CN104241688A - Lithium ion battery electrolyte and lithium ion battery - Google Patents
Lithium ion battery electrolyte and lithium ion battery Download PDFInfo
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- CN104241688A CN104241688A CN201310254376.0A CN201310254376A CN104241688A CN 104241688 A CN104241688 A CN 104241688A CN 201310254376 A CN201310254376 A CN 201310254376A CN 104241688 A CN104241688 A CN 104241688A
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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 provides an electrolyte for a lithium ion battery. The electrolyte comprises the following components: an organic solvent (A), conductive lithium salt (B) and additive (C), wherein the additive (C) contains metal organic compound and/or semi-metal organic compound. The invention also provides a lithium ion battery comprising the electrolyte. By adopting the electrolyte, the moisture of a lithium ion battery material can be eliminated, the inflation of the battery is reduced, the safety and capacity maintaining rate of the battery can be improved, and the cycling life of the battery can be prolonged.
Description
Technical field
The invention belongs to field of lithium ion battery, relate to a kind of electrolyte, and comprise the lithium ion battery of this electrolyte.
Background technology
Current, the fast development of electronic product, electrician tool, mobile product needs high performance battery.Lithium ion battery, relative to lead-acid battery, nickel-cadmium cell, the Ni-MH battery battery behavior that to have that operating voltage is high, energy density is high, have extended cycle life etc. excellent, is widely used in mobile phone, portable computer, video camera, camera etc.At present, high capacity lithium ion battery is on probation in electric automobile, by one of major impetus power supply becoming electric automobile, lithium ion battery is also progressively applied in artificial satellite, Aero-Space and energy storage, in order to meet the needs of lithium ion battery industry future development, high security, the adaptive lithium ion battery of high environment must be developed.
Lithium-ion electrolyte is one of large critical material (positive pole, negative pole, barrier film, electrolyte) of lithium ion battery four, being known as is lithium ion battery " blood ", between the both positive and negative polarity of battery, play the effect of conduction electron, be the guarantee that lithium ion battery obtains the advantage such as high voltage, high-energy-density.Organic solvent in lithium-ion electrolyte requires high-purity, anhydrous or moisture is extremely low, and nonaqueous electrolyte (such as lithium hexafluoro phosphate) is preferably anhydrous, not easily decomposes.Part organic solvent and nonaqueous electrolyte have stronger moisture absorption, lithium hexafluoro phosphate can with water generation hydrolysis, it is generally acknowledged that in lithium hexafluoro phosphate, moisture is the main cause causing its decomposition temperature to reduce.Electrolyte requires also very harsh to fluohydric acid content, hydrofluoric acid and positive electrode react, and cause positive electrode to lose activity; Hydrofluoric acid and negative material react, and generate lithium fluoride, increase the internal resistance of cell.Secondly, water and the higher meeting of hydrofluoric acid make battery core changing into, produce a large amount of gas in the process of aging and partial volume, battery produces more gas and makes battery flatulence in charge and discharge cycles process, cause the decline of battery core capacity, cycle performance declines, cycle life shortens, some even causes battery explosion.So, need the performance improving lithium ion battery each side just must reduce the content of moisture and hydrofluoric acid in electrolyte.
Relative to the lithium-ion-power cell taking carbon as negative pole, day by day come into one's own using lithium titanate as the electrode material of novel energy storage cell.When lithium titanate is as cell negative electrode material, in lithium ion deintercalation process, the structure of lithium titanate can keep the stable of height, and change in volume is almost nil in charge and discharge process, avoid the structural deterioration caused due to the flexible of electrode material in charge and discharge cycles, thus improve cycle performance and the useful life of electrode, decrease the capacity attenuation caused because of the increase of cycle-index, therefore lithium titanate has the cycle performance more excellent than carbon.Meanwhile, the electromotive force of lithium titanate is high, discharging voltage balance, and can not make electrolyte decomposition, be formed without SEI film, avoid SEI film rupture, and not easily produce Li dendrite, therefore lithium titanate battery has higher security performance.At 25 DEG C, the lithium ion diffusion coefficient of lithium titanate is 2 × 10
-8cm
2/ s, an order of magnitude larger than carbon negative pole material, high ionic diffusion coefficient makes lithium titanate can discharge and recharge rapidly.Above-mentioned advantage makes lithium titanate battery have in the field such as electric automobile, energy-storage battery to use widely, but the shortcoming of lithium titanate very easily absorbs water, thus find that a kind of to effectively reduce water in lithium ion battery, acid, the electrolyte of alcohol and impurity content and battery system extremely urgent.
