CN106848404B - A kind of lithium-ion battery electrolytes functional additive, lithium-ion battery electrolytes and lithium ion battery - Google Patents
A kind of lithium-ion battery electrolytes functional additive, lithium-ion battery electrolytes and lithium ion battery Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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- 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
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The present invention relates to a kind of lithium-ion battery electrolytes functional additive, lithium-ion battery electrolytes and lithium ion batteries, belong to technical field of lithium ion.Functional additive of the invention includes the component of following parts by weight: 0.5~3 part of vinylene carbonate, 0.1~2 part of difluoro dioxalic acid lithium borate, 0.1~2 part of difluorophosphate, 3~5 parts of fluorobenzene, 0.1~1 part of methane-disulfonic acid methylene ester；Electrolyte of the invention includes lithium salts, organic solvent and functional additive, functional additive each component mass percent in the electrolytic solution are as follows: vinylene carbonate 0.5%~3%, difluoro dioxalic acid lithium borate 0.1%~2%, difluorophosphate 0.1%~2%, fluorobenzene 3%~5%, methane-disulfonic acid methylene ester 0.1%~1%；The invention further relates to the lithium ion battery for using the electrolyte, the high temperature cyclic performance of the lithium ion battery is significantly increased.
Description
Technical field
The present invention relates to a kind of lithium-ion battery electrolytes functional additive, lithium-ion battery electrolytes and lithium-ion electrics
Pond belongs to technical field of lithium ion.
Background technique
Now about the energy and environmental protection problem be concerned, electric car have become automobile industry development trend and
One of direction.According to the needs of the strategy of sustainable development, the Chinese government actively promotes the research, exploitation and industry of electric car
Change, is in full swing from key components and parts to vehicle using work.
Although the technology path of various countries' Development of EV is different, crucial portion of the power battery as electric car
Part is constantly subjected to the attention of researcher for a long time.Lithium ion battery is because of its energy density height, good cycle, safe and reliable
Property high and environmental suitability it is strong the advantages that, that comes into being becomes power battery of new generation, can be widely applied to various shiftings
The fields such as power driven tools, automobile, device drives and energy storage.
The thermal adaptability of application with lithium ion battery in electric car field, lithium ion battery receives increasingly
Extensive concern.In China, for most area summer environment temperature generally up to 38 DEG C or so, circulating battery fever leads to battery
Actual temperature is up to 45 DEG C or so in group, has seriously affected the cycle life of battery.Currently, patent CN103985903A is disclosed
A kind of high-temperature behavior electrolyte of lithium manganate power battery, the non-aqueous organic solvent comprising 75wt%~88wt%, 10wt%~
The lithium salts of 17wt%, the film for additive of 0.5wt%~6wt%, the high temperature additive of 0.5wt%~5wt%, 0.5wt%~
The surfactant of 3wt% and the stabilizer of 0.001wt%~1wt%；The non-aqueous organic solvent is ethylene carbonate
(EC), one of propene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC) or methyl ethyl carbonate (EMC)
Or it is several；Lithium salts can be selected from LiPF6The composition of/LiFSI/LIDFOB, film for additive are vinylene carbonate (VC),
High temperature additive is methane-disulfonic acid methylene ester (MMDS), methane-disulfonic acid methylene ester (MMDS) and p-methyl benzenesulfonic acid isocyanates
(PTSI) one or both of combination；Surfactant is fluorine-containing surfactant.The battery is filled at 55 DEG C with 0.5C
After discharge cycles 140 times, specific discharge capacity is 90% or so, it is contemplated that after high current 1C charge and discharge 500 times, discharge ratio
Capacity is certainly less than 90%, so the electrolyte is not able to satisfy high current, the demand of electric discharge is repeated several times.Patent
CN104781976A (applying date 2014.02.20) discloses a kind of non-aqueous electrolytic solution, includes Non-aqueous Organic Solvents, lithium
Salt and electrolyte solution additive；The non-aqueous solvent includes linear carbonic ether and cyclic carbonate fat or a combination thereof；Institute
The lithium salts stated includes being selected from LiPF6、LiN(CF3SO2)2、LiN(C2F5SO2)2Equal lithium salts；Electrolyte solution additive is difluoro phosphorus
Sour lithium (LiDFP), vinylene carbonate methyl esters, sultone composition composition, but it is charged at 55 DEG C with 1C, and 3C discharges 500 times
Capacity retention ratio still cannot be met the requirements after circulation.Patent CN102064344A (applying date 2010.12.21) discloses one kind
Novel electrolyte for power battery is recycled under the conditions of high-temperature lithium ion battery by the additive in regulation formula system to improve
Performance, and demonstrate addition methane-disulfonic acid methylene ester (MMDS) circulation volume conservation rate can be significantly improved at room temperature,
But without disclosing its circulation volume conservation rate under the high temperature conditions.
