CN101771167B - High-capacity lithium-ion electrolyte, battery and preparation method of battery - Google Patents
High-capacity lithium-ion electrolyte, battery and preparation method of battery Download PDFInfo
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- CN101771167B CN101771167B CN2010101090859A CN201010109085A CN101771167B CN 101771167 B CN101771167 B CN 101771167B CN 2010101090859 A CN2010101090859 A CN 2010101090859A CN 201010109085 A CN201010109085 A CN 201010109085A CN 101771167 B CN101771167 B CN 101771167B
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Images
Classifications
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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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention relates to a high-capacity lithium-ion electrolyte, a battery and a preparation method of a battery, in particular to the high-capacity lithium-ion electrolyte and the battery using the high-capacity lithium-ion electrolyte and the preparation method of the battery. The electrolyte disclosed by the invention comprises lithium salt and non-aqueous organic solvent, and also consists of the following components in weight percent in terms of the total weight of the electrolyte: 0.5-7% of film-forming additive, 0-15% of flame-retardant additive, 2-10% of antiovefill additive, 0.01-2%of stabilizer and 0.01-1% of wetting agent; the electrolyte can enable the anode with high Ni content to work stably, and reduce the battery cost; the high-capacity lithium-ion battery can perform high ratio capacity and excellent safety and high temperature property and cyclic life fully due to the addition and synergetic functions of various functional additives.
Description
Technical field
The present invention relates to lithium-ion electrolyte and battery, high-capacity lithium-ion electrolyte specifically, and the preparation method who uses battery and the battery of this kind electrolyte.
Background technology
The battery that generally uses has four kinds at present: lead-acid battery, nickel-cadmium cell, Ni-MH battery and lithium ion battery.Lithium ion battery is generally believed to have following advantage: specific energy is big; The specific power height; Self discharge is little; Memory-less effect; Cycle characteristics is good; But repid discharge, and efficient height; Operating temperature range is wide; Therefore non-environmental-pollutions etc. are expected to enter best electrical source of power ranks of 21 century.
The performance of lithium ion battery depends primarily on structure and the performance of used inside battery material.These inside battery materials comprise positive electrode, negative material, electrolyte and barrier film etc.Negative material is generally selected material with carbon element for use, present development comparative maturity, and the selection of positive electrode has become the key factor that restriction lithium ion battery performance further improves, price further reduces.In the present lithium ion battery of commercially producing, the cost of positive electrode accounts for about 40% of entire cell cost, and therefore, the reduction of positive electrode price is directly determining the reduction of lithium ion battery price.
China entered the 3G epoch along with 2009, progressively the popularizing of 3G mobile and net book, and as if slight battery more and more become a serious big problem.In the 3G epoch, the online of mobile phone, recreation, audio-visually will obtain further extensive use.But all these application all need be carried out the operation of long period at mobile phone, need the battery of mobile phone can support the time of more growing.And hardware configuration is soaring, the lifting of CPU processing speed, and the bigger resolution of screen size is higher, needs the guarantee of electric power equally.Therefore the capacity that improves battery of mobile phone becomes an urgent demand.And high Ni content positive electrode is gone up beyond doubt most possible one of pressure battery material that the 3G epoch bring battery of alleviating at present.High Ni content positive electrode battery will become the first-selected power supply in following 3G epoch undoubtedly.Because the Ni resource is abundanter relatively, price is cheaper relatively, and specific capacity is higher than other all known anode material for lithium-ion batteries far away, becomes one of the most promising positive electrode.
Following 3G market has the requirement of battery: the energy density height can provide supply of electric power the long period; Can be in operate as normal under the higher temperature conditions, and the situation that safety problem and capacity, cycle performance are decayed does not significantly appear; Can fast charging and discharging; Low price.High Ni content positive electrode with its aboundresources, cheap, nontoxic, height ratio capacity, advantage such as can quick high-pressure discharge and recharge and become the most promising positive electrode of lithium ion battery, but high Ni material structure instability, cause malformation easily, reduce cycle performance, especially under hot conditions, store, capacity attenuation is more serious, and produces a large amount of gas, brings very big potential safety hazard.Except improving the cycle performance that improves LiMn2O4 by positive electrode modification and battery process, the excellent electrolyte of exploitation also is the important means of improving high Ni material compatibility.
