CN101202359A - Additive composition and electrolytic solution and lithium ion secondary battery containing the same - Google Patents
Additive composition and electrolytic solution and lithium ion secondary battery containing the same Download PDFInfo
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- CN101202359A CN101202359A CNA2006101658822A CN200610165882A CN101202359A CN 101202359 A CN101202359 A CN 101202359A CN A2006101658822 A CNA2006101658822 A CN A2006101658822A CN 200610165882 A CN200610165882 A CN 200610165882A CN 101202359 A CN101202359 A CN 101202359A
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Abstract
The invention provides an additive combination of li-ion secondary battery electrolyte; wherein, the combination has three different compounds. By adopting the additive combination provided by the invention, the circulation performance, the high-temperature storage performance, the low-temperature discharging performance and the ratio discharging performance of the battery are greatly improved as a whole, and the comprehensive performance of the battery is greatly improved.
Description
Technical field
The electrolyte and the lithium rechargeable battery that the present invention relates to a kind of compositions of additives of electrolyte of lithium-ion secondary battery and contain this compositions of additives.
Background technology
At present, basic composition is of lithium rechargeable battery commonly used, comprise 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, in the positive pole with lithium-metal composite oxides as positive active material, in the negative pole with materials such as graphite, silicon as negative electrode active material, barrier film is used to separate positive and negative electrode.Novel lithium rechargeable battery adopts the negative pole of material with carbon element as battery mostly, with LiCoO
2, LiNiO
2, LiMn
2O
4Deng embedding and take off the positive pole of the lithium material of embedding as battery.Wherein, electrolyte is an important component part of battery, and the performance of battery is had a significant impact.
The electrolyte of lithium rechargeable battery generally is made up of organic solvent and electrolyte lithium salt.And in electrolyte, adopt additive that some macro property of lithium rechargeable battery can significantly be provided, as electrode capacity, multiplying power impulse electricity performance, both positive and negative polarity matching performance, cycle performance or security performance etc.Pointed strong, the characteristics that consumption is little of additive can significantly be improved the performance of battery not improving or not improving production cost substantially, do not change under the situation of production technology.
The nonaqueous solvents that is used for lithium ion battery all will react on the boundary of carbon negative pole and electrolyte in battery first charge-discharge process inevitably, forms the passivation layer (SEI film) that covers carbon electrodes.It is insoluble that good SEI film has organic solvent, allows lithium ion freely to pass in and out electrode and solvent molecule can't pass through, thereby stop solvent molecule to insert destruction to electrode altogether, improved performances such as the cycle efficieny of battery and reversible capacity.Additive improves the SEI film properties so can be added in electrolyte, the ring-type C=C double key carbon acid esters that comprises ethylene carbonate such as interpolation forms skin covering of the surface as additive in negative terminal surface, improve output characteristic under the high-multiplying power discharge with this, improve cycle life, but this additive makes the high-temperature storage performance of battery and low temperature performance all relatively poor; For another example, the film for additive sultone has good filming performance, the cycle performance that can improve battery and high-temperature storage performance, but sultone makes the low temperature performance of battery relatively poor; Also have, the film for additive gamma-butyrolacton has good filming performance, can improve the cycle performance of battery, can improve the low temperature performance of battery and the reversible capacity that discharges first, but gamma-butyrolacton (GBL) makes the high-temperature storage performance of battery relatively poor.
CN1612403A discloses a kind of electrolyte composition, and this electrolyte composition comprises: lithium salts; Contain nitrogen-containing compound, propane sultone and 1, the organic solvent of 2-ethenylidene carbonic ester and/or cyclohexyl benzene.This electrolyte composition improved battery when the high-temperature operation fail safe and do not make the performance of battery become bad.It is relatively poor that but the shortcoming that contains the lithium rechargeable battery of this electrolyte is a low temperature performance.