Summary of the invention
In order to solve the problem, an object of the present invention is to provide a kind of electrolyte of lithium ion battery, this electrolyte comprises following component: organic solvent (A), electric conducting lithium salt (B) and additive (C), wherein additive (C) is containing at least one metallo-organic compound or semimetal organic compound.
In the present invention, metallic element in the metallo-organic compound that additive (C) contains is selected from least one in aluminium, gallium, indium, thallium, zinc, cadmium, lithium, magnesium and antimony, and the semimetallic elements in semimetal organic compound is selected from least one in boron, silicon, arsenic, tellurium and phosphorus.
In the present invention, in the metallo-organic compound in additive (C) and the organic group in semimetal organic compound at least containing a carbon number be less than or equal to 4 alkyl or carbon number be less than or equal to 4 hydrocarbon derivative group.Further, the alkyl that above-mentioned carbon number is less than or equal to 4 is selected from least one in alkyl and alkylene.The hydrocarbon derivative group that above-mentioned carbon number is less than or equal to 4 is selected from least one in alkoxyl, alkene oxygen base, ether and halogenated hydrocarbon group.
According to one embodiment of the present invention, metallo-organic compound is selected from trimethyl aluminium, triethyl aluminum (TEA), tri-n-hexyl aluminum, triisobutyl aluminium, three n-butylaluminum, diisobutyl aluminium hydride, triethyl group tri-chlorination two aluminium, sesquialter ethylmercury chloride aluminium (EASC), aluminium diethyl monochloride (DEAC), ethyl aluminum dichloride (EADC), sesquialter methyl chloride aluminium (MASC), dimethylaluminum chloride, dimethyl one aluminum methoxide, trimethyl gallium (TMGa), trimethyl indium (TMIn), trimethyl thallium, zinc methide, diethyl zinc (DEZn), dimethyl cadmium, lithium methide, isobutyl group lithium, tert-butyl group magnesium chloride, n-butylmagnesium chloride magnesium, at least one in ethylmagnesium bromide and trimethylantimony, semimetal organic compound boron triethyl, dimethoxydiphenylsilane, Cyclohexyl Methyl Dimethoxysilane, arsenic trimethide, at least one in tellurium diethyl (DETe) and tri-butyl phosphine.
In the present invention, metallo-organic compound and semimetal organic compound content in the electrolytic solution can the amount of the composition such as water contained by the concentration of metallo-organic compound in electrolyte and semimetal organic compound and positive/negative plate, acid and alcohol be determined in additive (C).The addition of additive (C) does not reach good effect very little, and addition may not react completely explosion caused due to reagent too much.
According to the embodiment of the present invention, the middle metallo-organic compound of additive (C) and semimetal organic compound account for the mass percentage of electrolyte component is 10ppm ~ 1%.Further, the middle metallo-organic compound of additive (C) and semimetal organic compound account for the mass percentage of electrolyte component is 10 ~ 5000ppm.
According to the embodiment of the present invention, metallo-organic compound and/or semimetal organic compound can be contained in additive (C) with its solution form.Solvent in above-mentioned solution is organic solvent (I).Further, organic solvent (I) is selected from least one in n-hexane, heptane, toluene, benzene, ether or oxolane.
In the present invention, organic solvent (A) is selected from least one in carbonic ester and derivative, carboxylate and derivative thereof, carboxylic acid amide and derivative, ether and derivative thereof and sulfur-bearing organic solvent and derivative thereof.