Summary of the invention
In order to promote lithium ion battery in the performance of hot conditions, the first purpose of this invention be to provide a kind of lithium from
Sub- battery electrolyte functional additive.
Second object of the present invention is to provide a kind of good lithium-ion battery electrolytes of high-temperature behavior, to improve lithium
The service life of ion battery at high temperature.
Third object of the present invention is to provide a kind of hot conditions, the lithium ion battery of superior performance.
To achieve the goals above, of the invention the technical solution adopted is as follows:
Lithium-ion battery electrolytes functional additive of the invention, the component including following parts by weight: carbonic acid Asia second
0.5~3 part of enester (VC), 0.1~2 part of difluoro dioxalic acid lithium borate (LiODFB), difluorophosphate (LiPOF2) 0.1~2 part,
3~5 parts of fluorobenzene (FB), 0.1~1 part of methane-disulfonic acid methylene ester (MMDS).
Lithium-ion battery electrolytes of the invention, including lithium salts, organic solvent, further include functional additive, the function
Additive includes the component of following parts by weight: 0.5~3 part of vinylene carbonate, 0.1~2 part of difluoro dioxalic acid lithium borate, two
0.1~2 part of lithium fluophosphate, 3~5 parts of fluorobenzene, 0.1~1 part of methane-disulfonic acid methylene ester.
The mass percent of each component of the functional additive in the electrolytic solution are as follows: vinylene carbonate 0.5%~
3%, difluoro dioxalic acid lithium borate 0.1%~2%, difluorophosphate 0.1%~2%, fluorobenzene 3%~5% and methane-disulfonic acid
Methylene ester 0.1%~1%.
The lithium salts is lithium hexafluoro phosphate (LiPF6), bis- (fluorine sulphonyl) imine lithiums (LiFSI), bis- (trifluoromethyl sulphurs
Acyl) one of imine lithium (LiTFSI) or a variety of.
The concentration of the lithium salts in the electrolytic solution is 0.5~2mol/L.
The organic solvent is the mixture of cyclic carbonate fat and chain carbonic ether.
The chain carbonic ether is diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate.
The cyclic carbonate fat is ethylene carbonate, propene carbonate.
The organic solvent composition is preferably that the mass percent of each component is ethylene carbonate 30%, diethyl carbonate
35%, methyl ethyl carbonate 15%, dimethyl carbonate 20%.
Difluorophosphate is added in organic solvent, durable ESI film can be formed on cathode, thus difluorophosphate
It can inhibit the decomposition for the positive electrode surface that may occur during high temperature circulation, and the oxidation of electrolyte solution can be prevented anti-
It answers.Based on the total amount of electrolyte solution, difluorophosphate (LiP (O) F2) content be 0.1~2wt%.Difluorophosphate
It is unobvious to the high temperature cyclic performance improvement of lithium ion battery in the case that content is lower than 0.1wt%, and content is higher than 2wt%
In the case where, during lithium ion battery charge and discharge, difluorophosphate possibly can not be completely consumed when forming ESI film, be filled
It decomposes, unreacted excessive difluorophosphate may form sediment in the electrolytic solution, reduce the impedance of lithium ion battery
Characteristic, and influence the cycle performance and service life of lithium ion battery.
Vinylene carbonate base ester can act synergistically together with difluorophosphate in the electrolytic solution, form stable SEI film.Carbon
The content of sour ethenylidene ester is preferably 0.5~3wt%, in the case where vinylene carbonate ester content is lower than 0.5wt%, carbonic acid
Ethenylidene ester cannot be acted on sufficiently with difluorophosphate, can not form expected SEI film, be higher than in vinylene carbonate base ester content
When 3wt%, side reaction occurs between vinylene carbonate base ester and positive active material, the SEI film being formed simultaneously also can be blocked up, leads
It causes impedance to increase, influences high-temperature lithium ion battery cycle performance.