Summary of the invention
The objective of the invention is to overcome the relatively poor shortcoming of low temperature performance that the additive that uses in the prior art makes lithium rechargeable battery, a kind of low temperature performance that makes lithium ion battery compositions of additives of electrolyte of lithium-ion secondary battery preferably is provided, and electrolyte and the lithium rechargeable battery that contains this compositions of additives is provided.
The invention provides a kind of compositions of additives of electrolyte of lithium-ion secondary battery, wherein, said composition contains the Compound C shown in compd B shown in the compd A shown in the formula (I), the formula (II) and the formula (III):
Wherein, R
1-R
14Identical or different, be selected from hydrogen independently of one another or contain the alkyl of 1-4 carbon atom.
The present invention also provides a kind of electrolyte of lithium rechargeable battery, and this electrolyte contains nonaqueous solvents, electrolyte and compositions of additives, and wherein, described compositions of additives is a compositions of additives 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.
Adopt the compositions of additives of electrolyte of lithium-ion secondary battery provided by the invention, can improve the low temperature performance of battery, the electrolyte that is added with compositions of additives of the present invention make battery at-10 ℃ or-20 ℃ of following discharge capacity height, middle threshold voltage is high and it is little to stop internal resistances; Can also prolong the cycle life of battery, the cycle performance of battery is improved a lot, circulate expand little, cycle-index is many, capacity surplus ratio height; Can also improve the high-temperature storage performance of battery, be apparent that especially battery recovers thickness when high-temperature storage and the internal resistance increase is very little; Also can improve the multiplying power discharging property of battery, it is very high at the multiplying power discharging property that discharges under as 5C, 3C under the big electric current to add battery behind the compositions of additives of the present invention.
Therefore, adopt compositions of additives provided by the invention, cycle performance, high-temperature storage performance, low temperature performance and the multiplying power discharging property of battery are all improved a lot, the combination property of battery is all improved a lot.
Description of drawings
Fig. 1 is the multiplying power discharging contrast of embodiment 1-8 and comparative example 1-4;
Fig. 2 is the circulation volume surplus ratio contrast of embodiment 1-8 and comparative example 1-4.
Embodiment
The compositions of additives of electrolyte of lithium-ion secondary battery provided by the invention, contain the Compound C shown in compd B shown in the compd A shown in the formula (I), the formula (II) and the formula (III):
Wherein, R
1-R
14Identical or different, be selected from hydrogen independently of one another or contain the alkyl of 1-4 carbon atom.
Under the preferable case, compd A can be 1,3-propane sultone, 1, one or more in 4-butane sultone, ethylmethane sulfonate and the butyl methyl sulfonate; Compd B can be gamma-butyrolacton; Compound C can be in tert-butyl benzene, 4-t-butyltoluene and the tert-amyl benzene one or more.
According to compositions of additives provided by the invention, described compd A is the 1-80 weight portion, be preferably the 1-25 weight portion, and described compd B is 1-80 weight portion, preferred 1-30 weight portion, and described Compound C is 1-60 weight portion, preferred 1-20 weight portion.
Adopt compositions of additives provided by the invention, can suppress the expansion under placing of the decomposition of nonaqueous solvents in the electrolyte of lithium rechargeable battery and high temperature, the overall gas amount significantly reduces, and interface impedance is little.Before first charge-discharge generation reduction reaction, formed stable SEI film in the negative terminal surface of battery, prevented the common insertion reaction of solvent and coming off of graphite effectively.And in compositions of additives of the present invention, compd B gamma-butyrolacton (GBL) can also form form compact and stable SEI film at the positive pole of battery when first charge-discharge, has not only stoped the slow reaction of solvent and anode but also have good Li
+Conductive performance; 1,3-propane sultone (PS) (boiling point is 238 ℃) can improve the flash-point of electrolyte and reduce vapour pressure; GBL (204 ℃ of fusing point-44 ℃, boiling points, conductivity 14.3mScm
-1) and the adding of tert-butyl benzene class (as 168.5 ℃ of tert-butyl benzene fusing point-58.1 ℃, boiling points) widened the temperature scope of application of electrolyte greatly and improved conductivity, therefore the circulation of the battery of compositions of additives of the present invention improves a lot little, the capacity restoration rate height of internal resistance and varied in thickness during high temperature storage; Low temperature discharge internal resistance down changes not quite middle threshold voltage height; Li when also having increased heavy-current discharge
+Conducting power.Therefore compositions of additives provided by the present invention all improves a lot on circulation, high temperature storage and low temperature discharge compared with independent additive component.