According to the embodiment of the present invention, above-mentioned carbonic ester can be selected from least one in dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), propene carbonate (PC), ethylene carbonate (EC) and methyl propyl carbonate (MPC); Carboxylate can be selected from least one in (PA) such as gamma-butyrolacton (γ-BL), methyl formate (MF), methyl acetate (MA), ethyl propionate (EP) and propyl acetates; Carboxylic acid amide can be selected from least one in dimethyl formamide, methylformamide and METHYLPYRROLIDONE; Ether can be selected from least one in 1,3-dioxolanes, oxolane, oxinane and 1,2-dimethoxy-ethane; Sulfur-bearing organic solvent can be selected from least one in first ethyl sulfone, ethylene sulfite, propylene sulfite, sulfuric acid propylene and 4-methyl ethyl sulfate.
In the present invention, electric conducting lithium salt (B) is selected from least one inorganic lithium salt or organic lithium salt.
According to embodiments of the invention, inorganic lithium salt is selected from lithium perchlorate (LiClO
4), hexafluoroarsenate lithium (LiAsF
6), LiBF4 (LiBF
4), lithium hexafluoro phosphate (LiPF
6) and lithium fluoride (LiF) at least one.Organic lithium salt is selected from least one in organic sulfonic acid base lithium salts, organic boronic lithium salts and organic phosphoric acid lithium salts.Wherein organic sulfonic acid base lithium salts is selected from trifluoromethyl sulfonic acid lithium (LiCF
3sO
3), two (trifluoromethane sulfonic acid) imine lithium (LiN (CF
3sO
2)
2) and three (trimethyl fluoride sulfonyl) lithium methide (LiC (CF
3sO
2)
3) at least one; Organic boronic lithium salts is selected from least one in two (catechol) lithium borate (LiBBB), dimalonic acid lithium borate (LiBMB) and di-oxalate lithium borate (LiBOB); Organic phosphoric acid lithium salts is selected from least one in three (catechol) lithium phosphate (LiTBP), three (perfluoro-ethyl) and three lithium fluophosphates (LiFAP).
According to embodiments of the invention, the concentration of electric conducting lithium salt (B) is 0.1 ~ 5mol/L.Lithium salt is too low, cause electrolyte conductive capability or lithium ion mobility ability poor; Excessive concentration, may cause lithium salts to be separated out at low temperatures.
Electrolyte provided by the present invention can also comprise additive (D) further.
According to the embodiment of the present invention, additive (D) is selected from least one in anti-overcharge additive, flame-retardant additive and conductive additive.
According to the embodiment of the present invention, additive (D) is selected from biphenyl (BP), vinylene carbonate (VC), aromatic radical adamantane, naphthalene derivatives, poly benzene, trimethyl phosphate (TMP), triphenyl phosphate (TPP), three (2,2,2-trifluoroethyl) phosphite ester, at least one in phenodiazine (mixing) benzene and three (five fluorinated phenyl) boron.
In existing lithium ion battery production technology, moisture in positive/negative plate is difficult to be baked to electrolyte level, and electrolyte also can absorb a small amount of moisture in injection process, these moisture entrapment, in lithium ion battery, produce worse impact by the performance of battery.Adopt the scheme of electrolyte provided by the invention, in electrolyte, the water effective of trace reduces, thus avoids the generation of hydrofluoric acid and alcohol, and the chromatic value of electrolyte also can reduce, and can also reduce the micro-moisture in pole piece significantly simultaneously.
Another object of the present invention is to provide a kind of lithium ion battery, comprises the positive pole containing positive electrode active materials and the negative pole containing negative active core-shell material, also containing electrolyte as above.
According to embodiments of the invention, the negative active core-shell material of above-mentioned lithium ion battery is lithium titanate.
Adopt electrolyte provided by the invention, can significantly reduce lithium ion battery material---especially for lithium titanate anode material---in moisture, thus the flatulence of lithium battery can be reduced, improve the fail safe of lithium battery, capability retention and cycle life.
Accompanying drawing explanation
Fig. 1, lithium titanate anode pole piece trimethyl aluminium removes reaction of moisture schematic diagram;
The performance comparison (one) of lithium ion battery prepared by the electrolyte of Fig. 2, comparative example 3, embodiment 6 and embodiment 7;
The performance comparison (two) of lithium ion battery prepared by the electrolyte of Fig. 3, comparative example 3, embodiment 6 and embodiment 7;
The performance comparison (three) of lithium ion battery prepared by the electrolyte of Fig. 4, comparative example 3, embodiment 6 and embodiment 7;
The performance comparison (four) of lithium ion battery prepared by the electrolyte of Fig. 5, comparative example 3, embodiment 6 and embodiment 7;
Flatulence comparison diagram after lithium ion battery charge and discharge cycles prepared by the electrolyte of Fig. 6, comparative example 3, embodiment 6 and embodiment 7, wherein (a) figure is comparative example 3, and (b) figure is embodiment 6, and (c) figure is embodiment 7.
