CN108075188A - A kind of nonaqueous lithium ion battery electrolyte and lithium ion battery - Google Patents

A kind of nonaqueous lithium ion battery electrolyte and lithium ion battery Download PDF

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Publication number
CN108075188A
CN108075188A CN201610999350.2A CN201610999350A CN108075188A CN 108075188 A CN108075188 A CN 108075188A CN 201610999350 A CN201610999350 A CN 201610999350A CN 108075188 A CN108075188 A CN 108075188A
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ion battery
lini
lithium ion
performance
electrolyte
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陈州文
王霹霹
赵苗苗
戴晓兵
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Zhuhai Smoothway Electronic Materials Co Ltd
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Zhuhai Smoothway Electronic Materials Co Ltd
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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
    • 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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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

Abstract

The invention discloses a kind of nonaqueous lithium ion battery electrolyte and lithium ion batteries.Nonaqueous lithium ion battery electrolyte contains electrolytic salt, non-aqueous organic solvent and functional additive, and it is (K) that functional additive, which is selected from chemical formula,m+4Pm+2O3m+7,(L)n/2+2Pn+2O3n+7Or (K)s(PO3)sIn a kind of compound or multiple several compounds combination；Wherein, K is the alkali metal element outside the first main group dehydrogenation；L is alkali earth metal of second main group in addition to beryllium in the periodic table of elements；(K)m+4Pm+2O3m+7In include anionic group Pm+2O3m+7 (m+4)‑, wherein, m is 0 or positive integer；(L)n/2+ 2Pn+2O3n+7In include anionic group Pn+2O3n+7 (n+4)‑, wherein, n is 0 or positive even numbers；(K)s(PO3)sIn include anionic group (PO3)s s‑, wherein, s is 3 or the integer more than 3.Battery made of nonaqueous lithium ion battery electrolyte of the present invention can form the high SEI films of dense uniform, lithium-ion-conducting when being melted into for the first time, improve battery first charge-discharge efficiency, improve battery normal-temperature circulating performance, high rate performance, high temperature cyclic performance, high-temperature storage performance, low temperature performance.

Description

A kind of nonaqueous lithium ion battery electrolyte and lithium ion battery
Technical field
The present invention relates to battery more particularly to a kind of nonaqueous lithium ion battery electrolytes and lithium ion battery.
Background technology
With increasingly miniaturization and the fast development of the portable electric appts of lightness, to being set for these portable electronics The demand of standby small-sized, light, the thin and high performance battery for providing power supply increasingly increases.But as battery is to small size, high energy Metric density is pursued, and constantly improves positive and negative anodes compacted density or the high-capacity cathode material for using cycle performance not good enough, therewith Also a series of performance issues of battery are brought, for example poor circulation, high-temperature behavior are poor, cryogenic property and high rate performance are poor, it is low Lithium is easily analysed during warm charge and discharge.
The reason for generating drawbacks described above is that lithium ion battery can form one layer during initial charge in negative terminal surface SEI films, at low ambient temperatures, if the SEI films formed are too thick, membrane impedance is higher, then lithium ion can not migrate through, and will occur Analyse lithium；During high temperature circulation, if the SEI films formed are not form compact and stable enough, SEI films gradually can be dissolved or ruptured, and be caused sudden and violent The cathode continuation of dew reacts with electrolyte, while consuming electrolyte so that battery capacity reduces.
The content of the invention
The technical problem to be solved in the present invention is to provide one kind can improve battery first charge-discharge efficiency, and it is normal to improve battery Warm cycle performance, high rate performance, high temperature cyclic performance, high-temperature storage performance, the nonaqueous lithium ion battery electricity of low temperature performance Solve liquid.
Another technical problems to be solved of the invention are to provide a kind of first charge-discharge efficiency height, battery normal temperature circulation The good lithium ion battery of energy, high rate performance, high temperature cyclic performance, high-temperature storage performance and low temperature performance.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is a kind of nonaqueous lithium ion battery electrolyte, Containing electrolytic salt, non-aqueous organic solvent and functional additive, it is (K) that functional additive, which is selected from chemical formula,m+4Pm+2O3m+7, (L)n/2+2Pn+2O3n+7Or (K)s(PO3)sIn a kind of compound or multiple several compounds combination；
Wherein, K is the alkali metal element outside the first main group dehydrogenation in the periodic table of elements；L is selected from period of element Alkali earth metal of second main group in addition to beryllium in table；
(K)m+4Pm+2O3m+7In include anionic group P as shown in structural formula (1)m+2O3m+7 (m+4)-, wherein, m for 0 or Positive integer；
(L)n/2+2Pn+2O3n+7In include anionic group P as shown in structural formula (2)n+2O3n+7 (n+4)-, wherein, n for 0 or Person's positive even numbers；
(K)s(PO3)sIn include anionic group (PO as shown in structural formula (2)3)s s-, wherein, s is 3 or more than 3 Integer；
Above-described functional additives for Li-ion battery electrolytes, the functional additive are
Above-described functional additives for Li-ion battery electrolytes, described states functional additive in non-aqueous organic solvent In molar concentration be 0.01%~1%.
