CN109301309A - A kind of electrolyte of high pressure nickel-cobalt-manganternary ternary anode material - Google Patents
A kind of electrolyte of high pressure nickel-cobalt-manganternary ternary anode material Download PDFInfo
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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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
This hair provides a kind of application of the electrolyte and the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material in lithium ion battery.The electrolyte includes electrolyte lithium salt, organic solvent, addictive with dual functions and other additives; the addictive with dual functions is 1; 1; 1- trimethyl-N- (triphenylphosphoranylidene) silanamines; it both can be with Disacidifying and dewatering; it can form a film again in anode; protection anode; reduce the generation of side reaction between anode and electrolyte; and impedance increase is smaller; it is formed by CEI film better heat stability, so as to effectively improve the high-temperature storage performance under lithium ion battery high-voltage performance and high pressure.
Description
Technical field
The present invention relates to lithium-ion battery electrolytes technical fields, specifically, being related to a kind of suitable for high pressure nickel cobalt manganese three
The electrolyte of first positive electrode and its application in lithium ion battery.
Background technique
Lithium-ion battery electrolytes are the important components in lithium ion battery, traditional lithium ion battery material anode
Using cobalt acid lithium, for cathode using graphite, the mode for improving this kind of lithium ion battery energy density usually passes through raising
The operating voltage of battery is realized, and high operating voltage will will lead to the fast decoupled and cobalt acid lithium material structure of electrolyte
Destruction be difficult to meet the actual needs so that battery cycle life substantially reduces.A large amount of research confirms, develops high energy
Metric density lithium ion battery one of the most effective ways are to substitute existing cobalt acid lithium material using higher capacity positive electrode.?
On the basis of this, nickel-cobalt-manganternary ternary anode material has obtained extensive research and development, is compared to cobalt acid lithium, ternary material due to
Containing Ni4+/Ni3+, Ni3+/Ni2+, Co4+/Co3+ redox couple, be more toxic, the Co content of price costly it is opposite
It is less, therefore have higher capacity, environmental-friendly and lower price, ternary material is widely used in power battery neck
Domain.
The high capacity advantage for playing ternary material itself needs to improve the operating voltage of battery.But it is existing with carbon
The electrolyte system that acid esters is solvent, lithium hexafluoro phosphate is lithium salts is unable to satisfy ternary battery high pressure operations demand.In height
It presses under operating condition, conventional batteries system positive electrode reactivity increases, and electrolyte is easy to happen oxidation reaction, so as to cause
Lithium ion battery capacity rapid decay under high voltage condition, electrode/electrolyte interface stability is poor, micro-moisture and free
Acid causes lithium salts and solvolysis in electrolyte serious, and cathode material structure is destroyed, a system such as transition metal ions dissolution aggravation
Column problem seriously restricts the promotion of ternary lithium ion battery operating voltage.
For improve high pressure resistant (> 4.2V) performance of ternary material lithium battery, there are two types of current solutions: 1) pass through by
Ternary material is prepared into mono-crystalline structures, improves the high voltage performance of ternary material, it also requires corresponding high pressure resistant electrolyte with
Matching；2) by using some additives, the oxygenolysis of electrolyte under high voltages can be effectively suppressed.It constructs excellent
Electrode/electrolyte interfacial film needs researcher to develop new electrolyte system, real by introducing functional additive into electrolyte
Present electrode surface constructs excellent solid interface film (SEI film), to improve battery under the premise of not influencing cycle life
Operating voltage, but corresponding solution rests on laboratory development phase mostly, and achievement large-scale application case is opposite
It is less.There is part about the electrolysis additive report for improving ternary material high-voltage performance at present, although under improving high pressure
Cycle performance, but since serious side reaction occurs for high temperature inferior pole piece and electrolyte, high-temperature behavior deterioration can not be obtained
Effectively solve.On the other hand, the additive reported at present is generally only used as Disacidifying and dewatering additive and is added in electrolyte, or
It is only used as film for additive to be added in electrolyte, and is then reported as difunctional additive fewer.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide one kind to be suitable for high pressure nickel-cobalt-manganternary ternary anode material
The application in lithium ion battery of electrolyte and the electrolyte.
The addictive with dual functions refers to that the additive has the double action of Disacidifying and dewatering and film forming.
In order to achieve the above objectives, in a first aspect, the present invention provide it is a kind of suitable for high pressure nickel-cobalt-manganternary ternary anode material
Addictive with dual functions 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silanamines of electrolyte, shown in structure such as formula (I).
