CN104752764A - Combined additive, electrolyte and lithium ion secondary cell - Google Patents
Combined additive, electrolyte and lithium ion secondary cell Download PDFInfo
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- CN104752764A CN104752764A CN201310730891.1A CN201310730891A CN104752764A CN 104752764 A CN104752764 A CN 104752764A CN 201310730891 A CN201310730891 A CN 201310730891A CN 104752764 A CN104752764 A CN 104752764A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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Abstract
The invention discloses a combined additive for a lithium ion secondary cell, an electrolyte containing the combined additive, and a cell containing the electrolyte. The combined additive contains methylene methanedisulfonate shown in the formula (1), phosphotriester shown in the formula (2) and vinylene carbonate, and a weight ratio of methylene methanedisulfonate shown in the formula (1) to phosphotriester shown in the formula (2) to vinylene carbonate is 0.04-100: 1: 0.1-100. The electrolyte containing the combined additive solves problems of the prior art, obviously improves capacity attenuation and thickness increasing of the cell containing the electrolyte in use or storage at a high temperature, reduces an electric capacity attenuation rate in circulation and greatly improves low temperature discharge properties.
Description
Technical field
The present invention relates to a kind of combined additive of electrolyte of lithium-ion secondary battery, a kind of electrolyte containing this combined additive and the lithium rechargeable battery containing this electrolyte.
Background technology
Along with the scarcity of traditional energy and running down of urban air pollution, electric automobile more and more receives everybody concern.Lithium rechargeable battery is a kind of novel chemical power source, because it has that energy density is large, operating voltage is high, the life-span is long, without the feature of environmental hazard, causes the broad interest of researchers.But the environment for use of automobile is comparatively severe relative to the compact battery such as battery of mobile phone, notebook.The factors such as the high-temperature behavior of battery, cryogenic property and life-span of recycling must be taken into account in this case.And after existing electrolyte improves the high-temperature behavior of battery often, the cryogenic property of battery will be poor, after improving the cryogenic property of battery, the high-temperature behavior of battery will be poor, can't accomplish that the effect of battery under high temperature and low temperature can both obtain the effect fully played simultaneously.
Publication number be CN1925206A prior art discloses a kind of power-type lithium ion battery electrolyte, publication number is CN101071863A prior art discloses a kind of lithium battery electrolytes, publication number is CN102064344A prior art discloses a kind of Novel electrolyte for power battery and publication number be CN102437373A prior art discloses a kind of electrolyte for lithium iron phosphate dynamic battery and preparation method thereof.But electrolyte disclosed in above prior art is all unsuitable for using in the battery of long-term electric automobile in various environment, the electrolyte such as adopting CN1925206A and CN101071863A to provide address only the safety problem that can not set off an explosion when application contains the battery of this electrolyte under the high temperature conditions, but high power capacity can not be kept at low ambient temperatures, and useful life is short, thus and be not suitable as the electrolyte of automobile power cell; And although the electrolyte adopting CN102064344A to provide at high temperature can obtain good cycle performance, can not solve high rate discharge when electric automobile uses in low temperature environment in actual life, be namely unfavorable for discharging in low temperature environment, useful life is short; Although the battery of the electrolyte provided containing CN102437373A can be used in low temperature and hot environment, its service life cycle is but very low, and capacitance when recycling reduces very fast, thus while wasting the energy, adds use cost.
In sum, capacitance when existing electrolyte exists that environment for use is limited, useful life is long, discharge rate is high and recycle underspeeds the defect such as fast.
Summary of the invention
The object of this invention is to provide a kind of combined additive of electrolyte of lithium-ion secondary battery, electrolyte containing this combined additive can overcome the defect of prior art, the capacity attenuation of the battery that obvious improvement contains this electrolyte at applied at elevated temperature or when storing and thickness swelling, and reducing the capacitance fall-off rate of circulation time, low temperature performance also has raising by a relatively large margin.
To achieve these goals, on the one hand, the invention provides a kind of combined additive of electrolyte of lithium-ion secondary battery, this combined additive contains the methane-disulfonic acid methylene ester shown in formula (1), the phosphotriester shown in formula (2) and vinylene carbonate, and the weight of the methane-disulfonic acid methylene ester shown in formula (1): the weight of the phosphotriester shown in formula (2): the weight of vinylene carbonate is 0.04-100:1:0.1-100;
Wherein, the R in formula (2)
1, R
2and R
3identical or different, be separately selected from hydrogen, one in substituted or unsubstituted straight or branched alkyl that carbon number is 1-20.