The preparation method of described electrolyte is: nonaqueous solvents, electrolyte and compositions of additives are mixed, and the mode of mixing and order are not limit, and all can not influence the performance of electrolyte.
The electrolyte of lithium rechargeable battery provided by the invention contains nonaqueous solvents, electrolyte and compositions of additives, and wherein, described compositions of additives is a compositions of additives provided by the invention.
According to electrolyte provided by the invention, the content of described compositions of additives be described electrolyte total amount 0.3-22 weight %, be preferably 0.2-5 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, for example adopts 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), fluorocarbon based sulfonic acid lithium (LiCF
3SO
3, Li (CF
3SO
2)
3, Li (CF
3SO
2)
2N), LiCF
3CO
2, Li (CF
3CO
2)
2N and Li[(C
2O
4)
2B] in one or more.The concentration of electrolyte in electrolyte is generally 0.5-1.5 mol, preferred 0.8-1.2 mol for it be known to those skilled in the art that.
According to electrolyte provided by the invention, described nonaqueous solvents can use the nonaqueous solvents of any routine well known by persons skilled in the art, for example adopts in vinyl carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), 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) and the oxolane 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: 0.2-3.0, the weight proportion of three kinds of solvents are 1: 1-3.0: 0.2-2, the weight proportion of four kinds of solvents are 1: 1-3: 0.1-1.5: 0.2-2.0.
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 lithium and cobalt oxides LiCoO
2, lithium nickel oxide LiNiO
2, lithium manganese oxide LiMn
2O
4, lithium phosphate molysite LiFePO
4And in the Li-Ni-Mn-O system one or more.
Described anodal kind and content with binding agent is conventionally known to one of skill in the art, for example, described positive pole can be selected from fluorine resin and/or polyolefin compound with binding agent, as in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) or the butadiene-styrene rubber (SBR) one or more.In general, described anodal content with binding agent is the 0.01-8 weight % of positive active material, is preferably 1-5 weight %.
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.
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
50 gram vinyl carbonic esters (EC), 50 gram Methylethyl carbonic esters (EMC) and 50 gram diethyl carbonate (DEC) are mixed into mixed solvent, in this mixed solvent, add 20.81 gram LiPF
6Electrolyte, be made into the electrolyte solution that concentration is 1M, add compositions of additives then, in the compositions of additives 1,3-propane sultone (PS) is 0.34 gram, gamma-butyrolacton (GBL) 10.69 grams, tert-butyl benzene 0.34 gram, and the content of compositions of additives is 6.4 weight % in the electrolyte that makes.
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 with 1, the 4-butane sultone is replaced PS, and in the compositions of additives 1, the 4-butane sultone is that 0.91 gram, GBL are that 7.25 grams, tert-butyl benzene are 2.71 grams, and the content of compositions of additives is 5.7 weight % in the electrolyte that makes.
Embodiment 3
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is to replace PS with ethylmethane sulfonate, ethylmethane sulfonate is that 1.43 grams, GBL are that 5.35 grams, tert-butyl benzene are 0.89 gram in the compositions of additives, and the content of compositions of additives is 4.3 weight % in the electrolyte that makes.
Embodiment 4
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is to replace PS with butyl methyl sulfonate, butyl methyl sulfonate is that 2.16 grams, GBL are that 3.60 grams, tert-butyl benzene are 3.60 grams in the compositions of additives, and the content of compositions of additives is 5.2 weight % in the electrolyte that makes.