Summary of the invention
The object of the invention is to provide the preparation method of a kind of high-capacity lithium-ion electrolyte, battery and battery, it provides a kind of battery by using high Ni content positive electrode, this electrolyte is by control non-aqueous organic solvent ratio, and add functional additives such as film for additive, flame-retardant additive, anti-overcharge additive, stabilizer, wetting agent, make and adopt the lithium ion battery of this electrolyte to have high specific capacity and excellent security energy, cycle life and high-temperature behavior, make it be easier to promote and use.
Technical solution of the present invention is that it has comprised lithium salts, non-aqueous organic solvent, also contains 0.5%～7% film for additive that accounts for the electrolyte total weight percent, 0%～15% flame-retardant additive, 2%～10% anti-overcharge additive, 0.01%～2% stabilizer, 0.01%～1% wetting agent;
Described wetting agent is selected from any or several in the nonionic surface active agent, any or several in the fluoro-alkyl sulfonic acid in the fluorine carbon surfactant, fluoro-alkyl sulfonic acid lithium, fluoro-alkyl phosphate, fluoro oxygen in ninth of the ten Heavenly Stems base benzene sulfonic acid sodium salt, fluoro oxygen in ninth of the ten Heavenly Stems base benzene sulfonic acid lithium or the fluoro APEO wherein, wherein fluoro can be perfluoro or part fluoro, and the alkyl of above-mentioned substance is C4～C10.
More than non-aqueous organic solvent of the present invention be selected from any or several in carbonic ester and halo derivatives thereof, carboxylate, the sulfuric ester; Described lithium salts is selected from LiPF
6, LiBF
4, any or several combinations among LiBOB or the LiODFB, content is 0.9mol/L～1.5mol/L.
Above-described carbonic ester and halo derivatives thereof are selected from ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, any or several in methyl ethyl carbonate, carbonic acid first propyl ester, chlorocarbonic acid vinyl acetate, chlorocarbonic acid propylene ester, dichloro-propene carbonate, three chloro propene carbonates, fluorinated ethylene carbonate, fluoro propene carbonate, two fluoro propene carbonates or the three fluoro propene carbonates; Described carboxylate is selected from any or several in methyl formate, Ethyl formate, methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, methyl butyrate or the ethyl butyrate; Described sulfuric ester is selected from one or more in ethylene sulfite, propylene sulfite or the sulfurous acid butene esters.
Film for additive of the present invention is selected from vinylene carbonate, vinylethylene carbonate, 1,3-sulfonic acid propiolactone, 1,4-sulfonic acid butyrolactone, vinyl sulfone(Remzaol, diphenyl sulphone (DPS), maleic anhydride, acetic anhydride, three (trimethyl silane) phosphate, three (trimethyl silane) borate, three (trimethyl silane) phosphite ester or N, any or several in N '-dimethyl trifluoroacetamide; Described flame-retardant additive be selected from organic phosphorus compound and derivative thereof as: trimethyl phosphate, methyl acid phosphate trimethyl, triethyl phosphate, triphenyl phosphate, phosphonitrile and derivative thereof are as any or several combinations in hexachlorocyclotriph,sphazene, three o-phenylenediamine basic rings, three phosphonitriles; Described anti-overcharge additive is selected from any or several combinations in phenylate and halo derivatives, phenyl compound, alkyl benzene ring derivatives, halogeno-benzene ring derivatives, thiophene, furans or the metallocenes.
Above-described stabilizer is selected from triethylamine, the N of amine, dinethylformamide, N, N-dimethylethanolamine, succimide, maleimide, N, N '-diisopropyl carbimide, N, N '-dicyclohexyl carbimide, N, one or more in N '-diisopropyl carbimide or two (trimethyl silicon based) phosphinylidyne diimine; Or the heptamethyldisilazane of alkyl silazane class, hexamethyldisiloxane, hexaphenyl ring three silazane or prestox cyclotetrasilazane one or more; Isocyanates hexamethylene diisocyanate, methyl diphenylene diisocyanate, chlorosulphonyl isocyanate or any or several in the Methyl benzenesulfonyl isocyanate.