Second aspect, the present invention provide a kind of electrolyte of high pressure nickel-cobalt-manganternary ternary anode material, including electrolyte lithium salt,
Organic solvent, addictive with dual functions and other additives, the addictive with dual functions are that (triphenyl is just by 1,1,1- trimethyl-N-
Phosphine subunit) silanamines.
Preferably, the addictive with dual functions is the quality of 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silanamines
Content is 0.5%~1.5%.
Preferably, the total concentration of the electrolyte lithium salt is 1.0~1.2mol/L.The electrolyte lithium salt is selected from hexafluoro phosphorus
Sour lithium (LiPF6), LiBF4 (LiBF4), double fluorine sulfimide lithiums (LiFSI), di-oxalate lithium borate (LiBOB), difluoro
One of Lithium bis (oxalate) borate (LiDFOB) or at least two combination.
Preferably, the organic solvent be selected from ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC),
At least two combination in diethyl carbonate (DEC), methyl ethyl carbonate (EMC).
It is further preferred that by the gross mass of the organic solvent be 100% in terms of, group become ethylene carbonate 20%~
40%, methyl ethyl carbonate 10%~50%, dimethyl carbonate 10%~40%.
Preferably, the mass content of other additives is 1%~2%.Other additives are selected from carbonic acid Asia second
Enester (VC), vinylethylene carbonate (VEC), fluorinated ethylene carbonate (FEC), 1,3- propane sultone (PS), 1,4- fourth sulphur
One of acid lactone (BS), sulfuric acid vinyl ester (DTD), propane sulfonic acid vinylene, sulfuric acid acrylic ester and propylene sulfite or
At least two combination.
The third aspect, the present invention provide the preparation method of the electrolyte of above-mentioned high pressure nickel-cobalt-manganternary ternary anode material, comprising:
S1: electrolyte lithium salt being added in organic solvent after purification, and stirring is completely dissolved lithium salts, and it is molten to obtain lithium salts
Liquid；
S2: addictive with dual functions 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silicon is added in above-mentioned lithium salt solution
Alkanamine and other additives stir, and stand, obtain the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material.
Fourth aspect, the present invention also provides the lithium-ion electrics of the electrolyte comprising above-mentioned high pressure nickel-cobalt-manganternary ternary anode material
Pond.
Nickel-cobalt-manganternary ternary anode material of the present invention is suitable for LiNi1/3Co1/3Mn1/3O2、LiNi0.4Co0.2Mn0.4O2、
LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2, etc..
The beneficial effects of the present invention are:
The electrolyte for the high pressure nickel-cobalt-manganternary ternary anode material with superperformance that the present invention provides a kind of, this electrolyte
In 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silanamines for containing, not only can with Disacidifying and dewatering, but also can anode at
Film, protection anode, reduces the generation of side reaction between anode and electrolyte, and impedance increase is smaller, and it is steady to be formed by CEI film heat
It is qualitative preferable, so as to effectively improve the high-temperature storage performance under lithium ion battery high-voltage performance and high pressure.
Detailed description of the invention
Fig. 1: 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silanamines acid suppression presses down water principle.
Specific embodiment
1, the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material
(1) addictive with dual functions 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silanamines
Addictive with dual functions 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silanamines (abbreviation TPTMSA), it is simultaneous
Tool film forming and acid suppression press down water characteristic, and acid suppression presses down the principle of water as shown in Figure 1, TPTMSA can be reacted with minor amount of water in electrolyte
Triphenylphosphine imines and trimethyl silanol are generated, and can be reacted with HF micro in electrolyte and generate triphenylphosphine imines and front three
Base silicon fluoride, to reach preferable Disacidifying and dewatering effect.
On the other hand, the P=N double bond in TPTMSA forms polymer film and overlays on positive electrode surface easily by positive oxidation polymerization,
It is formed passivating film (CEI film), inhibition anode is reacted with electrolyte interface, to effectively improve lithium ion battery high-voltage performance
With the high-temperature storage performance under high pressure.
Preferably, the quality of addictive with dual functions 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silanamines contains
Amount is 0.5%~1.5%, such as: 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%,
1.4% or 1.5%, etc..
When the content of 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silanamines in the electrolytic solution is lower than 0.5%
When, then do not have corresponding effect；When 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silanamines in the electrolytic solution
When content is higher than 1.5%, then the CEI film formed is too thick, and impedance is larger, and circulation is deteriorated.
