CN104752764B - A kind of combined additive and electrolyte and lithium rechargeable battery - Google Patents
A kind of combined additive and electrolyte and lithium rechargeable battery Download PDFInfo
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- CN104752764B CN104752764B CN201310730891.1A CN201310730891A CN104752764B CN 104752764 B CN104752764 B CN 104752764B CN 201310730891 A CN201310730891 A CN 201310730891A CN 104752764 B CN104752764 B CN 104752764B
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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 kind of combined additive for lithium rechargeable battery, the electrolyte containing the combined additive and the battery containing the electrolyte, the combined additive contains formula（1）Shown methane-disulfonic acid methylene ester, formula（2）Shown phosphotriester and vinylene carbonate, and formula（1）Shown methane-disulfonic acid methylene ester, formula（2）Shown phosphotriester and the weight ratio of vinylene carbonate are 0.04 100：1：0.1‑100.Electrolyte containing the combined additive can overcome the defect of prior art, it is obviously improved capacity attenuation and thickness swelling of the battery containing the electrolyte in applied at elevated temperature or storage, and capacitance fall-off rate when circulating is reduced, low temperature performance also has raising by a relatively large margin.
Description
Technical field
The present invention relates to a kind of combined additive of electrolyte of lithium-ion secondary battery, a kind of containing the combined additive
Electrolyte and the lithium rechargeable battery containing the electrolyte.
Background technology
With the scarcity of traditional energy and running down for urban air pollution, electric automobile is increasingly by everybody
Concern.Lithium rechargeable battery is a kind of new electrochmical power source, have that energy density is big, operating voltage is high because of it, long lifespan,
The characteristics of without environmental hazard, cause the broad interest of researchers.But the use environment of automobile is with respect to battery of mobile phone, notes
This grade compact battery is more severe.Have to take into account the high-temperature behavior, cryogenic property and recycling of battery in this case
The factor such as life-span.And after existing electrolyte is often the high-temperature behavior for improving battery, the cryogenic property of battery will compare
Poor, after the cryogenic property for improving battery, the high-temperature behavior of battery will be poor, can't accomplish battery in height simultaneously
Effect under gentle low temperature can access the effect fully played.
Publication No. CN1925206A prior art discloses a kind of power-type lithium ion battery electrolyte, publication number
For CN101071863A prior art discloses the prior art of a kind of lithium battery electrolytes, Publication No. CN102064344A
Disclose being used prior art discloses one kind for a kind of novel electrolyte for power battery and Publication No. CN102437373A
In electrolyte of lithium iron phosphate dynamic battery and preparation method thereof.But electrolyte disclosed in above prior art is unsuitable for length
Used in the battery of electric automobile of the phase in various environment, the electricity provided for example with CN1925206A and CN101071863A
Solution liquid address only the safety problem that will not be set off an explosion during battery of the application under the high temperature conditions containing the electrolyte, but not
High power capacity can be kept at low ambient temperatures, and service life is short, thus it is not appropriate for the electrolyte as automobile power cell；
Although and the electrolyte for using CN102064344A to provide can obtain preferable cycle performance at high temperature, can not solve
High rate discharge when electric automobile is used in low temperature environment in actual life, that is, be unfavorable for discharging in low temperature environment, use the longevity
Life is short；Although battery containing the CN102437373A electrolyte provided can be used in low temperature and hot environment, but it is circulated
Service life is but very low, and capacitance reduction when recycling is quickly, thus adds and make while the energy is wasted
Use cost.
In summary, existing electrolyte has that use environment is limited, service life is not grown, discharge rate is high and circulation makes
The defect such as the capacitance reduction speed of used time is fast.
The content of the invention
It is an object of the invention to provide a kind of combined additive of electrolyte of lithium-ion secondary battery, contain combination addition
The electrolyte of agent can overcome the defect of prior art, hence it is evident that improve the battery containing the electrolyte in applied at elevated temperature or storage
Capacity attenuation and thickness swelling, and capacitance fall-off rate during reduction circulation, low temperature performance also has by a relatively large margin
Improve.