Execution mode
In one embodiment of the invention, additive (C) is alkyl aluminum, and the reaction equation that it and water, hydrofluoric acid occur is as follows:
Alkyl aluminum except the cardinal principle of moisture, hydrofluoric acid and alcohol in electrolyte be that alkyl aluminum has very strong reproducibility, can with water, acids or alcohol compound generation intense reaction, generate alkane derivative and aluminum organic compound; Alkane and the aluminum organic compound of generation are very little to the performance impact of lithium ion battery, therefore hydrofluoric acid, moisture and other the impurity in alkyl aluminum removing electrolyte can be adopted, thus reduce moisture, acid, alcohol and other similar impurity to the impact of lithium ion battery, the colourity of lithium-ion electrolyte can also be reduced simultaneously.
In one embodiment of the invention, negative active core-shell material adopts lithium titanate battery, containing the electrolyte that with the addition of alkyl aluminum in this lithium titanate battery.The electrolyte adding alkyl aluminum is injected lithium titanate lithium ion battery, and the water that alkyl aluminum and lithium titanate adsorb reacts, and the moisture in removing lithium titanate, also modifies the surface of lithium titanate simultaneously.Water elimination in lithium titanate battery and the modification on lithium titanate surface, reduce the flatulence problem of lithium titanate battery to a great extent, improve the security performance of lithium titanate battery, capability retention and cycle life etc.Fig. 1 is lithium titanate anode pole piece alkyl aluminum removing moisture schematic diagram.
Specific embodiment
The present invention is set forth below in conjunction with specific embodiment and accompanying drawing.Should be appreciated that embodiment described herein only for explaining the present invention, not limiting the scope of the invention.
Comparative example 1
In vacuum glove box, prepare electrolyte, electrolyte consist of DMC:EMC:PC=1:1:1, VC addition is 2wt%, LiPF
6addition is 13.3wt%.The hydrofluoric acid concentration of sampling and testing electrolyte, moisture and colourity, test result is in table 1.
Embodiment 1
To get in comparative example 1 the electrolyte 150g of preparation, add the hexane solution of the 2mol/L trimethyl aluminium of 2.5mL wherein, after mixing, the hydrofluoric acid concentration of sampling and testing electrolyte, moisture and colourity, test result is in table 1.
Embodiment 2
To get in comparative example 1 the electrolyte 150g of preparation, add the hexane solution of the 2mol/L trimethyl aluminium of 5mL wherein, after mixing, the hydrofluoric acid concentration of sampling and testing electrolyte, moisture and colourity, test result is in table 1.
Table 1: the electrolyte adding trimethyl aluminium contrasts with the physical parameter test result of not adding
Test result in table 1 can be found out: compared with the electrolyte not adding trimethyl aluminium, with the addition of the electrolyte of trimethyl aluminium, and its hydrofluoric acid concentration, moisture and colourity all have certain reduction.
Comparative example 2
Get and do not add any doping electrolyte, test the fluohydric acid content of electrolyte, moisture and colourity, test result is in table 2.This do not add any doping electrolyte for the electrolyte prepared in comparative example 1 be long placed in after obtain, its colourity deepen and moisture, fluohydric acid content are higher.
Embodiment 3
Get the electrolyte 203.1g in comparative example 2, add the diethyl ether solution of the 1.6mol/L lithium methide of 1mL wherein, after mixing, the hydrofluoric acid concentration of sampling and testing electrolyte, moisture and colourity.Test result is in table 2.
Embodiment 4
Get the electrolyte 150g in comparative example 2, add the toluene solution of the 1mol/L zinc methide of 17.5mL wherein, after mixing, the hydrofluoric acid concentration of sampling and testing electrolyte, moisture and colourity.Test result is in table 2.