The battery that has used electrolyte of the present invention is to have comprised positive pole, negative pole, barrier film, plastic-aluminum combined film package bag, positive and negative lug and electrolyte; Wherein this anode is 93%～96% positive active material, 1%～3% conductive agent, 2%～4% binding agent; Battery cathode is 94%～97% negative electrode active material, 0%～2% conductive agent, 2%～4% binding agent; Wherein positive active material is selected from LiNi
xCo
1-xO
2, LiNi
xMn
yCo
1-x-yO
2, one or more the non-crystal mixtures among the LiCoO2, wherein x 〉=0.5, wherein LiNi
xCo
1-xO
2In x preferred 0.8～0.7, LiNi wherein
xMn
yCo
1-x-yO
2Middle x 〉=0.5, y≤0.3, preferred 8: 1: 1～5: 3: 2 of the ratio of Ni: Mn: Co; Negative electrode active material is selected from the one or more combination of native graphite, Delanium, compound and carbonaceous mesophase spherules; Conductive agent is selected from the one or more combination in acetylene black, graphite, carbon nano-tube or the gas-phase growth of carbon fibre (VGCF); Binding agent is selected from the one or more combination in Kynoar (PVDF), carboxymethyl cellulose (CMC), butadiene-styrene rubber (SBR) or the polytetrafluoroethylene (PTFE).
The preparation method of above battery of the present invention is:
A, just very positive active material, conductive agent, binding agent are mixed, be mixed with the slurry of viscosity 4000～6000cps with solvent, slurry is coated on the thick aluminum foil current collector of 10～20 μ m, dry pair roller becomes positive electrode, anodal small pieces are made in shearing, with laser welding anodal small pieces and positive pole ear are welded together;
B, negative pole are that negative electrode active material, conductive agent, binding agent are mixed, be mixed with slurry with solvent, slurry is coated on the thick Copper Foil collector of 5～15 μ m, dry pair roller becomes positive electrode, the negative pole small pieces are made in shearing, connect with spot welding machine negative pole small pieces and negative lug are welded together;
C, usefulness polypropylene and poly composite membrane are put into battery case as membrane coil coiled electricity core, inject above-mentioned electrolyte and seal and change into processing.
Advantage of the present invention is:
A, battery select for use the high Ni positive electrode of high power capacity as anodal main active substances, negative pole is selected for use the native graphite of height ratio capacity to make main active material to have improved the capacity of battery more than 10%, utilize special preparation method to make the positive pole energy steady operation of high Ni content, and reduced battery cost;
B, conductive agent are selected materials such as carbon nano-tube and VGCF for use, thereby have improved the conductivity of electrode;
C, electrolyte are selected choosing of higher boiling point non-aqueous organic solvent for use, can improve the stability under the high temperature resistant of electrolyte and the abuse state; Adding film for additive can form diaphragm on the both positive and negative polarity surface of battery, and the prevention positive and negative pole material contacts with electrolyte, suppresses electrolyte in the decomposition on both positive and negative polarity surface, improves the stability under the battery high-temperature; Add flame-retardant additive and anti-overcharge additive and can solve the safety problem of battery under the abuse state; Add wetting agent and can accelerate electrolyte to the infiltration of high power capacity electricity in-core portion, and improved the compatibility of electrode interface, and then improve the efficiency for charge-discharge of lithium ion battery; Add stabilization additives can the act synergistically decomposition that stops lithium salts and the rising of acidity, and then improve the storage time of electrolyte and circulation and the high-temperature stability of battery.The adding of multiple functional additive, synergy make above-mentioned high-capacity lithium ion cell can give full play to height ratio capacity and have excellent security energy, high-temperature behavior and cycle life.
Description of drawings
Fig. 1 is capacity and the cycle performance contrast of embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, Comparative Examples 1 battery.
Fig. 2 is embodiment 6, embodiment 7, embodiment 8, embodiment 9, embodiment 10, Comparative Examples 2 electrolyte, is prepared into capacity and the cycle performance contrast of high-capacity lithium ion cell.
Fig. 3 is embodiment 6, embodiment 7, embodiment 8, embodiment 9, embodiment 10, Comparative Examples 2 electrolyte, is prepared into 60 ℃ of discharge capacity contrasts that store after 7 days all over the sky down of high-capacity lithium ion cell high temperature.
