 described negative electrode material layer generally includes the conductive agent that negative electrode active material, binding agent and selectivity contain.Described negative electrode active material can adopt various negative electrode active materials commonly used in the prior art, for example material with carbon element.Described 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.Described 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.
Described 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 described 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 %.
The preparation method of described positive pole 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
Present embodiment illustrates compositions of additives provided by the invention, electrolyte and contains the battery of this electrolyte and their preparation method.
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 over-charge protective additives 1,8-two (dimethyl amine) naphthalene 3.44 grams (2wt%) are stirred to all solids material and all dissolve, and make organic electrolyte then.
1,8-two (dimethyl amine) naphthalene
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 1150 Milliampere Hours.
Embodiment 2
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is that described over-charge protective additive is 1-bromo-4-(dimethyl amine) naphthalene, and 1-bromo-4-(dimethyl amine) naphthalene is 17.2 grams (10%).
1-bromo-4-(dimethyl amine) naphthalene
Embodiment 3
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is that described solvent is that ethylene carbonate 60 grams and diethyl carbonate 120 restrain; Described over-charge protective additive is 1-(dimethyl amine) naphthalene, 1-(dimethyl amine) naphthalene 8.32 grams (4%).
1-(dimethyl amine) naphthalene
Embodiment 4
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is that described over-charge protective additive is 1-(chloromethyl ethylamine) naphthalene, 1-(chloromethyl ethylamine) naphthalene 8.6 grams (5%).
1-(chloromethyl ethylamine) naphthalene
Embodiment 5
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is that described over-charge protective additive is 6-chloroethyl-1-(dimethyl amine) naphthalene, 25.8 grams (15%).
6-chloroethyl-1-(dimethyl amine) naphthalene
Comparative example 1
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is that described over-charge protective additive is a cyclohexyl benzene, 3.44 grams (2%).
Comparative example 2
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, it is different that different is is that described over-charge protective additive is the 2-bromoanisole, 3.44 grams (2%).
Battery performance test
Overcharge test
The lithium ion battery of the foregoing description 1-5 and Comparative Examples 1-2 gained is respectively got 20,, be limited to 4.2V in the charging, and then battery was overcharged 2.5 hours with 1C, detect the state of battery with 1C constant-current constant-voltage charging 2.5 hours.
The result is as shown in table 1, and wherein, test back battery swell (battery container cubical expansivity＞20% is the battery swell), leakage do not occur, smolder, on fire, fracture phenomena is qualified.
Table 1
| Battery | Test result |
| Embodiment 1 | All qualified |
| Experimental example 2 | All qualified |
| Experimental example 3 | All qualified |
| Experimental example 4 | 9/10 is qualified, 1/10 swell |
| Experimental example 5 | 9/10 is qualified, 1/10 swell |
| Comparative example 1 | 5/10 is qualified, 4/10 swell, and 1/10 smolders |
| Comparative example 2 | 6/10 is qualified, 3/10 swell, and 1/10 smolders |
By the test result of table 1 as can be known, the embodiment 1-5 battery that contains electrolysis additive of the present invention overcharges at full electricity back 1C had only the minority swell under the situation in 2.5 hours, particularly the preferred situation embodiment 1-3 of the present invention is all qualified, swell do not occur, smolder, the phenomenon of on fire, blast, the anti-over-charging ability is strong, and security performance is excellent; And under the situation of overcharging equally, all occurred a plurality of battery swells in various degree and the battery phenomenon of smoldering arranged with the battery of the Comparative Examples 1-2 of other over-charge protective electrolyte additives, the anti-over-charging ability of battery a little less than, security performance is relatively poor.Therefore electrolysis additive of the present invention increases the anti-over-charging ability of electrolyte, and the security performance of battery improves.
The multiplying power discharging volume test
Lithium rechargeable battery (20 batteries of every kind of condition with the foregoing description 1-5 and comparative example 1-2 gained, get its mean value) 1C (800mA) constant voltage charge is to 4.2V, shelved 10 minutes, discharge with 5C (4000mA) then, cut-ff voltage 3.0V, then respectively with 4C (3200mA), 3C (2400mA), 2C (1600mA), 1C (800mA), 0.5C (400mA), 0.2C (160mA) constant-current discharge, cut-ff voltage 3.0V.The record discharge capacity is compared the discharging efficiency that obtains the different multiplying discharge with the 0.2C capacity.The result is as shown in table 2.