Embodiment 5
Get the electrolyte 150g in comparative example 2, add the hexane solution of the 2mol/L trimethyl aluminium of 7mL wherein, after mixing, the fluohydric acid content concentration of sampling and testing electrolyte, moisture and colourity.Test result is in table 2.
Table 2: the test result contrast adding the electrolyte of different metal organic compound
Comparative example 3
In vacuum glove box, prepare electrolyte, electrolyte forms: DMC:EMC:PC=1:1:1, VC addition is 2wt%, LiPF
6addition is 13.3wt%.
Embodiment 6
Get the electrolyte 150g of preparation in comparative example 3, add the hexane solution of the 2mol/L trimethyl aluminium of 2.5mL, mix.
Embodiment 7
Get the electrolyte 150g of preparation in comparative example 3, add the hexane solution of the 2mol/L trimethyl aluminium of 5.0mL, mix.
The electrolyte composition table of table 3 embodiment 6-7 and comparative example 3
Electrolyte in comparative example 3 and embodiment 6,7 is applied to lithium ion battery
The present invention is not construed as limiting lithium ion battery structure, can be Soft Roll, column type, square or coin shape, adopts lithium ion soft-package battery (10Ah) to test in the embodiment of the present invention.The positive and negative electrode material of battery is also not construed as limiting, positive electrode can be selected from cobalt acid lithium, LiMn2O4, lithium nickelate, aluminum-doped nickel lithium carbonate for lithium, LiFePO 4, nickel-cobalt-manganese ternary material etc., and negative material can be selected from graphite (native graphite or electrographite), lithium titanate, elemental silicon, carbon-silicon composite material, carbon tin composite material etc.In the embodiment of the present invention, positive electrode is nickel-cobalt-manganese ternary material, and negative material is lithium titanate.
Get active electrode material respectively, conductive black, binding agent PVDF mix by certain mass ratio, add 1-METHYLPYRROLIDONE, mix further, be coated with, roll-in after oven dry, cut, lamination, lithium ion battery Soft Roll made by the electrolyte injecting comparative example 3 and embodiment 6-7 respectively; Again through changing into, after the operation such as aging, partial volume, battery carries out charge and discharge cycles test at 60 DEG C of temperature.Below inject the battery of comparative example 3 electrolyte referred to as comparative example 3, inject the battery of embodiment 6 electrolyte referred to as embodiment 6, inject the battery of embodiment 7 electrolyte referred to as embodiment 7.
The charge-discharge property of battery: embodiment 6 initial charge capacity is 11066.9mAh, and discharge capacity is 11075.0mAh, and first charge-discharge efficiency is 100.1%; Embodiment 7 initial charge capacity is 10865.4mAh, discharge capacity 10760mAh, and first charge-discharge efficiency is 99.0%; Comparative example 3 initial charge capacity is 11461.9mAh, discharge capacity 11282.1mAh, first charge-discharge efficiency be 98.4%(wherein, first charge-discharge efficiency=discharge capacity/charging capacity × 100%).As can be seen from above data, first charge-discharge efficiency the increasing all than comparative example 3 of embodiment 6-7.
The charge-discharge energy of battery: embodiment 6 initial charge energy is 27429.4mWh, and discharge energy is 25361.4mWh, and first charge-discharge energy efficiency is 92.5%; Embodiment 7 initial charge energy is 26977.9mWh, discharge energy 24592.2mWh, and first charge-discharge energy efficiency is 91.2%; Comparative example 3 initial charge energy is 28110.4mWh, discharge energy 25840.3mWh, first charge-discharge energy efficiency be 91.9%(wherein, first charge-discharge energy efficiency=discharge energy/rechargeable energy × 100%).As can be seen from the data, the first charge-discharge energy efficiency of embodiment 6-7 and the suitable of comparative example 3.
At 60 DEG C, battery 60A charging 30A discharge cycles performance: as can be seen from Figure 4, in embodiment more than 6 cyclic process, capability retention is very high, and the sign of obviously decay; The capacity of embodiment 7 is slightly lower than comparative example 3, but relaxation phenomenon is also not obvious after repeatedly circulating; And capacity has decay in various degree in comparative example more than 3 cyclic process.As can be seen from Figure 5, in embodiment 6 cyclic process, energy is without any the sign of decay, although embodiment 7 energy is lower than comparative example 3 a little, it is almost also undamped, and in comparative example 3 cyclic process, energy has decay to a certain degree.