Three kinds of methane-disulfonic acid methylene ester, fluorobenzene and vinylene carbonate substances can act synergistically, and promote lithium ion battery
Battery forms the SEI film of dense uniform, and it is special in structure to be formed by SEI film, is not easy to decompose at relatively high temperatures and destroy,
Ensure that lithium ion battery under the high temperature conditions has preferable performance.
Third object of the present invention is to provide a kind of using lithium ion battery made of above-mentioned electrolyte, satisfaction industry
Production and life use the demand of lithium ion battery under the high temperature conditions.
In the present invention lithium ion battery the preparation method is as follows:
Step 1: battery core is made in positive plate, diaphragm and negative electrode tab, and battery core is packed into battery case, injects this hair
Lithium-ion battery electrolytes in bright, chemical conversion；
Step 2: carrying out high temperature at a temperature of being placed in 40 DEG C~85 DEG C after the lithium ion battery that the first step is obtained completely fills
Aging process；
Step 3: the battery pumping in second step, sealing, constant volume are obtained final lithium ion battery.
Positive active material used is LiCoO on the positive plate of the lithium ion battery2、LiFePO4、LiMn2O4、
LiMn1-yMyPO4、LiMn1-yMyO4And LiNixCoyMnzM1-x-y-zO2In any one or a few；Wherein, M is independent is
Any one in Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V, Ti, and 0≤y≤1,0≤x≤1,0≤z
≤ 1, x+y+z≤1.
Negative electrode active material in the negative electrode tab used of the lithium ion battery is artificial graphite, natural graphite, soft
Any one in carbon, Si/C negative electrode material or combination.
Diaphragm used in the lithium ion battery be polyethylene film (PE), polypropylene screen (PP), polypropylene, polyethylene/
One kind of polypropylene composite film (PP/PE/PP).
The material of shell used in the lithium ion battery is aluminum plastic film, in fiber glass reinforced polypropylene (PP), stainless steel, aluminium
One kind.
As the lithium ion battery in the present invention, battery core production method is one of winding, lamination.
The temperature and both parameters of high temperature ageing time of high temperature aging of the present invention have certain relationship.When high temperature ageing
Between reduced with the raising of high temperature ageing temperature: when 40 DEG C~50 DEG C of high temperature ageing temperature, the high temperature ageing time be 3~7 days；
When high temperature ageing temperature 50 C~60 DEG C, the high temperature ageing time is 1~3 day；When high temperature ageing temperature 60 C~85 DEG C, high temperature is old
The change time is 8h~1 day.
Compared with prior art, the characteristic of electrolyte of the invention is to take full advantage of vinylene carbonate, fluorobenzene, first
The synergistic effect of alkane disulfonic acid methylene ester three forms the good additive of high-temperature behavior, improves the high-temperature behavior of battery.Electricity
Difluorophosphate, two kinds of compositions containing lithium of difluoro dioxalic acid lithium borate are added in pond, two kinds of compositions containing lithium and lithium salts act on chemical conversion
Stage, which forms SEI film in graphite cathode surface, has good thermal stability, while also having lower impedance, therefore improve
The cycle performance of lithium ion battery under the high temperature conditions.
By adding above-mentioned electrolyte in lithium ion battery, the lithium battery of preparation has good property under the conditions of height
Can, it can satisfy the needs living needs of operation or industrial needs under the high temperature conditions, and its cycle performance is good, can apply
Longer time ensure that safety, and saved cost without replacing battery.
The SEI film that the improved-type functional additive of high temperature of the invention was formed in graphite cathode surface in the chemical conversion stage is with good
Good thermal stability has lower impedance simultaneously, therefore does not reduce the low of battery while promoting battery high-temperature cycle performance
Warm discharge performance；Using full electric high temperature ageing technique, battery carries out reconstruction in the SEI film that the chemical conversion stage is formed, film it is molten
Solution makes new film that there is porous structure to make so that electrolyte further contacts with electrode and continues to restore with redeposited
Finally formed SEI film is finer and close, stablizes, and achievees the purpose that improve battery high-temperature cycle performance.