(2) electrolyte lithium salt
The electrolyte lithium salt can be selected from lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), lithium perchlorate
(LiClO4), hexafluoroarsenate lithium (LiAsF6) etc. inorganic lithium salts, LiPF6-n(CF3)nPerfluors such as (integers of 0 < n < 6) replace complexing
Phosphoric acid class lithium salts, three catechol phosphoric acid ester lithium salts, dioxalic acid lithium borate (LiBOB) and difluorine oxalic acid boracic acid lithium (LiDFOB)
Etc. boric acid class lithium salts, LiN [(FSO2C6F4)(CF3SO2)], trifluoromethyl sulfonic acid lithium (LiSO3CF3), bis trifluoromethyl sulphonyl it is sub-
The lithium salts of sulfonimide such as amine lithium (LiTFSi) and LiCH (SO2CF3)2(LiTFSM) etc. Polyfluoroalkyls class lithium salts, can be
It is one such to be also possible to more than one and be applied in combination, and it is not limited to enumerated lithium salts, other energy generally in the art
The lithium salts for enough reaching similar effect can be used for the present invention.
In some embodiments of the present invention, the electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF6), LiBF4
(LiBF4), double fluorine sulfimide lithiums (LiFSI), di-oxalate lithium borate (LiBOB), in difluorine oxalic acid boracic acid lithium (LiDFOB)
It is a kind of or at least two combination.
Preferably, the total concentration of electrolyte lithium salt is 1.0~1.2mol/L in the electrolyte.
(3) organic solvent
Preferably, the organic solvent be selected from ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC),
At least two in diethyl carbonate (DEC), methyl ethyl carbonate (EMC), but it is not limited to enumerated organic solvent, other
The general organic solvent that can reach similar effect in field can be used for the present invention.
It is in terms of 100% by the gross mass of the organic solvent, group becomes ethylene carbonate in some embodiments of the present invention
20%~40%, methyl ethyl carbonate 10%~50%, dimethyl carbonate 10%~40%.
(4) other additives
Preferably, other additives are selected from vinylene carbonate (VC), vinylethylene carbonate (VEC), fluoro carbon
Vinyl acetate (FEC), 1,3- propane sultone (PS), 1,4- butyl sultone (BS), sulfuric acid vinyl ester (DTD), propane sulfonic acid are sub-
One of vinyl acetate, sulfuric acid acrylic ester and propylene sulfite or at least two combination.
Preferably, the mass content of other additives is 1%~2%.
2, the preparation method of the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material
The preparation method of the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material provided by the invention, comprising:
S1: electrolyte lithium salt being added in organic solvent after purification, and stirring is completely dissolved lithium salts, and it is molten to obtain lithium salts
Liquid；
S2: addictive with dual functions 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silicon is added in above-mentioned lithium salt solution
Alkanamine and other additives stir, and stand, obtain the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material.
Wherein, the purifying of the organic solvent refers to removal of impurities, the water removal operation of organic solvent, preferably passes through molecular sieve, work
Property charcoal is handled.The molecular sieve can useType,Type orType.
Preferably, the temperature that the electrolyte lithium salt dissolves in organic solvent is 10~20 DEG C.
Preferably, the time of the standing is 24-36h.
The electrolyte lithium salt, the selection of organic solvent and other additives and dosage and above-mentioned high pressure nickel-cobalt-manganese ternary are just
The electrolyte of pole material is identical.
3, lithium ion battery
Lithium ion battery provided by the invention includes positive plate, negative electrode tab, diaphragm and electrolyte.
The positive plate active material containing removal lithium embedded, conductive agent, collector and by this by active material and collector knot
The binder of conjunction；The removal lithium embedded active material is nickel-cobalt-manganese ternary material, such as: LiNi1/3Co1/3Mn1/3O2、
LiNi0.4Co0.2Mn0.4O2、 LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2, etc..
The negative electrode tab include can the active material of reversible removal lithium embedded, conductive agent, collector and by this by active material
Binder in conjunction with collector.
The active material of the reversible removal lithium embedded of energy includes lithium metal, lithium alloy, hard carbon, amorphous carbon, soft carbon, fibrous carbon
And it is a kind of or more in crystalline carbon.
The crystalline carbon includes natural graphite, electrographite, graphitization one of MCMB and mesophase asphalt carbon fiber.
The diaphragm be PE diaphragm, PP diaphragm, PE PP composite diaphragm or other commercially available diaphragms.
The electrolyte is the electrolyte of above-mentioned high pressure nickel-cobalt-manganternary ternary anode material.