Above-described functional additives for Li-ion battery electrolytes, the non-aqueous organic solvent is ethylene carbonate, carbon Acid propylene ester, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, methyl acetate, ethyl acetate, acetic acid third One or more kinds of mixtures in ester, butyl acetate, ethyl propionate, propyl propionate or butyl propionate.
Above-described functional additives for Li-ion battery electrolytes, the electrolytic salt are LiPF6、LiBF4、LiClO4、 LiBOB、LiDFOB、LiFAP、LiAsF6、LiSbF6、LiCF3S03、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiN(SO2CF3)2、 LiN(SO2C4F9)2、LiC(SO2CF3)3、LiPF3(C3F7)3、LiB(CF3)4、LiBF3(C2F5)、LiPO2F2、LiDMSI、 LiTESI, LiHPSI or LiPF4C2O4In one or more kinds of mixtures；
Above-described functional additives for Li-ion battery electrolytes, the electrolytic salt rubbing in non-aqueous organic solvent Your concentration is 0.5~2.5mol/L.
A kind of lithium ion battery, including anode, cathode, membrane and electrolyte, the electrolyte for above-mentioned non-aqueous lithium from Sub- battery electrolyte.
Above-described lithium ion battery, the material of the cathode include Delanium, native graphite, Si cathode and its conjunction Gold, Sn cathode and its alloy, lithium anode and its alloy, metal oxide MOx, metal nitride, LixMyOzOr Li4Ti5- xMxO12In one or more kinds of mixtures；The metal oxide MOxIn M be：Ti、V、Cr、Fe、Co、Ni、Cu、 Zn, Ge or Sn, x are the number of oxygen atom；The LixMyOzIn M be：Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ge or Sn, x, Y, the value of z meets the requirement for forming chemical molecular formula；The Li4Ti5-xMxO12In M for Mg, Al, Ba, Sr or Ta, 0≤x ≤1。
Above-described lithium ion battery, the material of the anode include the mixed of the one or more in following component Close object：Li4-xMxTi5O12, wherein M be Mg, Al, Ba, Sr or Ta, 0≤x≤1；MnO2；V2O5；LiV3O8；LiMC1xMC21-xPO4, Wherein MC1 or MC2 be Fe, Mn, Ni, Co, Cr or Ti, 0≤x≤1；Li3V2-xMx(PO4)3, wherein M for Cr, Co, Fe, Mg, Y, Ti, Nb or Ce, 0≤x≤1；LiVPO4F；LiMC1xMC21-xO2, wherein MC1 or MC2 for Fe, Mn, Ni, Co, Cr, Ti, Mg or Al, 0≤x≤1；LiMC1xMC2yMC31-x-yO2, wherein MC1, MC2 or MC3 be Fe, Mn, Ni, Co, Cr, Ti, Mg or Al, 0≤x ≤ 1,0≤y≤1；LiMn2-yXyO4, wherein X be Cr, Al or Fe, 0≤y≤1；LiNi0.5-yXyMn1.5O4, wherein X for Fe, Cr, Zn, Al, Mg, Ga, V or Cu, 0≤y<0.5；LiMC1yMC2zMC31-y-zO2, wherein MC1, MC2 or MC3 is Mn, Ni, Co, Cr, Fe Or their mixture, x=0.3~0.5, y≤0.5, z≤0.5；xLi2MnO3·(1-x)LiMC1yMC2zMC31-y-zO2, Middle MC1, MC2 or MC3 be Mn, Ni, Co, Cr, Fe or their mixture, x=0.3~0.5, y≤0.5, z≤0.5； Li2MSiO4, wherein M is Mn, Fe or Co；Li2MSO4, wherein M is Mn, Fe or Co；LiMSO4F, wherein M are Fe, Mn or Co； Li2-x(Fe1-yMny)P2O7, wherein 0≤x≤2,0≤y≤1；LiMn2O4；LiFePO4；LiCoO2；LiNi0.8Co0.15Al0.05O2； LiNi1/3Mn1/3Co1/3O2；LiNi0.5Mn0.3Co0.2O2；LiNi0.4Mn0.4Co0.2O2；LiNi0.5Mn1.5O4；xLi2MnO3·(1-x) LiNi1/3Mn1/3Co1/3O2, wherein, 0≤x≤1；Or LiCoPO4；In above-described positive electrode, wherein：LiCoO2； LiNi0.8Co0.15Al0.05O2；LiNi1/3Mn1/3Co1/3O2；LiNi0.5Mn0.3Co0.2O2；LiNi0.4Mn0.4Co0.2O2； LiNi0.5Mn1.5O4；LiCoPO4And xLi2MnO3·(1-x)LiNi1/3Mn1/3Co1/3O2, wherein, 0≤x≤1.