Specific embodiment
Embodiment 1
The ion battery electrolyte of the present embodiment is grouped as with functional additive by the group of following parts by weight: carbonic acid Asia second
2 parts of enester (VC), 0.3 part of difluoro dioxalic acid lithium borate (LiODFB), difluorophosphate (LiPOF2) 0.5 part, fluorobenzene (FB) 3
Part, 0.2 part of methane-disulfonic acid methylene ester (MMDS).
The present embodiment intermediate ion battery electrolyte includes lithium salts, organic solvent, functional additive, is more specifically for lithium salts
Lithium hexafluoro phosphate (LiPF6), the concentration of lithium hexafluoro phosphate in the electrolytic solution is 1.2mol/L, organic solvent used in the present embodiment
For the mixture of cyclic carbonate fat and chain carbonic ether, wherein cyclic carbonate fat is ethylene carbonate, mass percent 30%,
Chain carbonic ether be diethyl carbonate, methyl ethyl carbonate and dimethyl carbonate, mass percent be respectively diethyl carbonate 35%,
Methyl ethyl carbonate 15%, dimethyl carbonate 20%；Contained functional additive each component accounts for the mass percent of entire electrolyte
Respectively vinylene carbonate (VC) 2%, difluoro dioxalic acid lithium borate (LiODFB) 0.3%, difluorophosphate (LiPOF2)
0.5%, fluorobenzene (FB) 3%, methane-disulfonic acid methylene ester (MMDS) 0.2%.
Lithium ion battery preparation includes the preparation of positive plate, the preparation of negative electrode tab and lithium ion battery in the present embodiment
Preparation.Detailed process is as follows:
The preparation of positive plate:
By iron phosphate serving as positive active material (LiFePO4), conductive agent Super-P (SP), bonding agent PVDF is according to quality
Ratio 92: 4: 4 is added in nmp solvent the obtained anode sizing agent that is uniformly dispersed.Anode sizing agent is coated on Al foil, roller is carried out
Pressure, slice and baking process, are made positive plate.
The preparation of negative electrode tab:
By negative electrode active material artificial graphite, conductive agent SP, bonding agent SBR emulsion (SBR) and thickening agent carboxymethyl
The obtained cathode that is uniformly dispersed is added in solvent deionized water according to mass ratio 95: 1.0: 2.5: 1.5 and starches for sodium cellulosate (CMC)
Material.Negative electrode slurry is coated on Cu foil, the operation such as roll-in, slice and drying is carried out, negative electrode tab is made.
The double-deck microporous barrier of polypropylene (PP) that diaphragm uses with a thickness of 32 μm.
The preparation of lithium ion battery:
Above-mentioned positive plate, negative electrode tab and diaphragm are fabricated to battery core according to Z-shaped lamination process, battery core is packed into aluminum plastic film
In packaging bag, and vacuum bakeout is carried out, above-mentioned lithium-ion battery electrolytes are perfused, Vacuum Package, chemical conversion then are carried out to battery core.
Following high temperature ageing processing is carried out to above-mentioned lithium ion battery: battery core is completely charged to the rate of charge of 0.3C
Then 3.65V stands 5 days in 45 DEG C of baking oven, battery core is placed cooling a period of time at normal temperature after standing, is allowed to
It is restored to room temperature.
Final lithium ion battery is obtained to the battery pumping after high temperature ageing, sealing, constant volume.
Embodiment 2
The present embodiment intermediate ion battery electrolyte is grouped as with functional additive by the group of following parts by weight: carbonic acid Asia second
1 part of enester (VC), 1 part of difluoro dioxalic acid lithium borate (LiODFB), difluorophosphate (LiPOF2) 0.5 part, fluorobenzene (FB) 3.5
Part, 0.2 part of methane-disulfonic acid methylene ester (MMDS).