On the other hand, the present invention also provides a kind of electrolyte of lithium-ion secondary battery, and this electrolyte contains organic solvent, lithium salts and combined additive of the present invention, wherein, with the total weight of electrolyte, this electrolyte contains described combined additive 0.75-20 % by weight.
On the other hand, the present invention also provides a kind of lithium rechargeable battery, this battery battery container, electrode group and electrolyte, and electrode group and electrolyte are sealed in battery container, electrode group comprises positive pole, barrier film and negative pole, and described electrolyte is electrolyte provided by the invention.
Capacity attenuation when lithium rechargeable battery containing electrolyte of lithium-ion secondary battery provided by the invention obviously can improve at applied at elevated temperature or store and thickness swelling, and reducing the capacitance fall-off rate of circulation time, low temperature performance also has raising by a relatively large margin.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of combined additive of electrolyte of lithium-ion secondary battery, this combined additive contains the methane-disulfonic acid methylene ester shown in formula (1), the phosphotriester shown in formula (2) and vinylene carbonate, and the weight of the methane-disulfonic acid methylene ester shown in formula (1): the weight of the phosphotriester shown in formula (2): the weight of vinylene carbonate is 0.04-100:1:0.1-100;
Wherein, the R in formula (2)
1, R
2and R
3identical or different, be separately selected from hydrogen, one in substituted or unsubstituted straight or branched alkyl that carbon number is 1-20.
In the present invention, described carbon number be the substituted or unsubstituted straight or branched alkyl of 1-20 include but not limited in following alkyl one or more: methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, new butyl, amyl group, hexyl, octyl group, dodecyl and octadecyl.
When being used for lithium rechargeable battery containing above-mentioned electrolyte of lithium-ion secondary battery provided by the invention, namely can obviously improve battery applied at elevated temperature or store time capacity attenuation and thickness swelling, and reduce circulation time capacitance fall-off rate and improve low temperature performance.But the present inventor finds, under preferable case, in combined additive of the present invention, as R in formula (2)
1, R
2and R
3identical or different, separately be selected from hydrogen, a kind of in substituted or unsubstituted straight or branched alkyl that carbon number is 3-12 time, by containing this combined additive used for electrolyte in lithium rechargeable battery can improve further battery at applied at elevated temperature or store time capacity attenuation and thickness swelling.
In the present invention, described carbon number be the substituted or unsubstituted straight or branched alkyl of 3-12 include but not limited in following alkyl one or more: propyl group, isopropyl, butyl, isobutyl group, new butyl, amyl group, hexyl, octyl group, dodecyl and octadecyl.
Further, in the present invention, described carbon number be the substituted or unsubstituted straight or branched alkyl of 3-12 include but not limited in following alkyl one or more :-(CH
2)
7cH
3,-(CH
2)
9cH
3,-(CH
2)
11oCH
3,-(CH
2)
10oCH
2cH
3,-(CH
2)
9cH
2cl ,-(CH
2)
9cH
3,-(CH
2)
11cH
2cl ,-(CH
2)
15cH
3,-(CH
2)
15cH
2cl ,-(CH
2)
19cH
3with-(CH
2)
19cH
3.
When the present inventor is surprised to find that in electrolyte of lithium-ion secondary battery and contains trioctyl phosphate, surface tension and the viscosity of electrolyte can be reduced largely, and then improve wettability and the mobility on battery pole piece surface, make the solvation of lithium ion at low temperatures, desolvated and diffusion velocity all makes moderate progress.The branch chain of the length of trioctyl phosphate launches simultaneously, can network structure be formed, and to methane-disulfonic acid methylene ester (MMDS) and vinylene carbonate (VC), there is " induction " effect, it can be made dispersed, and by mesh in electrode surface film forming, the film of this formation is even and fine and close.MMDS is first evenly by mesh film forming, and membrane formation mechanism is identical with upper, thus make film evenly; VC is by same mesh film forming under long-chain " induction " effect of trioctyl phosphate afterwards, and this two-step film forming is even equally, and further increases consistency, therefore further preferably R
1, R
2and R
3for n-octyl.
Under preferable case, the weight ratio of the methane-disulfonic acid methylene ester shown in formula (1), the phosphotriester shown in formula (2) and vinylene carbonate in combined additive of the present invention is 4-80:1:5-80, and preferably the weight ratio of three is 10-50:1:15-50 further.