Embodiment
Embodiment 1
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
The battery of electrolyte of the present invention is to have comprised positive pole, negative pole, barrier film, plastic-aluminum combined film package bag, positive and negative lug and electrolyte; Wherein this anode is 93%～96% positive active material, 1%～3% conductive agent, 2%～4% binding agent; Battery cathode is 94%～97% negative electrode active material, 0%～2% conductive agent, 2%～4% binding agent; Wherein positive active material is selected from LiNi
xCo
1-xO
2, LiNi
xMn
yCo
1-x-yO
2In one or more non-crystal mixtures or/with LiCoO
2Arbitrary proportion combination, wherein x 〉=0.5, wherein LiNi
xCo
1-xO
2In x preferred 0.8～0.7, LiNi wherein
xMn
yCo
1-x-yO
2Middle x 〉=0.5, y≤0.3, preferred 8: 1: 1～5: 3: 2 of the ratio of Ni: Mn: Co; Negative electrode active material is selected from the one or more combination of native graphite, Delanium, compound and carbonaceous mesophase spherules; Conductive agent is selected from the one or more combination in acetylene black, graphite, carbon nano-tube or the gas-phase growth of carbon fibre (VGCF); Binding agent is selected from the one or more combination in Kynoar (PVDF), carboxymethyl cellulose (CMC), butadiene-styrene rubber (SBR) or the polytetrafluoroethylene (PTFE).
Comparative Examples 1
Anodal preparation: will slowly add 50g PVDF while stirring in the solvent NMP1800g adding slurry tank, slowly add 20g acetylene black and 20g VGCF stirring 1H after stirring 1H, the LiCoO2 that gets 1800g more slowly adds while stirring, behind no dry powder, add NMP (N-methyl pyrrolidone) adjusting slurry viscosity 4000～6000cps after opening high-speed stirred 2H, filter slurry with 150 eye mesh screens.Prepared slurry is coated on the thick aluminum foil current collector of 15 μ m, and dry back pair roller becomes positive electrode, shears and makes anodal small pieces, with laser welder anodal small pieces and positive pole ear is welded together.
The negative pole preparation:
To slowly add 13g CMC while stirring in the pure water 800g adding slurry tank, slowly add 8g VGCF stirring 1H after stirring 1H, the native graphite of getting 800g again slowly adds while stirring, behind no dry powder, add 12gSBR (butadiene-styrene rubber) continuation high-speed stirred 30min after opening high-speed stirred 2H, add water and regulate slurry viscosity 2000～3000cps, filter slurry with 100 eye mesh screens.Prepared slurry is coated on the thick Copper Foil collector of 10 μ m, and dry back pair roller becomes negative electrode, shears and makes the negative pole small pieces, with spot welding machine negative pole small pieces and negative lug is welded together.
With the both positive and negative polarity of above-mentioned processing, use polypropylene and poly composite membrane as membrane coil coiled electricity core, put into plastic-aluminum combined film package bag, inject electrolyte and the hot-press sealed of embodiment 6, make 053048 type flexible packing lithium ion battery.It is changed into the processing back test its capacity and cycle performance according to " GB/T 18287-2000 cell phone lithium ion battery general specification ".
Embodiment 1～5
The preparation method is identical with Comparative Examples 1, and just corresponding anodal preparation changes just like following table:
The battery of preparation gained is also tested its capacity and cycle performance according to " GB/T 18287-2000 cell phone lithium ion battery general specification ".
Comparative Examples 2
To be dissolved in as the LiPF6 of lithium salts in the mixed solvent of ethylene carbonate and cycle performance ester (EC)/dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC) (mass ratio is 1/1/1) and obtain solution, wherein the concentration of LiPF6 is 1.0M.Namely make electrolyte.This electrolyte is added in the battery of embodiment 1 and tested its capacity and cycle performance according to " GB/T18287-2000 cell phone lithium ion battery general specification " then.
Embodiment 6
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)/ethyl butyrate (EB) (mass ratio is 20/10/10/40/20) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.This electrolyte is added in the battery of embodiment 1 and tested its capacity and cycle performance according to " GB/T 18287-2000 cell phone lithium ion battery general specification " then.
Embodiment 7
Will be as LiBOB and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)/ethyl butyrate (EB) (mass ratio is 20/10/10/40/20) and obtain solution, wherein the concentration of LiBOB is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.This electrolyte is added in the battery of embodiment 1 and tested its capacity and cycle performance according to " GB/T 18287-2000 cell phone lithium ion battery general specification " then.