To achieve these goals, on the one hand, the present invention provides a kind of combination addition of electrolyte of lithium-ion secondary battery
Agent, the combined additive contains the sub- second of the methane-disulfonic acid methylene ester shown in formula (1), the phosphotriester shown in formula (2) and carbonic acid
Alkene ester, and the weight of the methane-disulfonic acid methylene ester shown in formula (1)：The weight of phosphotriester shown in formula (2)：Vinylene carbonate
The weight of ester is 0.04-100：1：0.1-100；
Wherein, the R in formula (2)1、R2And R3It is identical or different, it is separately taking for 1-20 selected from hydrogen, carbon number
One kind in generation or unsubstituted straight or branched alkyl.
On the other hand, the present invention also provides a kind of electrolyte of lithium-ion secondary battery, and the electrolyte contains organic solvent, lithium
Salt and combined additive of the present invention, wherein, with the gross weight meter of electrolyte, the electrolyte contains the combined additive
0.75-20 weight %.
On the other hand, the present invention also provides a kind of lithium rechargeable battery, and the battery includes battery container, electrode group and electricity
Liquid is solved, electrode group and electrolyte are sealed in battery container, electrode group includes positive pole, barrier film and negative pole, the electrolyte is this
The electrolyte provided is provided.
The lithium rechargeable battery of the electrolyte of lithium-ion secondary battery provided containing the present invention can be obviously improved in height
Capacity attenuation and thickness swelling when temperature is used or stored, and capacitance fall-off rate during reduction circulation, low temperature performance
Also there is raising by a relatively large margin.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of combined additive of electrolyte of lithium-ion secondary battery, the combined additive contains formula
(1) phosphotriester and vinylene carbonate shown in methane-disulfonic acid methylene ester, formula (2) shown in, and the first shown in formula (1)
The weight of alkane disulfonic acid methylene ester：The weight of 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、R2And R3It is identical or different, it is separately taking for 1-20 selected from hydrogen, carbon number
One kind in generation or unsubstituted straight or branched alkyl.
In the present invention, the carbon number includes but not limited for 1-20 substituted or unsubstituted straight or branched alkyl
One or more in following alkyl：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 the above-mentioned electrolyte of lithium-ion secondary battery that the present invention is provided, you can with bright
The aobvious capacity attenuation and thickness swelling for improving battery in applied at elevated temperature or storage, and capacitance fall-off rate when reducing circulation and
Improve low temperature performance.But it was found by the inventors of the present invention that under preferable case, in combined additive of the present invention
In, as R in formula (2)1、R2And R3It is identical or different, separately selected from hydrogen, the substitution or unsubstituted that carbon number is 3-12
Straight or branched alkyl in it is a kind of when, by the electrolyte containing the combined additive be used for lithium rechargeable battery can enter
One step improves capacity attenuation and thickness swelling of the battery in applied at elevated temperature or storage.
In the present invention, the carbon number includes but not limited for 3-12 substituted or unsubstituted straight or branched alkyl
One or more in following alkyl：Propyl group, isopropyl, butyl, isobutyl group, new butyl, amyl group, hexyl, octyl group, dodecane
Base and octadecyl.
Further, in the present invention, the carbon number is 3-12 substituted or unsubstituted straight or branched alkyl
One or more in including but not limited to following alkyl：-(CH2)7CH3、-(CH2)9CH3、-(CH2)11OCH3、-(CH2)10OCH2CH3、-(CH2)9CH2Cl、-(CH2)9CH3、-(CH2)11CH2Cl、-(CH2)15CH3、-(CH2)15CH2Cl、-(CH2)19CH3
With-(CH2)19CH3。
Present inventors discovered unexpectedly that when containing trioctyl phosphate in electrolyte of lithium-ion secondary battery, can be larger
The surface tension and viscosity of the reduction electrolyte of degree, and then improve the wettability and mobility on battery pole piece surface so that
The solvation of lithium ion, desolvated and diffusion velocity all make moderate progress under low temperature.While the branch chain of the length of trioctyl phosphate
Expansion, can form network structure, and have " induction " to methane-disulfonic acid methylene ester (MMDS) and vinylene carbonate (VC)
Effect, can make its dispersed, and by mesh in electrode surface film forming, the film of the formation is uniform and fine and close.MMDS is first equal
It is even by mesh film forming, and membrane formation mechanism with it is upper identical so that film is evenly；VC " is lured in the long-chain of trioctyl phosphate afterwards
Lead " act on lower by same mesh film forming, the two-step film forming is equally uniform, and further increases uniformity, therefore enters one
Walk preferred R1、R2And R3For n-octyl.