The nonaqueous lithium ion battery electrolyte of work(of the present invention can significantly improve the efficiency for the first time of lithium ion battery；By In its can promote electrolyte film forming more it is thin evenly, so as to be obviously improved the normal-temperature circulating performance of battery and room temperature multiplying power Discharge performance, and high temperature cyclic performance can be improved, improve low temperature analysis lithium situation, low temperature performance can also obtain greatly Improve.
Specific embodiment
The functional additive of lithium-ion battery electrolytes of the embodiment of the present invention be selected from chemical formula be (K)m+4Pm+2O3m+7, (L)n/2+2Pn+2O3n+7Or (K)s(PO3)sA kind of compound or multiple several compounds combination.
Wherein, K is the alkali metal element outside the first main group dehydrogenation in the periodic table of elements；L is selected from period of element Alkali earth metal of second main group in addition to beryllium in table；
(K)m+4Pm+2O3m+7In include anionic group P as shown in structural formula (1)m+2O3m+7 (m+4)-, wherein, m for 0 or Positive integer；
(L)n/2+2Pn+2O3n+7In include anionic group P as shown in structural formula (2)n+2O3n+7 (n+4)-, wherein, n for 0 or Person's positive even numbers；
(K)s(PO3)sIn include anionic group (PO as shown in structural formula (2)3)s s-, wherein, s is 3 or more than 3 Integer；
Lithium primary battery nonaqueous electrolytic solution of the present invention includes non-aqueous organic solvent and electrolytic salt, further includes function and adds Add agent.
Functional additive can be,
Molar concentration of the functional additive in nonaqueous lithium ion battery electrolyte is 0.01%~1%, preferably 0.05%.
Non-aqueous organic solvent is ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), carbonic acid diethyl Ester (DEC), methyl ethyl carbonate (EMC), gamma-butyrolacton (GBL), methyl acetate (MA), ethyl acetate (EA), propyl acetate (EP), one or more kinds of mixtures in butyl acetate, ethyl propionate, propyl propionate or butyl propionate.Except above-mentioned row That lifts is outer, can also be that there is no limit in the present invention for this well known to a person skilled in the art any conventional non-aqueous organic solvent.
Electrolytic salt is LiPF6、LiBF4、LiClO4、LiBOB、LiDFOB、LiFAP、LiAsF6、LiSbF6、LiCF3S03、 LiN(SO2CF3)2、LiN(SO2C2F5)2、LiN(SO2CF3)2、LiN(SO2C4F9)2、LiC(SO2CF3)3、LiPF3(C3F7)3、LiB (CF3)4、LiBF3(C2F5)、LiPO2F2, LiDMSI (difluoromethyl ring di-sulfonyl imides lithium), LiTESI (the double sulphurs of four fluoro ethyl rings Imide li), LiHPSI (hexafluoro propyl ring double sulfimide lithiums) or LiPF4C2O4In one or more kinds of mixtures, It is applicable in the present invention with electrolytic salt well known to a person skilled in the art any conventional electrolyte, it is unrestricted.It is described Concentration of the electrolytic salt in lithium-ion battery electrolytes is 0.5~2.5mol/L.
Anode, cathode, membrane and above-mentioned electrolyte included by the lithium ion battery of the present invention.
Cathode is included to be born selected from Delanium, native graphite, Si cathode and its alloy, Sn cathode and its alloy, lithium metal Pole and its alloy, metal oxide MOx, metal nitride, LixMyOzOr Li4Ti5-xMxO12In it is one or more kinds of mixed Close object, wherein metal oxide MOxIn M be：Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ge or Sn, x are the number of oxygen atom, LixMyOzIn M be：Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ge or Sn, the value of x, y, z, which meets, forms wanting for chemical molecular formula It asks, Li4Ti5-xMxO12In M for Mg, Al, Ba, Sr or Ta, 0≤x≤1.