Embodiment 8
Will be as LiODFB and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)/ethyl butyrate (EB) (mass ratio is 20/10/10/40/20) and obtain solution, wherein the concentration of LiODFB is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.This electrolyte is added in the battery of embodiment 1 and tested its capacity and cycle performance according to " GB/T 18287-2000 cell phone lithium ion battery general specification " then.
Embodiment 9
Will be as LiBF4, LiODFB and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)/ethyl butyrate (EB) (mass ratio is 20/10/10/40/20) and obtain solution, wherein the concentration of LiODFB is 0.1M, the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.This electrolyte is added in the battery of embodiment 1 and tested its capacity and cycle performance according to " GB/T 18287-2000 cell phone lithium ion battery general specification " then.
Embodiment 10
Will be as LiBF4, LiBOB and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)/ethyl butyrate (EB) (mass ratio is 20/10/10/40/20) and obtain solution, wherein the concentration of LiBOB is 0.1M, the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.
Embodiment 11
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)/ethyl propionate (EP) (mass ratio is 20/10/10/40/20) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.
Embodiment 12
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)/ethyl butyrate (EB)/perfluorocarbon acid vinyl acetate (FEC) (mass ratio is 15/10/10/40/20/5) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.
Embodiment 13
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)/ethyl butyrate (EB)/three fluoro propene carbonate (F3PC) (mass ratio is 15/10/10/40/20/5) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.
Embodiment 14
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)/sulfuric acid butene esters (BS) (mass ratio is 20/10/10/40/20) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.
Embodiment 15
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC) (mass ratio is 30/10/10/50) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.
Embodiment 16
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)/ethyl butyrate (EB) (mass ratio is 20/10/10/50/10) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), 1% of electrolyte total weight adds vinyl sulfone(Remzaol (VS), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.
Embodiment 17
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)/ethyl butyrate (EB) (mass ratio is 20/10/10/50/10) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), 1% of electrolyte total weight adds vinyl sulfone(Remzaol (VS), press 3% of electrolyte total weight and add 1,4-sulfonic acid butyrolactone (1,4-BS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.
Embodiment 18
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC) (mass ratio is 30/10/10/50) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds three (trimethyl silane) phosphate (TMSP), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.
Embodiment 19
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC) (mass ratio is 30/10/10/50) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1.5% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds maleic anhydride (MA), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.
Embodiment 20
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC) (mass ratio is 30/10/10/50) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1% of electrolyte total weight then and add vinylene carbonate (VC), 2% of electrolyte total weight adds N, N '-dimethyl trifluoroacetamide, press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 5% of electrolyte total weight and add biphenyl, namely make electrolyte.
Embodiment 21
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC) (mass ratio is 30/10/10/50) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1.5% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), 0.5% of electrolyte total weight adds three (trimethyl silane) phosphate (TMSP), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 6% of electrolyte total weight and add toluene, namely make electrolyte.
Embodiment 22
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC) (mass ratio is 30/10/10/50) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1.5% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), 0.5% of electrolyte total weight adds three (trimethyl silane) phosphate (TMSP), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add monoethanolamine, press 2% of electrolyte total weight and add toluene, press 5% of electrolyte total weight and add methyl phenyl ethers anisole, press 0.1% of electrolyte total weight and add full-fluorine octyl sulfuryl fluoride, namely make electrolyte.
Embodiment 23
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC) (mass ratio is 30/10/10/50) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1.5% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), 0.5% of electrolyte total weight adds three (trimethyl silane) phosphate (TMSP), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add triethylamine, press 2% of electrolyte total weight and add toluene, press 5% of electrolyte total weight and add methyl phenyl ethers anisole, press 0.01% of electrolyte total weight and add heptamethyldisilazane, press 0.5% of electrolyte total weight and add phenyl isocyanate, namely make electrolyte.
Embodiment 24
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC) (mass ratio is 30/10/10/50) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1.5% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), 0.5% of electrolyte total weight adds three (trimethyl silane) phosphate (TMSP), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.1% of electrolyte total weight and add triethylamine, press 2% of electrolyte total weight and add toluene, press 5% of electrolyte total weight and add methyl ether, press 0.01% of electrolyte total weight and add heptamethyldisilazane, press 0.5% of electrolyte total weight and add phenyl isocyanate, namely make electrolyte.