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to following preferred implementation side
Formula.It should be pointed out that for those skilled in the art on the basis of the inventive concept, several deformations for making and
It improves, belongs to protection scope of the present invention, in order to further describe the present invention, illustrate combined with specific embodiments below.
Embodiment 1
The preparation of the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material:
Moisture less than 10ppm glove box in, in 15 DEG C by organic solvent according to ethylene carbonate (EC): methyl ethyl carbonate
Ester (EMC): dimethyl carbonate (DMC)=1:1:1 mass fraction is uniformly mixed, and electrolyte lithium salt is added in dry water removal removal of impurities
LiPF6It is made into the solution of 1mol/L, is thoroughly mixed uniformly, TPTMSA and mass fraction that mass fraction is 0.5% is added
It for 1.0% VC, is uniformly mixed, stands for 24 hours, the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material is made.
The preparation of lithium ion battery:
The preparation of positive plate: by positive active material nickel-cobalt-manganese ternary material LiNi0.5Co0.2Mn0.3O2, conductive agent acetylene
Black, binder Kynoar (PVDF) 95:3:2 in mass ratio is thoroughly mixed in N-Methyl pyrrolidone system
It is even, it is coated on plus plate current-collecting body aluminium foil, obtains positive plate after drying cold pressing.
The preparation of negative electrode tab: by negative electrode active material graphite, conductive agent acetylene black, binder butadiene-styrene rubber (SBR), thickening
Agent carboxymethyl sodium cellulosate (CMC) 96:2:1.2:0.8 in mass ratio is thoroughly mixed uniformly in deionized water solvent system
Afterwards, it is coated on negative current collector copper foil, obtains negative electrode tab after drying and cold pressing.
Diaphragm: using PE porous polymer film as diaphragm.
The preparation of lithium ion battery: obtained positive plate, negative electrode tab are placed in baking oven after certain temperature is baked to
It moves into glove box.Then the positive plate handled well, diaphragm, negative electrode tab are put well in order, and inject above-mentioned preparation electrolyte,
Dressed up CR2025 button full battery.
Performance test:
Electrolyte moisture and acidity test: by the electrolyte prepared in glove box room temperature 1 day and 15 days, survey respectively
Moisture and acidity are tried, the results are shown in Table 1.
Normal-temperature circulating performance evaluation: at 25 DEG C, 150 circle of 1C, 3.0~4.4V circulation calculates its capacity retention ratio, as a result sees
Table 1.
The evaluation of high-temperature storage performance: by battery 0.2C charge and discharge 1 time at 25 DEG C, 25 DEG C of discharge capacity is recorded, then
0.2C constant current constant voltage is filled to 4.4V, stores 14 days under the conditions of 60 DEG C, tests after its high-temperature storage that 0.2C electric discharge is held at 25 DEG C
Amount, calculates its capacity retention ratio and recovery rate, the results are shown in Table 1.
Embodiment 2
In the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material: addictive with dual functions is the TPTMSA that mass fraction is 1%,
Other additives are the VC that mass fraction is 1.0%, other are same as Example 1.
Embodiment 3
In the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material: addictive with dual functions is that mass fraction is 0.5%
TPTMSA, other additives are the PS that mass fraction is 2.0%, other are same as Example 1.
Embodiment 4
In the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material: addictive with dual functions is that mass fraction is 1.5%
TPTMSA, other additives are the FEC that mass fraction is 1.5%, other are same as Example 1.
Embodiment 5
In the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material: addictive with dual functions is the TPTMSA that mass fraction is 1%,
Other additives are the DTD that mass fraction is 1.0%, other are same as Example 1.
Comparative example 1
Addictive with dual functions TPTMSA is not added in the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material, other and embodiment
1 is identical.
Comparative example 2
In the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material: addictive with dual functions TPTMSA replaces with mass fraction and is
0.5% N- tetraphenyl amination phosphine (TPPA), other additives are the VC that mass fraction is 1.0%, other and 1 phase of embodiment
Together, shown in the structure of TPPA such as formula (II).
Comparative example 3
In the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material: addictive with dual functions TPTMSA replaces with mass fraction and is
0.5% 2- (triphenylphosphanylidene) succinic anhydride (TPSA), other additives are the VC that mass fraction is 1.0%, other with
Embodiment 1 is identical, shown in the structure of TPSA such as formula (III).