To the preparation method of combined additive of the present invention, there is no particular limitation, can be method well known in the art.Such as, can be that 0.04-100:1:0.1-100 mixes with weight ratio by the phosphotriester shown in the methane-disulfonic acid methylene ester shown in formula (1), formula (2) and vinylene carbonate;
Wherein, the R in formula (2)
1, R
2and R
3identical or different, be separately selected from hydrogen, one in substituted or unsubstituted straight or branched alkyl that carbon number is 1-20.There is no particular limitation for the method for wherein said mixing, and for well known in the art, also there is no particular limitation for the addition sequence of above-mentioned three kinds of materials, can add with random order and mix.
The present invention also provides a kind of electrolyte for lithium rechargeable battery, this electrolyte contains organic solvent, lithium salts and the present invention any one combined additive above-mentioned, wherein, with the total weight of electrolyte, this electrolyte contains combined additive 0.75-20 % by weight.
By of the present invention above-mentioned used for electrolyte when the lithium rechargeable battery, just obviously can reduce the capacitance fall-off rate of circulation time and improve low temperature performance.But, the present inventor finds, when being 2-8 % by weight containing above-mentioned any one combined additive 1.7-10 % by weight of the present invention, further preferred compositions additive in preferred electrolyte, the attenuation rate of the circulation capacitance of the battery containing this electrolyte significantly reduces, and low temperature performance also can increase substantially.
Organic solvent in electrolyte of the present invention can be selected according to the kind of routine by those skilled in the art, such as organic solvent can be selected from gamma-butyrolacton, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, dipropyl carbonate, propene carbonate, methyl formate, methyl acrylate, methyl butyrate, ethyl acetate, ethylene sulfite, propylene sulfite, methyl sulfide, dimethyl sulfite, sulfurous acid diethyl ester, oxolane, acid anhydrides, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, N, dinethylformamide, one or more in sulfolane and methyl-sulfoxide.
Lithium salts in electrolyte of the present invention can be selected according to the kind of routine by those skilled in the art, and such as described lithium salts can for being selected from LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiSiF
6, LiB (C
6h
5)
4, LiCl, LiBr, LiI, LiAlCl
4, LiBOB, LiCF
3sO
3, LiC
4f
9sO
3and LiN (C
xf
2x+1sO
2) (C
yf
2y+1sO
2) in one or more, wherein, x and y is positive integer.
In the present invention, the organic solvent in preferred described electrolyte be selected from gamma-butyrolacton, ethylene carbonate, ethyl carbonate, diethyl carbonate and dimethyl carbonate one or more.In order to increase lithium salts solubility in organic solvent and the battery improved further containing this electrolyte at applied at elevated temperature or store time capacity attenuation and thickness swelling, the present invention preferably uses the mixed solvents of two kinds, three kinds or four kinds compositions in above-mentioned organic solvent.
In the present invention, preferred described lithium salts is for being selected from LiPF
6, LiClO
4, LiBF
4, LiAsF
6and LiSiF
6in one or more.
The further preferred described organic solvent of the present invention is the mixed solvent of ethyl carbonate, diethyl carbonate and dimethyl carbonate.
Under preferable case, the weight ratio of ethyl carbonate of the present invention, diethyl carbonate and dimethyl carbonate is 1:1-2:0.5-1.5, when further the weight ratio of preferred above-mentioned three is 1:1-1.5:0.8-1.2, the battery containing this electrolyte applied at elevated temperature or store time capacity attenuation and thickness swelling improve more remarkable.
Under further preferable case, the lithium salts in electrolyte of the present invention is LiPF
6.
Under preferable case, in electrolyte of the present invention, the concentration of lithium salts is 0.5-1.5mol/L; Further in preferred electrolyte, the concentration of lithium salts is 0.8-1.2mol/L.
In addition, as required, electrolyte provided by the present invention can also contain various functional additive, such as, can contain film for additive, flame-retardant additive etc.Described film for additive can be well known to a person skilled in the art various additive, such as, in carbon dioxide, carbon disulfide, sulfur dioxide, ethylene sulfite (ES), propylene sulfite (PS) and lithium carbonate one or more.