Embodiment 25
Will be as LiBF4 and the LiPF of lithium salts
6Be dissolved in the mixed solvent of ethylene carbonate (EC)/propene carbonate (PC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC) (mass ratio is 30/10/10/50) and obtain solution, wherein the concentration of LiBF4 is 0.2M, LiPF
6Concentration be 1M.In this solution, press 1.5% of electrolyte total weight then and add vinylene carbonate (VC), 0.5% of electrolyte total weight adds vinylethylene carbonate (VEC), 0.5% of electrolyte total weight adds three (trimethyl silane) phosphate (TMSP), press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone (1,3-PS), press 0.05% of electrolyte total weight and add triethylamine, press 5% of electrolyte total weight and add toluene, press 5% of electrolyte total weight and add hexachlorocyclotriph,sphazene, press 0.01% of electrolyte total weight and add heptamethyldisilazane, press 0.5% of electrolyte total weight and add phenyl isocyanate, namely make electrolyte.
Claims (3)
1. a high-capacity lithium-ion electrolyte is characterized in that: will be as the LiBF of lithium salts
4And LiPF
6Be dissolved in ethylene carbonate/propylene carbonate/methyl ethyl carbonate/diethyl carbonate, above-mentioned four kinds of material masses are than being to obtain solution in 30/10/10/50 the mixed solvent, wherein LiBF
4Concentration be 0.2M, LiPF
6Concentration be 1M, in this solution, press 1.5% of electrolyte total weight then and add vinylene carbonate, 0.5% of electrolyte total weight adds vinylethylene carbonate, 0.5% of electrolyte total weight adds three (trimethyl silane) phosphate, press 5% of electrolyte total weight and add 1,3-sulfonic acid propiolactone, press 0.1% of electrolyte total weight and add triethylamine, press 2% of electrolyte total weight and add toluene, press 5% of electrolyte total weight and add methyl ether, press 0.01% of electrolyte total weight and add heptamethyldisilazane, press 0.5% of electrolyte total weight and add phenyl isocyanate, namely make electrolyte.
2. right to use requires a kind of high-capacity lithium ion cell of 1 described electrolyte, it is characterized in that this battery has comprised positive pole, negative pole, barrier film, plastic-aluminum combined film package bag, positive and negative lug and electrolyte; Wherein this anode is 93%～96% positive active material, 1%～3% conductive agent, 2%～4% binding agent; Battery cathode is 94%～97% negative electrode active material, 0%～2% conductive agent, 2%～4% binding agent; Wherein positive active material is selected from LiNi
xCo
1-xO
2, LiNi
xMn
yCo
1-x-yO
2In one or more non-crystal mixture, wherein LiNi
xCo
1-xO
2Middle x is 0.8～0.7, wherein LiNi
xMn
yCo
1-x-yO
2Middle x 〉=0.5, y≤0.3, the ratio of Ni: Mn: Co is 8: 1: 1～5: 3: 2; Negative electrode active material is selected from the one or more combination of native graphite, Delanium, compound and carbonaceous mesophase spherules; Conductive agent is selected from the one or more combination in acetylene black, graphite, carbon nano-tube or the gas-phase growth of carbon fibre; Binding agent is selected from the one or more combination in Kynoar, carboxymethyl cellulose, butadiene-styrene rubber or the polytetrafluoroethylene.
3. the preparation method of a kind of high-capacity lithium ion cell according to claim 2 is characterized in that:
A, just very conductive agent, binding agent are mixed stir 0.5～1.5 hour after, positive active material is added in the said mixture up to no dry powder again, high-speed stirred is 1～3 hour then, be mixed with the slurry of viscosity 4000～6000cps with solvent, slurry is coated on the thick aluminum foil current collector of 10～20 μ m, dry pair roller becomes positive electrode, shears and makes anodal small pieces, with laser welding anodal small pieces and positive pole ear is welded together;
B, negative pole are that conductive agent, binding agent were mixed stirring after 0.5～1.5 hour, negative electrode active material is added in the said mixture up to no dry powder again, high-speed stirred is 1～3 hour then, be mixed with behind the slurry with solvent and continued high-speed stirred 15～60 minutes, slurry is coated on the thick Copper Foil collector of 5～15 μ m, dry pair roller becomes negative electrode, shears and makes the negative pole small pieces, with spot welding machine negative pole small pieces and negative lug is welded together;
C, usefulness polypropylene and poly composite membrane are put into battery case as membrane coil coiled electricity core, inject above-mentioned electrolyte and seal and change into processing.
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