Under preferable case, the methane-disulfonic acid methylene ester shown in formula (1), formula (2) institute in combined additive of the invention
The phosphotriester and the weight ratio of vinylene carbonate shown is 4-80：1：5-80, the weight ratio of further preferred three is 10-
50：1：15-50.
To the preparation method of combined additive of the present invention, there is no particular limitation, can be side well known in the art
Method.For example, can be by the methane-disulfonic acid methylene ester shown in formula (1), the phosphotriester and vinylene carbonate shown in formula (2)
Using weight ratio as 0.04-100：1：0.1-100 is mixed；
Wherein, the R in formula (2)1、R2And R3It is identical or different, it is separately taking for 1-20 selected from hydrogen, carbon number
One kind in generation or unsubstituted straight or branched alkyl.There is no particular limitation for the method for wherein described mixing, is this area
Interior known, also there is no particular limitation for the addition sequence of above-mentioned three kinds of materials, can be added and be mixed with random order.
The present invention also provides a kind of electrolyte for lithium rechargeable battery, and the electrolyte contains organic solvent, lithium salts
With above-mentioned any one combined additive of the present invention, wherein, with the gross weight meter of electrolyte, the electrolyte contains combined additive
0.75-20 weight %.
When the above-mentioned electrolyte of the present invention is used for into lithium rechargeable battery, it becomes possible to capacitance when substantially reduction is circulated
Attenuation rate simultaneously improves low temperature performance.But, it was found by the inventors of the present invention that it is preferred that containing the above-mentioned of the present invention in electrolyte
When any one combined additive 1.7-10 weight %, further preferred combined additive are 2-8 weight %, contain the electrolyte
The attenuation rate of circulation capacitance of battery significantly reduce, and low temperature performance can also be increased substantially.
Organic solvent in electrolyte of the present invention can be carried out by those skilled in the art according to conventional species
Selection, for example organic solvent can be selected from gamma-butyrolacton, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate
Ester, methyl propyl carbonate, dipropyl carbonate, propene carbonate, methyl formate, methyl acrylate, methyl butyrate, ethyl acetate, Asia
Sulfuric acid vinyl ester, propylene sulfite, methyl sulfide, dimethyl sulfite, sulfurous acid diethyl ester, tetrahydrofuran, acid anhydrides, N- methyl
In pyrrolidones, N-METHYLFORMAMIDE, N- methylacetamides, acetonitrile, N,N-dimethylformamide, sulfolane and dimethyl sulfoxide
One or more.
Lithium salts in electrolyte of the present invention can be selected by those skilled in the art according to conventional species,
Such as described lithium salts can be selected from LiPF6、LiClO4、LiBF4、LiAsF6、LiSiF6、LiB(C6H5)4、LiCl、LiBr、LiI、
LiAlCl4、LiBOB、LiCF3SO3、LiC4F9SO3And LiN (CxF2x+1SO2)(CyF2y+1SO2) in one or more, wherein, x
It is positive integer with y.
In the present invention, it is preferred to which the organic solvent in the electrolyte is selected from gamma-butyrolacton, ethylene carbonate, carbonic acid two
One or more in ethyl ester and dimethyl carbonate.Contain to increase lithium salts solubility in organic solvent and further improve
There are capacity attenuation and thickness swelling of the battery of the electrolyte in applied at elevated temperature or storage, present invention preferably uses above-mentioned organic
The mixed solvent of two kinds, three kinds or four kinds compositions in solvent.