At 60 DEG C, battery 60A charges the capability retention after 30A discharge cycles: the embodiment 6 217 weeks capacity that circulate increase by 3.1%, and conservation rate is 103.1%; Embodiment 7 circulates about 120 weeks capacity attenuations about 2.53%, and conservation rate is 97.47%; Comparative example 3 circulates about 160 weeks capacity attenuations about 6.1%, conservation rate is 93.9%, show that the capability retention of embodiment 6 and 7 is apparently higher than comparative example 3 by data, the battery adding trimethyl aluminium hexane solution is described in electrolyte, and the capability retention after its charge and discharge cycles is apparently higher than un-added battery.
As can be seen here, the performance of lithium ion battery adding the hexane solution of trimethyl aluminium is obviously better than un-added lithium ion battery; As seen from Figure 4: 1) lithium ion battery circulates repeatedly at identical conditions, add the capacity of lithium ion battery of the hexane solution of trimethyl aluminium apparently higher than the lithium ion battery do not added, and almost undamped; 2) lithium battery circulates repeatedly at identical conditions, and add the capability retention of the lithium ion battery of the hexane solution of trimethyl aluminium apparently higher than the lithium ion battery do not added, and battery performance is stablized, capability retention is high.
Repeatedly after charge and discharge cycles, the flatulence situation of battery: after battery preparation, measure the thickness of battery; Battery, after repeatedly Capacity fading is to 80% of initial capacity, is thought that the cycle life of battery stops, is stopped circulation, measure the thickness of battery, calculate the expansion rate of battery.
Thickness × 100% before expansion rate=(thickness before the thickness-circulation after the circulation)/circulation of battery.Test result is in table 4.
The expansion rate contrast of table 4: embodiment 6-7 and comparative example 3 battery
As can be seen from Table 4, after embodiment 6 and 7 charging cycle, the expansion rate of battery is 2.26% and 2.70%, substantially without flatulence phenomenon; And the expansion rate of comparative example 3 is 26.42%, there is obvious flatulence phenomenon.Illustrate in battery that the amount producing gas after with the addition of trimethyl aluminium significantly reduces, cell integrated performance is improved.
Claims (21)
1. for an electrolyte for lithium ion battery, comprise following component: organic solvent (A), electric conducting lithium salt (B) and additive (C), wherein, additive (C) is containing at least one metallo-organic compound or semimetal organic compound.
2. electrolyte according to claim 1, it is characterized in that, metallic element in described metallo-organic compound is selected from least one in aluminium, gallium, indium, thallium, zinc, cadmium, lithium, magnesium and antimony, and the semimetallic elements in semimetal organic compound is selected from least one in boron, silicon, arsenic, tellurium and phosphorus.
3. electrolyte according to claim 1, is characterized in that, in the organic group in described metallo-organic compound and semimetal organic compound, at least containing a carbon number be less than or equal to 4 alkyl or carbon number be less than or equal to 4 hydrocarbon derivative group.
4. electrolyte according to claim 3, it is characterized in that, the alkyl that described carbon number is less than or equal to 4 is selected from least one in alkyl and alkylene, and the hydrocarbon derivative group that carbon number is less than or equal to 4 is selected from least one of alkoxyl, alkene oxygen base, ether and halogenated hydrocarbon group.
5. according to the arbitrary described electrolyte of claim 1-4, it is characterized in that, described metallo-organic compound is selected from trimethyl aluminium, triethyl aluminum (TEA), tri-n-hexyl aluminum, triisobutyl aluminium, three n-butylaluminum, diisobutyl aluminium hydride, triethyl group tri-chlorination two aluminium, sesquialter ethylmercury chloride aluminium (EASC), aluminium diethyl monochloride (DEAC), ethyl aluminum dichloride (EADC), sesquialter methyl chloride aluminium (MASC), dimethylaluminum chloride, dimethyl one aluminum methoxide, trimethyl gallium (TMGa), trimethyl indium (TMIn), trimethyl thallium, zinc methide, diethyl zinc (DEZn), dimethyl cadmium, lithium methide, isobutyl group lithium, tert-butyl group magnesium chloride, n-butylmagnesium chloride magnesium, at least one in ethylmagnesium bromide and trimethylantimony, semimetal organic compound boron triethyl, dimethoxydiphenylsilane, Cyclohexyl Methyl Dimethoxysilane, arsenic trimethide, at least one in tellurium diethyl (DETe) and tri-butyl phosphine.