The present embodiment intermediate ion battery electrolyte includes lithium salts, organic solvent, functional additive, is more specifically this implementation
Lithium salts is lithium hexafluoro phosphate (LiPF in example6) and bis- (fluorine sulphonyl) imine lithiums (LiFSI), lithium hexafluoro phosphate in the electrolytic solution dense
Degree is 0.6mol/L, and the bis- concentration of (fluorine sulphonyl) imine lithium in the electrolytic solution are 0.4mol/L, organic molten used in the present embodiment
Agent is the mixture of cyclic carbonate fat and chain carbonic ether, and wherein cyclic carbonate fat is ethylene carbonate, and mass percent is
30%, chain carbonic ether is diethyl carbonate, methyl ethyl carbonate and dimethyl carbonate, and mass percent is respectively diethyl carbonate
35%, methyl ethyl carbonate 15%, dimethyl carbonate 20%；Contained functional additive each component accounts for the quality hundred of entire electrolyte
Divide than being respectively vinylene carbonate (VC) 1%, difluoro dioxalic acid lithium borate (LiODFB) 1%, difluorophosphate (LiPOF2)
0.5%, fluorobenzene (FB) 3.5%, methane-disulfonic acid methylene ester (MMDS) 0.2%.
Positive plate, negative electrode tab and diaphragm and implementation used in the preparation method of high temperature lithium ion battery in the present embodiment
Example 1 is identical, only difference is that battery high-temperature aging condition is 60 DEG C and stands 2 days.
Embodiment 3
The present embodiment intermediate ion battery electrolyte is grouped as with functional additive by the group of following parts by weight: carbonic acid Asia second
1.5 parts of enester (VC), 1 part of difluoro dioxalic acid lithium borate (LiODFB), difluorophosphate (LiPOF2) 0.2 part, fluorobenzene (FB) 3.5
Part, 0.2 part of methane-disulfonic acid methylene ester (MMDS).
The present embodiment intermediate ion battery electrolyte includes lithium salts, organic solvent, functional additive, is more specifically this implementation
Lithium salts is lithium hexafluoro phosphate (LiPF in example6) and bis- (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI), lithium hexafluoro phosphate be electrolysed
Concentration in liquid is 0.6mol/L, and the concentration of bis- (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI) in the electrolytic solution is 0.4mol/
L, organic solvent used in the present embodiment are the mixture of cyclic carbonate fat and chain carbonic ether, and wherein cyclic carbonate fat is carbonic acid
Vinyl acetate, mass percent 30%, chain carbonic ether are diethyl carbonate, methyl ethyl carbonate and dimethyl carbonate, quality hundred
Divide than being respectively diethyl carbonate 35%, methyl ethyl carbonate 15%, dimethyl carbonate 20%；Contained functional additive each component
The mass percent for accounting for entire electrolyte is respectively vinylene carbonate (VC) 1.5%, difluoro dioxalic acid lithium borate (LiODFB)
1%, difluorophosphate (LiPOF2) 0.2%, fluorobenzene (FB) 3.5%, methane-disulfonic acid methylene ester (MMDS) 0.2%.
Positive plate, negative electrode tab and diaphragm and implementation used in the preparation method of high temperature lithium ion battery in the present embodiment
Example 1 is identical, only difference is that battery high-temperature aging condition is 85 DEG C of standing 12h.
Embodiment 4
The present embodiment intermediate ion battery electrolyte is grouped as with functional additive by the group of following parts by weight: carbonic acid Asia second
2 parts of enester (VC), 0.5 part of difluoro dioxalic acid lithium borate (LiODFB), difluorophosphate (LiPOF2) 1.0 parts, fluorobenzene (FB) 5
Part, 0.5 part of methane-disulfonic acid methylene ester (MMDS).
The present embodiment intermediate ion battery electrolyte includes lithium salts, organic solvent, functional additive, is more specifically this implementation
Lithium salts is lithium hexafluoro phosphate (LiPF in example6) and bis- (fluorine sulphonyl) imine lithiums (LiFSI), lithium hexafluoro phosphate in the electrolytic solution dense
Degree is 1.0mol/L, and the concentration of bis- (fluorine sulphonyl) imine lithiums (LiFSI) in the electrolytic solution is 0.2mol/L, used in the present embodiment
Organic solvent is the mixture of cyclic carbonate fat and chain carbonic ether, and wherein cyclic carbonate fat is ethylene carbonate, quality percentage
Than being 30%, chain carbonic ether is diethyl carbonate, methyl ethyl carbonate and dimethyl carbonate, and mass percent is respectively carbonic acid two
Ethyl ester 35%, methyl ethyl carbonate 15%, dimethyl carbonate 20%；Contained functional additive each component accounts for the matter of entire electrolyte
Measuring percentage is respectively vinylene carbonate (VC) 2%, difluoro dioxalic acid lithium borate (LiODFB) 0.5%, difluorophosphate
(LiPOF2) 1.0%, fluorobenzene (FB) 5%, methane-disulfonic acid methylene ester (MMDS) 0.5%.