Embodiment 5
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is that PS is that 2.71 grams, GBL are that 2.71 grams, tert-butyl benzene are 4.52 grams in the compositions of additives, and the content of compositions of additives is 5.5 weight % in the electrolyte that makes.
Embodiment 6
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is that PS is that 3.58 grams, GBL are that 1.79 grams, tert-butyl benzene are 2.68 grams in the compositions of additives, and the content of compositions of additives is 4.5 weight % in the electrolyte that makes.
Embodiment 7
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is that PS is that 5.48 grams, GBL are that 0.91 gram, 4-t-butyltoluene are 5.48 grams in the compositions of additives, and the content of compositions of additives is 6.5 weight % in the electrolyte that makes.
Embodiment 8
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is to replace tert-butyl benzene with tert-amyl benzene, and PS is that 9.93 grams, GBL are that 9.93 grams, tert-amyl benzene are 7.94 grams in the compositions of additives, and the content of compositions of additives is 14 weight % in the electrolyte that makes.
Comparative example 1
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is not add compositions of additives.
Comparative example 2
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is only to add additive PS 3.49 grams, and content of additive is 2 weight % in the electrolyte that makes.
Comparative example 3
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is only to add additive GBL 3.49 grams, and content of additive is 2 weight % in the electrolyte that makes.
Comparative example 4
Prepare electrolyte and lithium rechargeable battery according to the method identical with embodiment 1, different is only to add additive tert-butyl benzene 3.49 grams, and content of additive is 2 weight % in the electrolyte that makes.
Each composition proportion is listed in the table 1 in the electrolyte of embodiment 1-8 and comparative example 1-4.
Battery performance test
1, partial volume capacity and thickness, internal resistance are measured:
Lithium rechargeable battery (30 batteries of every kind of condition with the foregoing description 1-8 and comparative example 1-4 gained, get its mean value), 100 milliamperes are charged to 3.9 volts earlier, place after 24 hours, with 550 milliamperes of constant-current constant-voltage charging to 4.2 volts, be discharged to 3.0 volts with 550 milliamperes then, it is exactly partial volume capacity (discharge stream mA * discharge time h) that battery is charged to the capacity of emitting behind the 4.2V; Battery after the solid measure returned be charged to 3.9 volts and take off calliper Thickness Measurement by Microwave (power taking pond mid-point); The internal resistance instrument is surveyed internal resistance.Table 2 is listed in measured capacity, cell thickness and internal resistance.
Table 1
| PS (gram) | 1,4-butane sultone (gram) | Ethylmethane sulfonate (gram) | Butyl methyl sulfonate (gram) | GBL (gram) | Tert-butyl benzene (gram) | 4-t-butyltoluene (gram) | Tert-amyl benzene (gram) | |
| |
0.34 | - | - | 0.2 | 10.69 | 0.34 | - | - |
| Embodiment 2 | - | 0.91 | - | - | 7.25 | 2.17 | - | - |
| Embodiment 3 | - | - | 1.43 | - | 5.35 | 0.89 | - | - |
| Embodiment 4 | - | - | - | 2.16 | 3.60 | 3.60 | - | - |
| Embodiment 5 | 2.71 | - | - | - | 2.71 | 4.52 | - | - |
| Embodiment 6 | 3.58 | - | - | - | 1.79 | 2.68 | - | - |