6. electrolyte according to claim 1, is characterized in that, the mass percentage that described metallo-organic compound and semimetal organic compound account for electrolyte component is 10ppm ~ 1%.
7. electrolyte according to claim 6, is characterized in that, the mass percentage that described metallo-organic compound and semimetal organic compound account for electrolyte component is 10 ~ 5000ppm.
8. electrolyte according to claim 1, is characterized in that, described metallo-organic compound and/or semimetal organic compound are contained in as a solution in additive (C).
9. electrolyte according to claim 8, is characterized in that, the solvent of described solution is selected from organic solvent (I).
10. electrolyte according to claim 9, is characterized in that, described organic solvent (I) is selected from least one in n-hexane, heptane, toluene, benzene, ether and oxolane.
11. electrolyte according to claim 1, it is characterized in that, described organic solvent (A) is selected from least one in carbonic ester and derivative, carboxylate and derivative thereof, carboxylic acid amide and derivative, ether and derivative thereof and sulfur-bearing organic solvent and derivative thereof.
12. electrolyte according to claim 11, it is characterized in that, described carbonic ester can be selected from least one in dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), propene carbonate (PC), ethylene carbonate (EC) and methyl propyl carbonate (MPC).
13. electrolyte according to claim 11, is characterized in that, described carboxylate can be selected from least one in (PA) such as gamma-butyrolacton (γ-BL), methyl formate (MF), methyl acetate (MA), ethyl propionate (EP) and propyl acetates.
14. electrolyte according to claim 11, is characterized in that, described carboxylic acid amide can be selected from least one in dimethyl formamide, methylformamide and METHYLPYRROLIDONE.
15. electrolyte according to claim 11, is characterized in that, described ether can be selected from least one in 1,3-dioxolanes, oxolane, oxinane and 1,2-dimethoxy-ethane.
16. electrolyte according to claim 11, is characterized in that, described sulfur-bearing organic solvent can be selected from least one in first ethyl sulfone, ethylene sulfite, propylene sulfite, sulfuric acid propylene and 4-methyl ethyl sulfate.
17. electrolyte according to claim 1, is characterized in that, described electric conducting lithium salt (B) is selected from least one inorganic lithium salt or organic lithium salt.
18. electrolyte according to claim 17, is characterized in that, described inorganic lithium salt is selected from lithium perchlorate (LiClO
4), hexafluoroarsenate lithium (LiAsF
6), LiBF4 (LiBF
4), lithium hexafluoro phosphate (LiPF
6) and lithium fluoride (LiF) at least one.
19. electrolyte according to claim 17, is characterized in that, described organic lithium salt is selected from trifluoromethyl sulfonic acid lithium (LiCF
3sO
3), two (trifluoromethane sulfonic acid) imine lithium (LiN (CF
3sO
2)
2), three (trimethyl fluoride sulfonyl) lithium methide (LiC (CF
3sO
2)
3), two (catechol) lithium borate (LiBBB), dimalonic acid lithium borate (LiBMB), di-oxalate lithium borate (LiBOB), three (catechol) lithium phosphate (LiTBP) and at least one of three (perfluoro-ethyl) three in lithium fluophosphate (LiFAP).
20. 1 kinds of lithium ion batteries, comprise the positive pole containing positive electrode active materials, the negative pole containing negative active core-shell material, and electrolyte as claimed in claim 1.