To the preparation method of described electrolyte, there is no particular limitation in the present invention, it can be known method, such as, the preparation method of described electrolyte can comprise and is added in organic solvent by lithium salts and combined additive, then stirring makes it fully dissolve, is uniformly dispersed, and gained solution is electrolyte provided by the invention.Wherein, the addition sequence not requirement of lithium salts and combined additive, can add respectively, also can add simultaneously.
The present invention also provides 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 positive pole, barrier film and negative pole, and described electrolyte is any one electrolyte above-mentioned of the present invention.
The structure of described electrode group has been conventionally known to one of skill in the art, and in general, described 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 have also been conventionally known to one of skill in the art, do not repeat them here.
Consisting of of described 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.Described collector has been 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.Described positive electrode has been conventionally known to one of skill in the art, and generally include the conductive agent that positive active material, adhesive and selectivity contain, described positive active material can be selected from the positive active material of lithium rechargeable 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); Described conductive agent can be one or more of acetylene black, electrically conductive graphite or conductive carbon fibre; Described adhesive can be Kynoar (PVDF).
The preparation method of described positive pole is well known in the art, such as can by LiFePO
4, electric conducting material, adhesive by weight for 100:4-10:3-10 ratio mixing and with appropriate NMP(N-methyl pyrrolidone) stir into slurry, this slurry is applied on the Al paper tinsel of 12-20 μm, drying, compacting obtain positive plate.
Described negative pole can adopt negative pole known in the field, in general, and the negative material that negative pole comprises negative current collector and coating and/or is filled on this negative current collector.Described conductive current collector is conventionally known to one of skill in the art, such as, can be selected from one or more in aluminium foil, Copper Foil, nickel plated steel strip, Punching steel strip.Anticathode material of the present invention has no particular limits, and like the prior art, described negative material generally includes the conductive agent that negative electrode active material, adhesive and selectivity contain.Described negative electrode active material can adopt various negative electrode active materials conventional in prior art, such as material with carbon element.Described 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., described organic polymer sinter can be by phenolic resins, epoxy resin etc. being sintered and the product of gained after carbonizing; Described adhesive can be polytetrafluoroethylene (PTFE); Described Kynoar (PVDF).
The preparation method of described negative pole is well known in the art, such as, can be that powdered graphite and polytetrafluoroethylene (PTFE), the sodium carboxymethylcellulose (CMC) of 12 μm obtains negative material paste for 100:2-7:1-3 using deionized water as solvent by weight by average grain diameter.Dry on the Copper Foil this negative material paste being spread upon 10-16 μm, compacting obtains negative plate.
To the preparation method of lithium rechargeable battery, there is no particular limitation in the present invention, the various preparation methods that can be known to the skilled person, such as, the preparation method of this battery can comprise and arranges barrier film by between positive pole and negative pole, forms electrode group, this electrode group is held in the cell housing, inject electrolyte, then battery container is airtight, wherein, described electrolyte is electrolyte provided by the invention.Except described electrolyte is electrolyte provided by the invention, other step is conventionally known to one of skill in the art, does not repeat them here.
Below will be described the present invention by embodiment.In following examples, come in situation about being not particularly illustrated, raw materials used all from being purchased.Voltage of the present invention and capacitance are obtained by test cabinet (trade mark is new Weir 500A/5V) test, and internal resistance is obtained by internal resistance instrument (trade mark is BK-6802/300A) test.
Preparation example 1
By methane-disulfonic acid methylene ester, vinylene carbonate and trioctyl phosphate by weight ratio as shown in table 1 below mixing obtained combined additive A1-A5, D1.
Table 1
Preparation example 2
Get respectively 48mL ethyl carbonate, 64mL diethyl carbonate and 48mL dimethyl carbonate, 24.32g lithium salts and as shown in table 2 below % by weight combined additive mixing with obtained electrolyte B1-B5 and DD1, DD2.
Table 2
| Electrolyte | The kind of combined additive | % by weight of combined additive |
| B1 | A1 | 5 |
| B2 | A2 | 1.7 |
| B3 | A3 | 10 |
| B4 | A4 | 5 |
| B5 | A5 | 5 |
| DD1 | D1 | 5 |
| DD2 | A1 | 0.5 |
Preparation example 3
The preparation of positive pole:
By 2820 grams of LiFePO
4, 90 grams of aluminium foils, 90 grams of electrically conductive graphites and 90 grams of PVDF mixing stir into slurry with 1350 grams of NMP, this slurry is applied on the aluminium foil of 16 μm, through 125 DEG C of dryings 1 hour, after roll-in, cut-parts, obtain the positive plate of about 3000 millimeters × 150 millimeters × 0.125 millimeter.