In the present invention, it is preferred to which the lithium salts is selected from LiPF6、LiClO4、LiBF4、LiAsF6And LiSiF6In one kind
Or it is a variety of.
The further preferably organic solvent of the invention is the mixing of ethylene carbonate, diethyl carbonate and dimethyl carbonate
Solvent.
Under preferable case, the weight ratio of ethylene carbonate of the present invention, diethyl carbonate and dimethyl carbonate is 1：
1-2：0.5-1.5, the weight ratio of still more preferably above-mentioned three is 1：1-1.5：During 0.8-1.2, the electricity containing the electrolyte
Capacity attenuation and thickness swelling of the pond in applied at elevated temperature or storage improve more notable.
In the case of further preferably, the lithium salts in electrolyte of the present invention is LiPF6。
Under preferable case, the concentration of lithium salts is 0.5-1.5mol/L in electrolyte of the present invention；Still more preferably
The concentration of lithium salts is 0.8-1.2mol/L in electrolyte.
In addition, as needed, electrolyte provided by the present invention can also the additive containing various functions, for example may be used
To contain film for additive, flame-retardant additive etc..The film for additive can be added well known to a person skilled in the art various
Plus agent, such as carbon dioxide, carbon disulfide, sulfur dioxide, ethylene sulfite (ES), propylene sulfite (PS) and lithium carbonate
In one or more.
There is no particular limitation for preparation method of the present invention to the electrolyte, can be known method, for example, described
The preparation method of electrolyte can include lithium salts and combined additive being added in organic solvent, and then stirring makes it fully molten
Solve, be uniformly dispersed, resulting solution is the electrolyte that the present invention is provided.Wherein, the addition sequence of lithium salts and combined additive does not have
Require, can be separately added into, can also add simultaneously.
The present invention also provides a kind of lithium rechargeable battery, and the battery includes battery container, electrode group and electrolyte, electrode
Group and electrolyte are sealed in battery container, and electrode group includes positive pole, barrier film and negative pole, and the electrolyte is above-mentioned for the present invention's
Any one electrolyte.
The structure of the electrode group is known to those skilled in the art, in general, and the electrode group is included successively
Winding or stacked positive pole, barrier film and negative pole, barrier film are located between positive pole and negative pole.Winding or stacked mode have also been ability
Well known to field technique personnel, it will not be repeated here.
The composition of the positive pole is known to those skilled in the art, in general, and positive pole includes collector and coating
And/or the positive electrode of filling on a current collector.The collector is known to those skilled in the art, for example, can be selected from
Aluminium foil, copper foil, nickel plated steel strip or Punching steel strip.The positive electrode is known to those skilled in the art, generally includes just
The conductive agent that pole active material, adhesive and selectivity contain, the positive active material can be selected from lithium rechargeable battery
Conventional positive active material, such as LixNi1-yCoO2(0.9≤x≤1.1,0≤y≤1.0), LimMn2-nAnO2(A is transition gold
Category, 0.9≤m≤1.1,0≤n≤1.0), Li1+aMbMn2-bO4(- 0.1≤a≤0.2,0≤b≤1.0, M be lithium, boron, magnesium,
One or more in the elements such as aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, sulphur), LiFe1-x-yMxNyPO4
(0.001≤x, y≤0.1, M, N are the one or more in the elements such as magnesium, strontium, aluminium, tin, antimony, vanadium, yttrium, titanium)；The conductive agent
Can be the one or more of acetylene black, electrically conductive graphite or conductive carbon fibre；Described adhesive can be Kynoar
(PVDF)。
The preparation method of the positive pole, for example can be by LiFePO to be well known in the art4, conductive material, adhesive
It is 100 by weight：4-10：3-10 ratio is mixed and stirs into slurry with appropriate NMP (1-METHYLPYRROLIDONE), and this is starched
Material is applied on 12-20 μm of Al paper tinsels, and positive plate is obtained through drying, compacting.