Positive plate, negative electrode tab and diaphragm and implementation used in the preparation method of high temperature lithium ion battery in the present embodiment
Example 1 is identical, and the preparation method is the same as that of Example 1 for lithium ion battery, only difference is that battery high-temperature aging technique is 85 DEG C
Stand 12h.
Embodiment 5
The present embodiment intermediate ion battery electrolyte is grouped as with functional additive by the group of following parts by weight: carbonic acid Asia second
1.5 parts of enester (VC), 1.5 parts of difluoro dioxalic acid lithium borate (LiODFB), difluorophosphate (LiPOF2) 0.2 part, fluorobenzene (FB) 5
Part, 0.5 part of methane-disulfonic acid methylene ester (MMDS).
The present embodiment intermediate ion battery electrolyte includes lithium salts, organic solvent, functional additive, is more specifically this implementation
Lithium salts is lithium hexafluoro phosphate (LiPF in example6) and bis- (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI), lithium hexafluoro phosphate be electrolysed
Concentration in liquid is 0.6mol/L, and the concentration of bis- (trimethyl fluoride sulfonyl) imine lithiums (LiTFSI) in the electrolytic solution is 0.4mol/
L, organic solvent used in the present embodiment are the mixture of cyclic carbonate fat and chain carbonic ether, and wherein cyclic carbonate fat is carbonic acid
Vinyl acetate, mass percent 30%, chain carbonic ether are diethyl carbonate, methyl ethyl carbonate and dimethyl carbonate, quality hundred
Divide than being respectively diethyl carbonate 35%, methyl ethyl carbonate 15%, dimethyl carbonate 20%；Contained functional additive each component
The mass percent for accounting for entire electrolyte is respectively vinylene carbonate (VC) 1.5%, difluoro dioxalic acid lithium borate (LiODFB)
1.5%, difluorophosphate (LiPOF2) 0.2%, fluorobenzene (FB) 3.5%, methane-disulfonic acid methylene ester (MMDS) 0.2%.
Positive plate, negative electrode tab and diaphragm and implementation used in the preparation method of high temperature lithium ion battery in the present embodiment
Example 1 is identical, only difference is that battery high-temperature aging technique is 45 DEG C and stands 5 days.
High-temperature behavior test is carried out to finally obtained lithium ion battery.
Comparative example
This comparative example and being different only in that in lithium salts contained by electrolyte for embodiment 1 do not contain difluoro dioxalic acid lithium borate
(LiODFB), difluorophosphate (LiPOF2), fluorobenzene (FB), methane-disulfonic acid methylene ester (MMDS), and lithium-ion electric obtained
High temperature ageing processing is not done in pond.Other are same as Example 1.
Experimental example
By the lithium ion battery prepared in Examples 1 to 5 and the lithium ion battery of comparative example preparation under the conditions of 60 DEG C, into
The test of row 1C/1C cycle performance, 1C multiplying power charge to 3.65V, and 1C multiplying power discharging to 2.5V, after recycling 500 times, measurement capacity is protected
Holdup.
1 high temperature cyclic performance test result of table
| Embodiment | Cycle-index | Capacity retention ratio |
| Comparative example | 500 | 85.6% |
| Embodiment 1 | 500 | 92.60% |
| Embodiment 2 | 500 | 94.1% |
| Embodiment 3 | 500 | 93.8% |
| Embodiment 4 | 500 | 92.1% |
| Embodiment 5 | 500 | 94.7% |
Embodiment and comparative example recycle 500 times under the conditions of 60 DEG C, and capacity retention ratio is as shown in table 1, is added of the invention
The lithium ion battery of functional additive, capacity retention ratio are compared than being added without the lithium ion battery of the functional additive, capacity
Holding significantly improves, and capacity retention ratio is 92.1~94.7%, which sufficiently proves using lithium ion battery of the invention
The lithium ion battery of electrolyte functional additive and electrolyte has good high temperature cyclic performance.