Table 2
By the test result of table 2 as can be known; the embodiment 1-5 battery multiplying power discharging property that contains electrolysis additive of the present invention is better than the battery multiplying power discharging property that contains other over-charge protective additives; even particularly optimization experiment example 1-3 battery is with the heavy-current discharge of 5C; its discharge capacity still can keep its when 0.2C more than 65%; even be higher than 70%; and the discharge capacity sustainment rate of the battery of comparative example 1-2 under different multiplying is all lower, especially obviously outstanding inferior position when 4C, 5C high-multiplying power discharge.Therefore electrolysis additive of the present invention increases the conductivity of electrolyte, and the multiplying power discharging property of battery improves.
The cycle performance test
The lithium ion battery of the foregoing description 1-5 and Comparative Examples 1-2 gained is carried out cycle performance test (20 batteries of every kind of condition are got its mean value).Method of testing is: under 60 ℃ of conditions, battery is charged to 4.2V with the 1C constant-current constant-voltage charging, shelved 5 minutes, be discharged to 3.0V with 1C, the gained capacity is designated as initial capacity.Repeat above step 300 time, obtain the capacity that 300 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 3.
Table 3
From the test result of table 3 as can be known; the embodiment 1-5 battery that contains electrolysis additive of the present invention is at 60 ℃ obviously higher than the battery circulation volume surplus ratio that contains other over-charge protective additives down, and wherein the battery capacity surplus ratio of experimental example 1-3 is more than 85%.The cycle performance of battery be improved significantly.
Therefore, adopt additive provided by the invention to make security performance, multiplying power discharging property and the high temperature cyclic performance of battery all obtain very big raising of arriving, 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 naphthalene derivatives shown in the formula I
Formula I
Wherein, R
1, R
2Be selected from the alkyl that contains 1-20 carbon atom independently of one another or contain the haloalkyl of 1-20 carbon atom; R
3～R
9Be selected from hydrogen, halogen atom independently of one another, contain 1-20 carbon atom alkyl, contain the haloalkyl of 1-20 carbon atom or contain in the amido of 1-20 carbon atom any one.
2, additive according to claim 1 is characterized in that, R
1, R
2Be selected from the straight chained alkyl that contains 1-20 carbon atom respectively.
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 0.1-40%.
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 0.5-10%.
5, a kind of electrolyte of lithium rechargeable battery, this electrolyte contains solvent, electrolyte and additive, it is characterized in that, and described additive is any described additive of claim 1-4.
6, electrolyte according to claim 5 is characterized in that, is benchmark with the quality of electrolyte, and the quality percentage composition of described additive is 0.1-40%.
7, according to claim 5 or 6 described electrolyte, it is characterized in that, is benchmark with the quality of electrolyte, and the quality percentage composition of described additive is 0.5-10%.
8, 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.
9, 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.
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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807722A (en) * | 2010-04-09 | 2010-08-18 | 中国科学技术大学 | Electrolyte of safe lithium ion battery |
| CN101840793A (en) * | 2010-04-29 | 2010-09-22 | 株洲日望电子科技有限公司 | Super capacitor and preparation method thereof |
| CN102881941A (en) * | 2012-10-13 | 2013-01-16 | 兰州理工大学 | Electrolyte of lithium ion battery |
| CN104600364A (en) * | 2015-02-06 | 2015-05-06 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery applying same |
| US20180183101A1 (en) * | 2016-12-27 | 2018-06-28 | Toyota Jidosha Kabushiki Kaisha | Nonaqueous electrolytic solution and lithium secondary battery |
-
2008
- 2008-06-03 CN CNA2008100678071A patent/CN101599556A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807722A (en) * | 2010-04-09 | 2010-08-18 | 中国科学技术大学 | Electrolyte of safe lithium ion battery |
| CN101840793A (en) * | 2010-04-29 | 2010-09-22 | 株洲日望电子科技有限公司 | Super capacitor and preparation method thereof |
| CN102881941A (en) * | 2012-10-13 | 2013-01-16 | 兰州理工大学 | Electrolyte of lithium ion battery |
| CN104600364A (en) * | 2015-02-06 | 2015-05-06 | 宁德新能源科技有限公司 | Electrolyte and lithium ion battery applying same |
| US20180183101A1 (en) * | 2016-12-27 | 2018-06-28 | Toyota Jidosha Kabushiki Kaisha | Nonaqueous electrolytic solution and lithium secondary battery |
| US10892522B2 (en) * | 2016-12-27 | 2021-01-12 | Toyota Jidosha Kabushiki Kaisha | Nonaqueous electrolytic solution and lithium secondary battery |
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