The preparation of negative pole:
Be that powdered graphite and 30 grams of PTFE, 20 grams of CMC of 12 μm obtain negative material paste using 1600mL deionized water as solvent by 1395 grams of average grain diameters.The Copper Foil this negative material paste being coated on 12 micron thickness, through 125 DEG C of dryings 1 hour, obtains the negative plate of about 3020 millimeters × 160 millimeters × 0.100 millimeter after roll-in, cut-parts.
Embodiment 1-5
The positive and negative plate obtain above-mentioned preparation example 3 and the polypropylene diaphragm of 20 micron thickness are wound into the electrode group of square lithium ion secondary battery, and this electrode assembling is entered in rectangular cell aluminum hull, subsequently electrolyte B1-B5 obtained before 160mL is injected in the battery case of embodiment 1-5 respectively, sealing, make lithium rechargeable battery C1-C5, design capacity is 22.700 ampere-hours (Ah).
Embodiment 6
By obtained for the mixing of the 1-isobutyl-3,5-dimethylhexylphosphoric acid of the methane-disulfonic acid methylene ester of 30 weight portions, the vinylene carbonate of 35 weight portions and 1 weight portion combined additive A6.
Get respectively 48mL ethyl carbonate, 64mL diethyl carbonate and 48mL dimethyl carbonate, 24.32g lithium salts and 5 % by weight combined additive A6 mix with obtained electrolyte B6.
The positive and negative plate obtain above-mentioned preparation example 3 and the polypropylene diaphragm of 20 micron thickness are wound into the electrode group of square lithium ion secondary battery, and this electrode assembling is entered in rectangular cell aluminum hull, subsequently electrolyte B6 obtained before 160mL is injected in battery case, sealing, make lithium rechargeable battery C6, design capacity is 22.700 ampere-hours (Ah).
Embodiment 7
By the octadecyl phosphate of the methane-disulfonic acid methylene ester of 10 weight portions, the vinylene carbonate of 50 weight portions and 1 weight portion by the obtained combined additive A7 of mixing.
Get respectively 48mL ethyl carbonate, 64mL diethyl carbonate and 48mL dimethyl carbonate, 24.32g lithium salts and 5 % by weight combined additive A7 mix with obtained electrolyte B7.
The positive and negative plate obtain above-mentioned preparation example 3 and the polypropylene diaphragm of 20 micron thickness are wound into the electrode group of square lithium ion secondary battery, and this electrode assembling is entered in rectangular cell aluminum hull, subsequently electrolyte B7 obtained before 160mL is injected in battery case, sealing, make lithium rechargeable battery C7, design capacity is 22.700 ampere-hours (Ah).
Comparative example 1-2
The polypropylene diaphragm of above-mentioned positive and negative plate and 20 micron thickness is wound into the electrode group of square lithium ion secondary battery, and this electrode assembling is entered in rectangular cell aluminum hull, subsequently electrolyte DD1, DD2 obtained before 160mL are injected in the battery case of comparative example 1-2 respectively, sealing, make lithium rechargeable battery DDD1, DDD2, design capacity is 22.700 ampere-hours (Ah).
< test case >
The parameter of obtained battery C1-C7, DDD1-DDD2 is as shown in table 3.
Table 3
| Battery | Electrolyte | Voltage (V) | Thickness (mm) | DC internal resistance (M ω) | |
| Embodiment 1 | C1 | B1 | 3.3341 | 19.62 | 1.5 |
| Embodiment 2 | C2 | B2 | 3.334 | 19.72 | 1.6 |
| Embodiment 3 | C3 | B3 | 3.3336 | 19.68 | 1.7 |
| Embodiment 4 | C4 | B4 | 3.3337 | 19.70 | 1.6 |
| Embodiment 5 | C5 | B5 | 3.3334 | 19.68 | 1.6 |
| Embodiment 6 | C6 | B6 | 3.3334 | 19.65 | 1.6 |
| Embodiment 7 | C7 | B7 | 3.3331 | 20.68 | 1.7 |
| Comparative example 1 | DDD1 | DD1 | 3.3341 | 20.57 | 1.6 |
| Comparative example 2 | DDD2 | DD2 | 3.3341 | 20.50 | 1.6 |
Battery C1-C7, DDD1-DDD2 are stored 30 days at 60 DEG C, the data of each battery are as shown in table 4 below.Wherein, residual capacity (%) refers to that battery is full of the percentage that electricity stores remaining capacity and initial capacity after 30 days at 60 DEG C; It is complete that recovery capacity (%) refers to that battery is full of electricity storage its electric discharge of relief in 30 days at 60 DEG C, the electricity discharged after then it being full of again electricity and the percentage of initial capacity.