The negative pole can use negative pole known in the field, in general, and negative pole includes negative current collector and coating
And/or it is filled in the negative material on the negative current collector.The conductive current collector is known to those skilled in the art, for example
Can be selected from the one or more in aluminium foil, copper foil, nickel plated steel strip, Punching steel strip.The present invention is not special to negative material
Limitation, like the prior art, what the negative material generally include negative electrode active material, adhesive and selectivity contained leads
Electric agent.The negative electrode active material can use various negative electrode active materials commonly used in the prior art, such as carbon material.It is described
Carbon material can be non-graphitic carbon, graphite or the charcoal obtained by polyacetylene high polymer material by high-temperature oxydation, it is possible to use
Other carbon materials are such as pyrolytic carbon, coke, organic polymer sinter, activated carbon, and the organic polymer sinter can be with
Be as phenolic resin, epoxy resin etc. are sintered and after carbonizing obtained by product；Described adhesive can be polytetrafluoroethylene (PTFE)
(PTFE)；The Kynoar (PVDF).
The preparation method of the negative pole, for example can be by powdered graphite that average grain diameter is 12 μm to be well known in the art
It is 100 by weight with polytetrafluoroethylene (PTFE) (PTFE), sodium carboxymethylcellulose (CMC)：2-7：1-3 is used as solvent using deionized water
It is mixed to get negative material paste.The negative material paste is applied on 10-16 μm of copper foil dry, compacting and obtains negative pole
Piece.
There is no particular limitation for preparation method of the present invention to lithium rechargeable battery, can be public for those skilled in the art
The various preparation methods known, for example, the preparation method of the battery can include that barrier film will be set between positive pole and negative pole, constitute electricity
Pole group, the electrode group is accommodated in the cell housing, injects electrolyte, then that battery container is closed, wherein, the electrolyte
The electrolyte provided for the present invention.In addition to the electrolyte that the electrolyte provides for the present invention, other steps are this area
Well known to technical staff, it will not be repeated here.
The present invention will be described in detail by way of examples below.In following examples, in the feelings being not particularly illustrated
Condition is come, it is raw materials used be all from it is commercially available.The voltage and capacitance of the present invention is surveyed by test cabinet (trade mark is new Weir 500A/5V)
Try and obtain, internal resistance is obtained by internal resistance instrument (trade mark is BK-6802/300A) test.
Preparation example 1
Methane-disulfonic acid methylene ester, vinylene carbonate and trioctyl phosphate are mixed by weight ratio as shown in table 1 below
Combined additive A1-A5, D1 is made.
Table 1
Preparation example 2
48mL ethylene carbonates, 64mL diethyl carbonates and 48mL dimethyl carbonates, 24.32g lithium salts and as follows are taken respectively
The combined additive of weight % shown in table 2 mixes that electrolyte B1-B5 and DD1, DD2 is made.
Table 2
| Electrolyte | The species of combined additive | The 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 LiFePO4, 90 grams of aluminium foils, 90 grams of electrically conductive graphites and 90 grams of PVDF mixing and stirred with 1350 grams of NMP
Into slurry, on the aluminium foil that the slurry is applied to 16 μm, dried 1 hour through 125 DEG C, about 3000 millimeters are obtained after roll-in, cut-parts
× 150 millimeters × 0.125 millimeter of positive plate.
The preparation of negative pole：
It is that 12 μm of powdered graphite and 30 grams of PTFE, 20 grams of CMC are made with 1600mL deionized waters by 1395 grams of average grain diameters
Negative material paste is mixed to get for solvent.The negative material paste is coated on 12 microns of thick copper foils and dry through 125 DEG C
Dry 1 hour, about 3020 millimeters × 160 millimeters × 0.100 millimeter of negative plate is obtained after roll-in, cut-parts.
Embodiment 1-5
The positive and negative plate and 20 microns of thick polypropylene diaphragms that above-mentioned preparation example 3 is obtained are wound into rectangular lithium ion two
The electrode group of primary cell, and the electrode group is fitted into rectangular cell aluminum hull, then by electrolyte obtained before 160mL
B1-B5 is injected separately into embodiment 1-5 battery case, sealing, lithium rechargeable battery C1-C5 is made, design capacity is
22.700 ampere-hour (Ah).