| Embodiment 7 | 5.48 | - | - | - | 0.91 | - | 5.48 | - |
| Embodiment 8 | 9.93 | - | - | - | 9.93 | - | - | 7.94 |
| Comparative example 1 | - | - | - | - | - | - | - | - |
| Comparative example 2 | 3.49 | - | - | - | - | - | - | - |
| Comparative example 3 | - | - | - | - | 3.49 | - | - | - |
| Comparative example 4 | - | - | - | - | - | 3.49 | - | - |
Table 2
| Capacity | Thickness | | |
| Embodiment | |||
| 1 | 1148.6 | 5.36 | 40.2 |
| Embodiment 2 | 1149.5 | 5.35 | 40.0 |
| Embodiment 3 | 1151.4 | 5.34 | 40.8 |
| Embodiment 5 | 1152.5 | 5.32 | 40.1 |
| Embodiment 4 | 1154.2 | 5.29 | 40.7 |
| Embodiment 6 | 1154.8 | 5.3 | 40.5 |
| Embodiment 7 | 1151.7 | 5.33 | 40.9 |
| Embodiment 8 | 1155.1 | 5.34 | 40.7 |
| Comparative example 1 | 1136.3 | 5.52 | 42.6 |
| Comparative example 2 | 1133.7 | 5.42 | 41.5 |
| Comparative example 3 | 1135.6 | 5.41 | 41.8 |
| Comparative example 4 | 1136.3 | 5.40 | 41.3 |
As can be seen from Table 2, the adding of compositions of additives makes the capacity of battery improve, reduce the internal resistance of battery and the generation of gas.This is mainly owing to the decomposition that has formed better SEI film and reduced solvent.
2, high-temperature behavior test
The lithium rechargeable battery of the foregoing description 1-8 and comparative example 1-4 gained is carried out the high-temperature behavior test, method of testing is: battery is lied prostrate with 1100 milliamperes of constant-current constant-voltage chargings to 4.2, survey open circuit voltage, internal resistance (is an initial voltage, initial internal resistance and original depth), afterwards battery is placed (85 ± 2) ℃ following storage 48 hours, after storing expiration, measure the thickness (85 ℃ storage after thickness) of battery, under (23 ± 7) ℃, shelve about 1 hour the back then and survey open circuit voltage, internal resistance, and battery is discharged to 3.0 volts with 1100 milliamperes, the discharge capacity (residual capacity) of good every the battery of record.After battery being full of electricity again and shelving 5 minutes, current discharges to 3.0 volt with 1100 milliamperes circulates three times continuously, writes down the capacity (recovery capacity) of each circulation, internal resistance (recovery internal resistance) and the thickness (recovery thickness) that the 3rd circulation is full of electricity.Capacity restoration rate, thickness increase, internal resistance increase and internal resistance according to following formula counting cell change:
Recovery capacity/initial capacity * 100% of capacity restoration rate (%)=the 3rd circulation;
Thickness increases (millimeter)=recovery thickness-original depth
Internal resistance increases (milliohm)=recovery internal resistance-initial internal resistance
Internal resistance variation=recovery internal resistance/initial internal resistance * 100%.
The test result that above-mentioned capacity restoration rate, thickness increase, internal resistance increase and internal resistance change is listed in the table 3.
As can be seen from Table 3, the battery of embodiment of the invention 1-8 is compared with the battery of comparative example 1-4 under 85 ℃ high temperature, has all suppressed the rising of cell thickness and internal resistance preferably, and has improved the capacity restoration rate.85 ℃ of high-temperature storage performances of battery (being high warm nature) of this explanation embodiment of the invention improve significantly.