1 embodiment of table and comparative example electrolyte and lithium battery test result
By the data in table 1 it is found that adding compared with not adding addictive with dual functions or adding the electrolyte of TPPA and TPSA
The water content and acidity for adding the electrolyte of addictive with dual functions TPTMSA are substantially reduced, and the lithium ion battery prepared 3.0~
After 4.4V is recycled 150 weeks, 15% or more battery capacity conservation rate raising, meanwhile, the capacity retention ratio of 60 DEG C of storages, 14 days batteries
It also improves to some extent with recovery rate, shows that the addictive with dual functions TPTMSA of the invention added has and preferably remove
Aqueous energy, and can form a film in anode, the effective high-temperature storage performance improved under lithium ion battery high-voltage performance and high pressure.
And TPPA cannot be reacted with acid and water, acid anhydrides is reacted with minor amount of water and acid since steric hindrance is too big in TPSA, and activity is not strong, therefore,
The water content and acidity of electrolyte are higher.
Claims (10)
1. one kind 1,1, the application of 1- trimethyl-N- (triphenylphosphoranylidene) silanamines are being used as high pressure nickel-cobalt-manganese ternary just
The addictive with dual functions of the electrolyte of pole material.
2. a kind of electrolyte of high pressure nickel-cobalt-manganternary ternary anode material, including electrolyte lithium salt, organic solvent, addictive with dual functions
With other additives, which is characterized in that the addictive with dual functions is 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silane
Amine.
3. the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material according to claim 2, which is characterized in that described difunctional
The mass content of additive 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silanamines is 0.5%~1.5%.
4. the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material according to claim 2, which is characterized in that the electrolyte
The total concentration of lithium salts is 1.0~1.2mol/L.
5. the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material according to claim 2, which is characterized in that the electrolyte
Lithium salts is in lithium hexafluoro phosphate, LiBF4, double fluorine sulfimide lithiums, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium
It is a kind of or at least two combination.
6. the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material according to claim 2, which is characterized in that described organic molten
At least two group of the agent in ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate
It closes.
7. the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material according to claim 6, which is characterized in that with described organic
The gross mass of solvent is 100% meter, and group becomes ethylene carbonate 20%~40%, methyl ethyl carbonate 10%~50%, carbonic acid two
Methyl esters 10%~40%.
8. the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material according to claim 2, which is characterized in that described other to add
The mass content for adding agent is 1%~2%, and other additives are selected from vinylene carbonate, vinylethylene carbonate, fluoro carbon
Vinyl acetate, 1,3- propane sultone, 1,4- butyl sultone, sulfuric acid vinyl ester, propane sulfonic acid vinylene, sulfuric acid acrylic ester and
One of propylene sulfite or at least two combination.
9. a kind of preparation method of the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material, comprising:
S1: electrolyte lithium salt being added in organic solvent after purification, and stirring is completely dissolved lithium salts, obtains lithium salt solution；
S2: addictive with dual functions 1,1,1- trimethyl-N- (triphenylphosphoranylidene) silanamines are added in above-mentioned lithium salt solution
It with other additives, stirs, stands, obtain the electrolyte of high pressure nickel-cobalt-manganternary ternary anode material.
10. a kind of lithium ion of the electrolyte comprising the described in any item high pressure nickel-cobalt-manganternary ternary anode materials of claim 2-8
Battery.
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| CN110350239A (en) * | 2019-07-08 | 2019-10-18 | 无锡市明杨新能源有限公司 | High magnification lithium ion battery with high energy density |
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| JP5095883B2 (en) * | 2000-09-07 | 2012-12-12 | 株式会社ブリヂストン | Non-aqueous electrolyte secondary battery additive and non-aqueous electrolyte secondary battery |
| CN100362689C (en) * | 2002-12-26 | 2008-01-16 | 株式会社普利司通 | Additive for nonaqueous electrolytic solution of secondary battery and nonaqueous electrolyte secondary battery |
| CN101442140A (en) * | 2007-11-22 | 2009-05-27 | 比亚迪股份有限公司 | Non-water electrolytic solution and preparation method thereof and lithium ion battery containing the same |
| CN102893443A (en) * | 2010-05-21 | 2013-01-23 | 三井化学株式会社 | Nonaqueous electrolyte solution containing silyl ester group-containing phosphonic acid derivative, and lithium secondary battery |
| CN105789698A (en) * | 2016-03-04 | 2016-07-20 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110350239A (en) * | 2019-07-08 | 2019-10-18 | 无锡市明杨新能源有限公司 | High magnification lithium ion battery with high energy density |
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