21. lithium ion batteries according to claim 20, is characterized in that, described negative active core-shell material is lithium titanate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310254376.0A CN104241688A (en) | 2013-06-24 | 2013-06-24 | Lithium ion battery electrolyte and lithium ion battery |
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|---|---|---|---|
| CN201310254376.0A CN104241688A (en) | 2013-06-24 | 2013-06-24 | Lithium ion battery electrolyte and lithium ion battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106898819A (en) * | 2017-04-14 | 2017-06-27 | 陈旻彧 | A kind of novel electrolyte and preparation method thereof and lithium battery |
| CN107069088A (en) * | 2016-12-20 | 2017-08-18 | 中国科学院成都有机化学有限公司 | A kind of linear siloxane additive and its for high-temperature electrolyte of lithium ion battery |
| CN107666011A (en) * | 2016-07-28 | 2018-02-06 | 微宏动力系统（湖州）有限公司 | A kind of nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery |
| CN112898154A (en) * | 2021-01-21 | 2021-06-04 | 宁波南大光电材料有限公司 | Method for removing water in ethyl lactate |
| CN113823836A (en) * | 2020-06-19 | 2021-12-21 | 微宏动力系统（湖州）有限公司 | Electrolyte, lithium ion battery and electric device |
| CN116565210A (en) * | 2023-07-07 | 2023-08-08 | 北京金羽新材科技有限公司 | Metal lithium protective layer, preparation method thereof and application thereof in lithium secondary battery |
| JP7458932B2 (en) | 2020-03-11 | 2024-04-01 | Ｍｕアイオニックソリューションズ株式会社 | Non-aqueous electrolyte for power storage devices and power storage devices |
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| US20090286157A1 (en) * | 2008-05-16 | 2009-11-19 | Zonghai Chen | Surface modification agents for lithium batteries |
| CN101632187A (en) * | 2007-02-21 | 2010-01-20 | 杰富意化学株式会社、 | Anode material for lithium-ion secondary battery, its preparation method, lithium ion secondary battery cathode and lithium rechargeable battery |
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| CN101632187A (en) * | 2007-02-21 | 2010-01-20 | 杰富意化学株式会社、 | Anode material for lithium-ion secondary battery, its preparation method, lithium ion secondary battery cathode and lithium rechargeable battery |
| US20090286157A1 (en) * | 2008-05-16 | 2009-11-19 | Zonghai Chen | Surface modification agents for lithium batteries |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107666011A (en) * | 2016-07-28 | 2018-02-06 | 微宏动力系统（湖州）有限公司 | A kind of nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery |
| CN107666011B (en) * | 2016-07-28 | 2020-07-28 | 微宏动力系统（湖州）有限公司 | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery |
| CN107069088A (en) * | 2016-12-20 | 2017-08-18 | 中国科学院成都有机化学有限公司 | A kind of linear siloxane additive and its for high-temperature electrolyte of lithium ion battery |
| CN106898819A (en) * | 2017-04-14 | 2017-06-27 | 陈旻彧 | A kind of novel electrolyte and preparation method thereof and lithium battery |
| JP7458932B2 (en) | 2020-03-11 | 2024-04-01 | Ｍｕアイオニックソリューションズ株式会社 | Non-aqueous electrolyte for power storage devices and power storage devices |
| CN113823836A (en) * | 2020-06-19 | 2021-12-21 | 微宏动力系统（湖州）有限公司 | Electrolyte, lithium ion battery and electric device |
| CN113823836B (en) * | 2020-06-19 | 2023-12-19 | 微宏动力系统（湖州）有限公司 | Electrolyte, lithium ion battery and electric device |
| CN112898154A (en) * | 2021-01-21 | 2021-06-04 | 宁波南大光电材料有限公司 | Method for removing water in ethyl lactate |
| CN116565210A (en) * | 2023-07-07 | 2023-08-08 | 北京金羽新材科技有限公司 | Metal lithium protective layer, preparation method thereof and application thereof in lithium secondary battery |
| CN116565210B (en) * | 2023-07-07 | 2023-09-22 | 北京金羽新材科技有限公司 | Metal lithium protective layer, preparation method thereof and application thereof in lithium secondary battery |
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Address after: 313000 Huzhou economic and Technological Development Zone, Zhejiang, Hung Fung Road, No. 2198 Applicant after: Microvast Power System (Huzhou) Co., Ltd. Address before: 313000 Zhejiang Province, Huzhou City Road No. 1555 building B Applicant before: Microvast Power System (Huzhou) Co., Ltd. |
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