Table 3
| The capacity surplus ratio | Thickness increases (millimeter) | Internal resistance increases (milliohm) | Internal resistance changes | |
| |
74.03 | 0.73 | 4 | 9.7％ |
| Embodiment 2 | 75.71 | 0.69 | 3.9 | 9.5％ |
| Embodiment 3 | 78.54 | 0.69 | 3.6 | 8.8％ |
| Embodiment 4 | 79.38 | 0.68 | 3.5 | 8.6％ |
| Embodiment 5 | 83.05 | 0.64 | 3.7 | 9.0％ |
| Embodiment 6 | 81.64 | 0.58 | 3.1 | 7.7％ |
| Embodiment 7 | 81.58 | 0.66 | 3.8 | 9.3％ |
| Embodiment 8 | 82.12 | 0.63 | 3.3 | 8.1％ |
| Comparative example 1 | 56.32 | 1.23 | 8.5 | 20.0％ |
| Comparative example 2 | 68.23 | 0.85 | 5.5 | 13.3％ |
| Comparative example 3 | 61.09 | 1.07 | 6.4 | 15.3％ |
| Comparative example 4 | 63.22 | 0.89 | 6.15 | 14.9％ |
3, low temperature performance test
The lithium rechargeable battery of the foregoing description 1-8 and comparative example 1-4 gained is carried out the high-temperature behavior test, method of testing is: battery is lied prostrate with 1100 constant-current constant-voltage chargings to 4.2, then be discharged to 3.0 volts with the 1C milliampere, discharge capacity is an initial capacity, then battery is lied prostrate with 1100 milliamperes of constant-current constant-voltage chargings to 4.2 again,-10 ℃ down with 1100 milliamperes of discharges, the capacity when record is discharged to 3.0 volts, 2.75 volts respectively is with, middle threshold voltage and termination internal resistance; Again-10 ℃ of following discharge batteries are lied prostrate with 1100 milliamperes of constant-current constant-voltage chargings to 4.2, under-20 ℃,, write down the capacity when being discharged to 3.0 volts, 2.75 volts, middle threshold voltage respectively and stop internal resistance with 1100 milliamperes of discharges.Under-10 ℃ and-20 ℃, record respectively be discharged to 3.0 volts, 2.75 volts the time capacity, middle threshold voltage and termination internal resistance list in table 4.
Table 4
As can be seen from Table 4, because the battery of embodiment of the invention 1-8 has formed good SEI film, therefore the embodiment that has added compositions of additives has higher conductivity and the low internal resistance of cell and high middle threshold voltage with respect to comparative example at low temperatures, and the capacity surplus ratio obviously improves.
4, heavy-current discharge performance
The lithium rechargeable battery of the foregoing description 1-8 and comparative example 1-4 gained is carried out the high rate performance test, and method of testing is: battery is lied prostrate with 1100 constant-current constant-voltage chargings to 4.2, then be discharged to 3.0 volts with 220 milliamperes, discharge capacity is the 0.2C capacity; Then battery is lied prostrate with 1100 milliamperes of constant-current constant-voltage chargings to 4.2, be discharged to 3.0 volts with 1100 milliamperes, discharge capacity is the 1C capacity; Again with 1100 milliamperes of constant-current constant-voltage chargings to 4.2 volt, be discharged to 3.0 volts with 2200 milliamperes, discharge capacity is the 2C capacity; With 1100 milliamperes of constant-current constant-voltage chargings to 4.2 volt, be discharged to 3.0 volts with 3300 milliamperes, discharge capacity is the 3C capacity; With 1100 milliamperes of constant-current constant-voltage chargings to 4.2 volt, be discharged to 3.0 volts with 5500 milliamperes, discharge capacity is the 5C capacity.
Multiplying power is calculated as follows: capacity under x multiplying power=xC/0.2C capacity.
The multiplying power of each example of gained the results are shown in table 5, and is shown among Fig. 1.