Table 4
As can be seen from the result shown in table 3 and table 4, the battery containing electrolyte provided by the invention can improve thickness swelling, capacity surplus ratio, the capacity restoration rate of battery high-temperature storage.And the thickness swelling of the high temperature storage of battery in comparative example 1-2 is large, capacity surplus ratio and recovery rate relatively low.And the battery of electrolyte provided by the invention is obviously little compared with comparative example in the pressure drop after storing 30 days at 60 DEG C.
Following table 5 is for illustration of battery C1-C7, DDD1, DDD2 discharge-rate test result under normal temperature (25 DEG C).Wherein 5C mean voltage refers to that the voltage obtained tested by battery when normal temperature 5C discharges; 10C mean voltage refers to that the voltage obtained tested by battery when normal temperature 10C discharges.
Table 5
| Discharge capacity (Ah) | 5C mean voltage (V) | 10C mean voltage (V) | |
| C1 | 22.625 | 2.846 | 2.5535 |
| C2 | 22.610 | 2.761 | 2.5037 |
| C3 | 22.612 | 2.761 | 2.4834 |
| C4 | 22.525 | 2.657 | 2.4235 |
| C5 | 22.523 | 2.637 | 2.4135 |
| C6 | 22.582 | 2.752 | 2.4732 |
| C7 | 22.585 | 2.727 | 2.4714 |
| DDD1 | 17.36 | 2.354 | 1.8750 |
| DDD2 | 19.52 | 2.125 | 1.9510 |
Result as shown in Table 5 can be found out, the high rate performance of the battery containing electrolyte provided by the invention is good, and the obvious battery more provided by the invention of the high rate performance of the battery of comparative example is poor.
Following table 6 is for illustration of battery C1-C7, DDD1, DDD2 discharge-rate test result under low temperature (-20 DEG C).Wherein, 1C discharge capacity ratio (%) refers to battery percentage of 1C discharge capacity under 1C discharge capacity and normal temperature (25 DEG C) under low temperature (-20 DEG C); 5C discharge capacity ratio (%) refers to battery percentage of 5C discharge capacity under 5C discharge capacity and normal temperature (25 DEG C) under low temperature (-20 DEG C).
Table 6
| 1C discharge capacity ratio (%) | 5C discharge capacity ratio (%) | |
| C1 | 95.37 | 81.98 |
| C2 | 95.35 | 78.91 |
| C3 | 95.09 | 77.35 |
| C4 | 95.01 | 75.84 |
| C5 | 95.07 | 75.94 |
| C6 | 94.99 | 77.05 |
| C7 | 95.00 | 75.14 |
| DDD1 | 84.23 | 52.36 |
| DDD2 | 85.30 | 50.21 |
Result as shown in Table 6 can be found out, the capacity of the battery containing electrolyte provided by the invention when low temperature is significantly higher, and the capacity of the battery in comparative example when low temperature is obviously on the low side.
Following table 7 is for illustration of battery C1-C7, DDD1, DDD2 recovery capacity (%) under high temperature (60 DEG C) after cycle charge-discharge, and this recovery capacity (%) refers to the capacity of battery in cyclic process and the percentage of initial capacity.