Embodiment 6
By the dodecane of the methane-disulfonic acid methylene ester, the vinylene carbonate of 35 parts by weight and 1 parts by weight of 30 parts by weight
Base phosphate is mixed to prepare combined additive A6.
48mL ethylene carbonates, 64mL diethyl carbonates and 48mL dimethyl carbonates, 24.32g lithium salts and 5 weights are taken respectively
The combined additive A6 for measuring % mixes that electrolyte B6 is made.
The positive and negative plate and 20 microns of thick polypropylene diaphragms that above-mentioned preparation example 3 is obtained are wound into rectangular lithium ion two
The electrode group of primary cell, and the electrode group is fitted into rectangular cell aluminum hull, then by electrolyte B6 obtained before 160mL
It is injected into battery case, seals, lithium rechargeable battery C6 is made, design capacity is 22.700 ampere-hours (Ah).
Embodiment 7
By the octadecane of the methane-disulfonic acid methylene ester, the vinylene carbonate of 50 parts by weight and 1 parts by weight of 10 parts by weight
Base phosphate is by being mixed to prepare combined additive A7.
48mL ethylene carbonates, 64mL diethyl carbonates and 48mL dimethyl carbonates, 24.32g lithium salts and 5 weights are taken respectively
The combined additive A7 for measuring % mixes that electrolyte B7 is made.
The positive and negative plate and 20 microns of thick polypropylene diaphragms that above-mentioned preparation example 3 is obtained are wound into rectangular lithium ion two
The electrode group of primary cell, and the electrode group is fitted into rectangular cell aluminum hull, then by electrolyte B7 obtained before 160mL
It is injected into battery case, seals, lithium rechargeable battery C7 is made, design capacity is 22.700 ampere-hours (Ah).
Comparative example 1-2
Above-mentioned positive and negative plate and 20 microns of thick polypropylene diaphragms are wound into the electrode of square lithium ion secondary battery
Group, and the electrode group is fitted into rectangular cell aluminum hull, then electrolyte DD1, DD2 obtained before 160mL are noted respectively
Enter into comparative example 1-2 battery case, seal, lithium rechargeable battery DDD1, DDD2 is made, design capacity is 22.700 ampere-hours
(Ah)。
<Test case>
The parameter that battery C1-C7, DDD1-DDD2 is made 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, remain
Covolume amount (%) refers to fully charged remaining capacity and the percentage of initial capacity after being stored 30 days at 60 DEG C of battery；Recover to hold
Amount (%) refers to that battery is fully charged complete in storing 30 days reliefs its electric discharges at 60 DEG C, is then again filled with what is discharged after electricity
The percentage of electricity and initial capacity.
Table 4
The battery of the electrolyte provided it can be seen from the result shown in table 3 and table 4 containing the present invention can improve battery
The thickness swelling of high temperature storage, capacity surplus ratio, capacity restoration rate.And the thickness of the high temperature storage of the battery in comparative example 1-2
Expansion is big, capacity surplus ratio and recovery rate are relatively low.And the battery for the electrolyte that the present invention is provided is store at by 60 DEG C
Deposit the pressure drop after 30 days substantially small compared with comparative example.
Table 5 below is used to illustrate the discharge-rate test result of battery C1-C7, DDD1, DDD2 under normal temperature (25 DEG C).Wherein
5C mean voltages refer to that battery tests obtained voltage when normal temperature 5C discharges；10C mean voltages refer to that battery is put in normal temperature 10C
Obtained voltage is tested when electric.
Table 5
| Discharge capacity (Ah) | 5C mean voltages (V) | 10C mean voltages (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 |
The high rate performance that result as shown in Table 5 can be seen that the battery of the electrolyte provided containing the present invention is good, and
Substantially the battery more of the invention provided is poor for the high rate performance of the battery of comparative example.