Claims (4)
1. a kind of lithium-ion battery electrolytes, including lithium salts, organic solvent, it is characterised in that: it further include functional additive, it is described
The mass percent of each component of functional additive in the electrolytic solution are as follows: vinylene carbonate 0.5% ~ 3%, difluoro dioxalic acid boric acid
Lithium 0.1% ~ 2%, difluorophosphate 0.1% ~ 2%, fluorobenzene 3% ~ 5% and methane-disulfonic acid methylene ester 0.1% ~ 1%；The lithium salts is hexafluoro
One of lithium phosphate, bis- (fluorine sulphonyl) imine lithiums, bis- (trimethyl fluoride sulfonyl) imine lithiums are a variety of, and the lithium salt is
0.5 ~2mol/L；The organic solvent is the mixture of cyclic carbonate fat and chain carbonic ether.
2. lithium-ion battery electrolytes according to claim 1, it is characterised in that: the chain carbonic ether includes carbonic acid two
Ethyl ester, methyl ethyl carbonate and dimethyl carbonate.
3. a kind of using lithium ion battery made of electrolyte described in any one of claim 1 ~ 2.
4. lithium ion battery according to claim 3, which is characterized in that the preparation method of the lithium ion battery includes old
Change processing, the aging temperature of the aging process is 40 DEG C ~ 50 DEG C, ageing time is 3 ~ 7 days or aging temperature is 50 DEG C
~60 DEG C, ageing time is 1~3 day or aging temperature is 60 DEG C~85 DEG C, ageing time is the h of 8 h~24.
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| CN201710097438.XA CN106848404B (en) | 2017-02-22 | 2017-02-22 | A kind of lithium-ion battery electrolytes functional additive, lithium-ion battery electrolytes and lithium ion battery |
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| CN201710097438.XA CN106848404B (en) | 2017-02-22 | 2017-02-22 | A kind of lithium-ion battery electrolytes functional additive, lithium-ion battery electrolytes and lithium ion battery |
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| EP4087007A4 (en) * | 2021-03-17 | 2022-12-28 | Ningde Amperex Technology Limited | Electrolyte and electrochemical device comprising same |
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Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090286155A1 (en) * | 2006-08-22 | 2009-11-19 | Mitsubishi Chemical Corporation | Lithium difluorophosphate, electrolyte containing lithium difluorophosphate, process for producing lithium difluorophosphate, process for producing nonaqueous electrolyte, nonaqueous electrolyte, and nonaqueous electrolyte secondary battery containing the same |
| CN102201596B (en) * | 2006-12-06 | 2015-04-08 | 三菱化学株式会社 | Nonaqueous electrolyte solution and nonaqueous electrolyte secondary battery |
| WO2016063964A1 (en) * | 2014-10-22 | 2016-04-28 | 三井化学株式会社 | Lithium secondary battery |
| CN106299472A (en) * | 2015-05-25 | 2017-01-04 | 深圳市沃特玛电池有限公司 | A kind of high security lithium ion battery electrolyte and application thereof |
| CN105591158B (en) * | 2016-03-21 | 2019-01-15 | 东莞市杉杉电池材料有限公司 | A kind of tertiary cathode material lithium ion battery and its electrolyte |
| CN105742710A (en) * | 2016-05-03 | 2016-07-06 | 深圳市沃特玛电池有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN106025359A (en) * | 2016-07-08 | 2016-10-12 | 珠海市赛纬电子材料股份有限公司 | Lithium ion power battery non-water electrolyte |
| CN106129456B (en) * | 2016-07-21 | 2019-04-23 | 中航锂电（洛阳）有限公司 | A kind of electrolyte functional additive, long circulating lithium-ion battery electrolytes and lithium ion battery |
| CN106058319B (en) * | 2016-07-29 | 2018-11-30 | 厦门大学 | One kind has the electrolyte and the preparation method and application thereof of polyanionic functional group |
-
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP4087007A4 (en) * | 2021-03-17 | 2022-12-28 | Ningde Amperex Technology Limited | Electrolyte and electrochemical device comprising same |
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