Table 5
| 5C | 3C | 2C | 1C | 0.2 | |
| Embodiment | |||||
| 1 | 60.8 | 79.1 | 95.2 | 97.4 | 100 |
| Embodiment 2 | 65.4 | 83.2 | 96.6 | 99.2 | 100 |
| Embodiment 3 | 64.6 | 82.4 | 95.8 | 98.7 | 100 |
| Embodiment 4 | 63.3 | 80.9 | 95.3 | 98.2 | 100 |
| Embodiment 5 | 61.2 | 78.5 | 95.1 | 98.5 | 100 |
| Embodiment 6 | 59.8 | 77.0 | 94.5 | 98.4 | 100 |
| Embodiment 7 | 59.7 | 76.9 | 95.2 | 99.6 | 100 |
| Embodiment 8 | 62.9 | 80.4 | 95.4 | 98.3 | 100 |
| Comparative example 1 | 50.6 | 69.7 | 91.2 | 96.0 | 100 |
| Comparative example 2 | 53.2 | 72.6 | 92.0 | 96.9 | 100 |
| Comparative example 3 | 56.8 | 75.6 | 94.1 | 98.0 | 100 |
| Comparative example 4 | 54.4 | 73.9 | 92.4 | 97.3 | 100 |
As can be seen from Figure 1, the embodiment 1-8 that adds compositions of additives compares with comparative example 1-4, and multiplying power is higher, demonstrates superior Li ionic conduction performance during high-multiplying power discharge.
5, cycle performance test
The lithium rechargeable battery of the foregoing description 1-8 and comparative example 1-4 gained is carried out the cycle performance test, method of testing is: battery is packed into battery on the ability meter BS-9300 with correct method, earlier charge to 4.2 volts with 1100 milliamperes of constant-current constant-voltage chargings, shelved 5 minutes, be discharged to 3.0 volts with 1100, so circulation, the capacity surplus ratio for the treatment of reaches till 70%, writes down each circulation volume, the internal resistance of discharge attitude, middle threshold voltage; Draw the circulation volume surplus ratio and list in the table 6, and be compared among Fig. 2.
Capacity/1st time circulation volume * 100% of the capacity surplus ratio of X circulation=X circulation
Table 6
| Cycle-index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Ratio is than 4 |
| 1 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| 5 | 98.5 | 98.7 | 98.7 | 98.8 | 99.2 | 99.3 | 98.6 | 98.5 | 98.6 | 98.6 | 98.6 | 98.4 |
| 10 | 96.6 | 96.6 | 97.1 | 97.4 | 97.5 | 97.4 | 97.1 | 96.8 | 96.6 | 96.6 | 96.7 | 96.6 |
| 30 | 94.6 | 94.7 | 95.1 | 95.0 | 95.6 | 95.7 | 95.2 | 94.9 | 94.1 | 94.3 | 94.5 | 94.5 |
| 60 | 93.2 | 93.1 | 94.1 | 93.9 | 94.4 | 94.3 | 94.0 | 93.9 | 92.3 | 92.9 | 93.1 | 93.0 |
| 90 | 91.8 | 91.7 | 92.9 | 92.9 | 93.3 | 93.2 | 92.8 | 92.6 | 90.4 | 91.7 | 91.8 | 91.6 |
| 120 | 90.5 | 90.4 | 91.5 | 91.4 | 92.4 | 92.1 | 91.4 | 91.3 | 88.4 | 89.4 | 90.4 | 90.4 |
| 150 | 89.6 | 89.5 | 90.6 | 90.6 | 91.4 | 91.2 | 90.5 | 90.4 | 86.9 | 88.3 | 89.4 | 89.4 |
| 180 | 88.6 | 88.5 | 89.5 | 89.8 | 90.5 | 90.3 | 89.6 | 89.4 | 85.6 | 87.1 | 88.1 | 88.4 |
| 210 | 87.4 | 87.3 | 88.4 | 88.9 | 89.6 | 89.2 | 88.4 | 88.0 | 84.2 | 85.6 | 86.5 | 86.9 |
| 240 | 86.4 | 86.3 | 87.3 | 88.0 | 88.6 | 88.1 | 87.5 | 87.2 | 82.9 | 84.7 | 85.3 | 85.7 |
| 270 | 85.6 | 85.3 | 86.3 | 87.2 | 87.7 | 87.2 | 86.7 | 86.3 | 81.3 | 83.7 | 84.3 | 84.4 |
| 300 | 84.5 | 84.4 | 85.4 | 86.4 | 87.0 | 86.5 | 85.8 | 85.4 | 80.0 | 82.6 | 83.2 | 83.3 |
| 330 | 83.6 | 83.4 | 84.5 | 85.5 | 86.3 | 85.8 | 84.8 | 84.6 | 78.4 | 81.2 | 82.0 | 81.8 |
| 360 | 82.8 | 82.5 | 83.5 | 84.6 | 85.7 | 85.1 | 83.9 | 83.6 | 76.7 | 80.4 | 80.9 | 80.4 |
| 390 | 81.9 | 81.6 | 82.5 | 83.8 | 85.0 | 84.4 | 83.0 | 82.7 | 74.4 | 78.8 | 79.5 | 79.4 |
| 420 | 80.9 | 80.4 | 81.5 | 83.0 | 84.3 | 83.6 | 82.1 | 81.8 | 72.2 | 77.6 | 78.1 | 78.2 |