Table 6 below is used to illustrate the discharge-rate test result of battery C1-C7, DDD1, DDD2 under low temperature (- 20 DEG C).Its
In, 1C discharge capacities ratio (%) refers to that battery 1C discharge capacities under low temperature (- 20 DEG C) are held with 1C electric discharges under normal temperature (25 DEG C)
The percentage of amount；5C discharge capacities ratio (%) refers to battery under low temperature (- 20 DEG C) under 5C discharge capacities and normal temperature (25 DEG C)
The percentage of 5C discharge capacities.
Table 6
| 1C discharge capacities ratio (%) | 5C discharge capacities 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 seen that capacity of the battery of the electrolyte provided containing the present invention in low temperature and show
Write higher, and capacity of the battery in low temperature in comparative example is substantially relatively low.
Table 7 below is used to illustrate the recovery capacity of battery C1-C7, DDD1, DDD2 under high temperature (60 DEG C) after cycle charge-discharge
(%), the recovery capacity (%) refers to battery in the capacity of 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, which can be seen that the circulation of the battery of the electrolyte provided containing the present invention at high temperature, to be made
It is substantially high compared with comparative example with the life-span.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (11)
1. a kind of combined additive of electrolyte of lithium-ion secondary battery, it is characterised in that the combined additive contains formula (1) institute
Phosphotriester and vinylene carbonate shown in the methane-disulfonic acid methylene ester that shows, formula (2), and the sulphur of methane two shown in formula (1)
The weight of sour methylene ester：The weight of 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、R2And R3It is identical or different, separately selected from carbon number is 1-20 substitution or does not take
One kind in the straight or branched alkyl in generation.
2. combined additive according to claim 1, wherein, R1、R2And R3It is identical or different, separately selected from carbon
Atomicity is one kind in 3-12 substituted or unsubstituted straight or branched alkyl.
3. combined additive according to claim 2, wherein, R1、R2And R3For n-octyl.
4. combined additive according to claim 1, wherein, the weight of the methane-disulfonic acid methylene ester shown in formula (1)：Formula
(2) weight of the phosphotriester shown in：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)：Formula
(2) weight of the phosphotriester shown in：The weight of vinylene carbonate is 10-50：1：15-50.
6. a kind of electrolyte of lithium-ion secondary battery, it is characterised in that add in the electrolyte containing organic solvent, lithium salts and combination
Plus agent, wherein, with the gross weight meter of electrolyte, the electrolyte contains the combined additive 0.75-20 weight %, and described group
It is the combined additive described in any one in claim 1-5 to close additive.
7. electrolyte according to claim 6, wherein, the electrolyte contains the combined additive 1.7-10 weight %.
8. electrolyte according to claim 6, wherein, the organic solvent is ethylene carbonate, diethyl carbonate and carbon
The mixed solvent of dimethyl phthalate, the weight of ethylene 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 the ethylene carbonate：The weight of diethyl carbonate：Carbon
The weight of dimethyl phthalate is 1：1-1.5：0.8-1.2.
10. electrolyte according to claim 7, wherein, the lithium salts is LiPF6, the concentration of lithium salts is 0.8- in electrolyte
1.2mol/L。
11. a kind of lithium rechargeable battery, the battery includes battery container, electrode group and electrolyte, electrode group and electrolysis are liquid-tight
It is enclosed in battery container, electrode group includes positive pole, barrier film and negative pole, it is characterised in that the electrolyte is claim 6-10
Electrolyte described in middle any one.
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| CN110247114A (en) | 2015-12-18 | 2019-09-17 | 深圳新宙邦科技股份有限公司 | A kind of electrolyte for lithium ion battery and lithium ion battery |
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| CN110911744B (en) * | 2018-09-17 | 2021-09-17 | 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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| CN102064344A (en) * | 2010-12-21 | 2011-05-18 | 东莞市杉杉电池材料有限公司 | Novel electrolyte for power battery |
| CN102263292A (en) * | 2011-06-24 | 2011-11-30 | 九江天赐高新材料有限公司 | Non-aqueous electrolytic solution used for lithium secondary batteries |
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| CN102263292A (en) * | 2011-06-24 | 2011-11-30 | 九江天赐高新材料有限公司 | Non-aqueous electrolytic solution used for lithium secondary batteries |
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