Table 7
| Cycle-index | C1 | C2 | C3 | C4 | C5 | C6 | C7 | DDD1 | DDD2 |
| 0 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| 10 | 98.96 | 98.98 | 98.95 | 98.87 | 98.77 | 98.75 | 98.47 | 94.53 | 95.85 |
| 50 | 98.10 | 98.38 | 98.56 | 96.48 | 96.68 | 97.56 | 96.58 | 91.03 | 94.45 |
| 100 | 95.39 | 95.79 | 95.88 | 94.47 | 94.77 | 94.84 | 94.87 | 89.06 | 92.51 |
| 150 | 94.30 | 94.67 | 94.74 | 93.19 | 93.29 | 93.71 | 93.29 | 88.45 | 91.22 |
| 200 | 94.51 | 94.48 | 94.41 | 93.09 | 93.10 | 93.41 | 93.19 | 86.29 | 91.12 |
| 250 | 94.04 | 94.01 | 94.03 | 93.03 | 93.03 | 93.13 | 93.20 | 84.20 | 90.18 |
| 300 | 93.88 | 93.41 | 93.35 | 92.23 | 92.23 | 92.31 | 92.23 | 82.10 | 88.37 |
| 350 | 92.52 | 92.87 | 92.98 | 91.96 | 91.86 | 91.78 | 91.86 | 81.12 | 86.74 |
| 400 | 92.10 | 92.39 | 92.62 | 91.78 | 91.82 | 91.62 | 91.72 | 80.32 | 85.57 |
| 450 | 91.84 | 91.89 | 91.46 | 90.80 | 90.80 | 90.56 | 90.81 | 78.30 | 84.87 |
| 500 | 91.44 | 91.39 | 91.36 | 90.00 | 89.68 | 90.39 | 90.58 | 75.46 | 82.76 |
Result as shown in Table 7 can be found out, obviously comparatively comparative example is high for the service life cycle at high temperature of the battery containing electrolyte provided by the invention.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned execution mode, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible compound mode.
In addition, also can carry out combination in any between various different execution mode of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. the combined additive of an electrolyte of lithium-ion secondary battery, it is characterized in that, this combined additive contains the methane-disulfonic acid methylene ester shown in formula (1), the phosphotriester shown in formula (2) and vinylene carbonate, and the weight of the methane-disulfonic acid methylene ester shown in formula (1): the weight of the phosphotriester shown in formula (2): the weight of vinylene carbonate is 0.04-100:1:0.1-100;
Wherein, the R in formula (2)
1, R
2and R
3identical or different, be separately selected from hydrogen, one in substituted or unsubstituted straight or branched alkyl that carbon number is 1-20.
2. combined additive according to claim 1, wherein, R
1, R
2and R
3identical or different, be separately selected from hydrogen, one in substituted or unsubstituted straight or branched alkyl that carbon number is 3-12.
3. combined additive according to claim 2, wherein, R
1, R
2and R
3for n-octyl.
4. combined additive according to claim 1, wherein, the weight of the methane-disulfonic acid methylene ester shown in formula (1): the weight of the phosphotriester shown in formula (2): the weight of vinylene carbonate is 4-80:1:5-80.
5. combined additive according to claim 4, wherein, the weight of the methane-disulfonic acid methylene ester shown in formula (1): the weight of the phosphotriester shown in formula (2): the weight of vinylene carbonate is 10-50:1:15-50.
6. an electrolyte of lithium-ion secondary battery, it is characterized in that, containing organic solvent, lithium salts and combined additive in this electrolyte, wherein, with the total weight of electrolyte, this electrolyte contains described combined additive 0.75-20 % by weight, and described combined additive is the combined additive in claim 1-5 described in any one.
7. electrolyte according to claim 6, wherein, this electrolyte contains described combined additive 1.7-10 % by weight.
8. electrolyte according to claim 6, wherein, described organic solvent is the weight of the mixed solvent of ethyl carbonate, diethyl carbonate and dimethyl carbonate, ethyl carbonate: the weight of diethyl carbonate: the weight of dimethyl carbonate is 1:1-2:0.5-1.5.
9. electrolyte according to claim 8, wherein, the weight of described ethyl carbonate: the weight of diethyl carbonate: the weight of dimethyl carbonate is 1:1-1.5:0.8-1.2.
10. electrolyte according to claim 7, wherein, described lithium salts is LiPF6, and in electrolyte, the concentration of lithium salts is 0.8-1.2mol/L.
11. 1 kinds of lithium rechargeable batteries, this battery battery container, electrode group and electrolyte, electrode group and electrolyte are sealed in battery container, and electrode group comprises positive pole, barrier film and negative pole, it is characterized in that, described electrolyte is the electrolyte in claim 6-10 described in any one.
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| WO2017075851A1 (en) * | 2015-11-04 | 2017-05-11 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| US10530016B2 (en) | 2015-12-18 | 2020-01-07 | Shenzhen Capchem Technology Co., Ltd. | Electrolyte for lithium-ion battery and lithium-ion battery |
| CN110911744A (en) * | 2018-09-17 | 2020-03-24 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
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| CN110911744A (en) * | 2018-09-17 | 2020-03-24 | 深圳新宙邦科技股份有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
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