| 450 | 79.7 | 79.2 | 79.9 | 82.1 | 83.6 | 82.8 | 81.2 | 80.7 | 70.0 | 76.2 | 76.7 | 77.0 |
| 480 | 78.1 | 77.6 | 78.9 | 81.3 | 82.9 | 81.9 | 80.3 | 79.3 | 67.2 | 74.5 | 75.0 | 75.9 |
From table 6 or Fig. 2 as can be seen, the embodiment 1-8 that adds compositions of additives obviously strengthens with respect to comparative example 1-4 cycle performance.
From above test result as can be seen, compositions of additives provided by the invention all improves a lot cycle performance, high-temperature storage performance, low temperature performance and the multiplying power discharging property of lithium rechargeable battery, and the combination property of battery is all improved a lot.
Claims (10)
1. the compositions of additives of an electrolyte of lithium-ion secondary battery is characterized in that, said composition contains the Compound C shown in compd B shown in the compd A shown in the formula (I), the formula (II) and the formula (III):
Wherein, R
1-R
14Identical or different, be selected from hydrogen independently of one another or contain the alkyl of 1-4 carbon atom.
2. compositions of additives according to claim 1, wherein, the content of described compd A, compd B and Compound C is that described compd A is the 1-80 weight portion, and described compd B is the 1-80 weight portion, and described Compound C is the 1-60 weight portion.
3. compositions of additives according to claim 2, wherein, described compd A is the 1-25 weight portion, and described compd B is the 1-30 weight portion, and described Compound C is the 1-20 weight portion.
4. according to claim 1,2 or 3 described compositions of additives, wherein, described compd A is 1,3-propane sultone, 1, one or more in 4-butane sultone, ethylmethane sulfonate and the butyl methyl sulfonate; Described compd B is a gamma-butyrolacton; Described Compound C is one or more in tert-butyl benzene, 4-t-butyltoluene and the tert-amyl benzene.
5. the electrolyte of a lithium rechargeable battery, this electrolyte contains nonaqueous solvents, electrolyte and compositions of additives, it is characterized in that, and described compositions of additives is any described compositions of additives of claim 1-4.
6. electrolyte according to claim 5 wherein, is benchmark with electrolyte, and the content of described compositions of additives is 0.3-22 weight %.
7. electrolyte according to claim 6, wherein, the content of described compositions of additives is 0.2-5 weight %.
8. electrolyte according to claim 5, wherein, described nonaqueous solvents is selected from one or more in vinyl carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, methyl formate, methyl acrylate, methyl butyrate, ethyl acetate, ethene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite and the oxolane; Wherein, described electrolyte is selected from LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiSiF
6, LiB (C
6H
5)
4, LiCl, LiBr, LiAlCl
4, LiCF
3SO
3, Li (CF
3SO
2)
3, Li (CF
3SO
2)
2N), LiCF
3CO
2, Li (CF
3CO
2)
2N and Li[(C
2O
4)
2B] in one or more.
9. according to claim 5 or 8 described electrolyte, wherein, the concentration of described electrolyte in described electrolyte is the 0.5-1.5 mol.
10. 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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