Anode includes one or more kinds of mixtures in following component：Li4-xMxTi5O12, wherein M for Mg, Al, Ba, Sr or Ta, 0≤x≤1；MnO2；V2O5；LiV3O8；LiMC1xMC21-xPO4, wherein MC1 or MC2 are Fe, Mn, Ni, Co, Cr or Ti, 0≤x≤1；Li3V2-xMx(PO4)3, wherein M be Cr, Co, Fe, Mg, Y, Ti, Nb or Ce, 0≤x≤1；LiVPO4F； LiMC1xMC21-xO2, wherein MC1 or MC2 are Fe, Mn, Ni, Co, Cr, Ti, Mg or Al, 0≤x≤1；LiMC1xMC2yMC31-x- yO2, wherein MC1, MC2 or MC3 be Fe, Mn, Ni, Co, Cr, Ti, Mg or Al, 0≤x≤1,0≤y≤1；LiMn2-yXyO4, wherein X be Cr, Al or Fe, 0≤y≤1；LiNi0.5-yXyMn1.5O4, wherein X be Fe, Cr, Zn, Al, Mg, Ga, V or Cu, 0≤y<0.5； LiMC1yMC2zMC31-y-zO2, wherein MC1, MC2 or MC3 be Mn, Ni, Co, Cr, Fe or their mixture, x=0.3~0.5, Y≤0.5, z≤0.5；xLi2MnO3·(1-x)LiMC1yMC2zMC31-y-zO2, wherein MC1, MC2 or MC3 for Mn, Ni, Co, Cr, Fe or their mixture, x=0.3~0.5, y≤0.5, z≤0.5；Li2MSiO4, wherein M is Mn, Fe or Co；Li2MSO4, Wherein M is Mn, Fe or Co；LiMSO4F, wherein M are Fe, Mn or Co；Li2-x(Fe1-yMny)P2O7, wherein 0≤x≤2,0≤y≤ 1；LiMn2O4；LiFePO4；LiCoO2；LiNi0.8Co0.15Al0.05O2；LiNi1/3Mn1/3Co1/3O2；LiNi0.5Mn0.3Co0.2O2； LiNi0.4Mn0.4Co0.2O2；LiNi0.5Mn1.5O4；xLi2MnO3·(1-x)LiNi1/3Mn1/3Co1/3O2, wherein, 0≤x≤1；Or LiCoPO4；In more than positive electrode, wherein：LiCoO2；LiNi0.8Co0.15Al0.05O2；LiNi1/3Mn1/3Co1/3O2； LiNi0.5Mn0.3Co0.2O2；LiNi0.4Mn0.4Co0.2O2；LiNi0.5Mn1.5O4；LiCoPO4And xLi2MnO3·(1-x)LiNi1/ 3Mn1/3Co1/3O2, 0≤x≤1, available for conventional voltage and high voltage system.
Positive electrode material used in lithium ion battery is not particularly limited in the present invention, such as:LiCo02、LiNi02、 LiMn02、LiMn2O4、LiNixCoyMnzO2(x+y+z=1) etc. containing the compound transition metal oxide of lithium or these contain The substance or these transition metal combined oxidations containing lithium of a variety of transition metal mixing in the compound transition metal oxide of lithium A part of transition metal of object is by the substance of other metal replacements；Can also be phosphate LiMPO4(M Fe, Mn, Co or it is mixed It closes)；It can also be Ti02、V205、Mo03Wait oxides；Or it is TiS2, FeS sulfides；Either polyacetylene, it is poly- to benzene, it is poly- The electroconductive polymers such as aniline and polypyrrole；Or activated carbon；Or the polymer generated free radicals；Or carbon material etc..
Lithium ion battery in the present invention is to negative material it is not also specifically limited, can absorb and discharge lithium Lithium metal, alloy and intermetallic compound, various carbon materials, Delanium, native graphite, the Si/C of lithium and other metals are multiple Close cathode, Sn/C composite negative poles, metal oxide, metal nitride, activated carbon or electric conductive polymer etc..
It is also not particularly limited for the structure of the nonaqueous lithium ion battery of the present invention.For example, the nonaqueous lithium ion is electric Pond can be Coin-shaped battery, including an anode, a cathode and single or multiple membranes；Or cylinder type or diamond-shaped (wrap Include Soft Roll, aluminum hull, box hat, plastic casing) battery, including an anode, a cathode and membrane coil, membrane can be well known micro- Hole polyolefin film, fabric or non-woven.
The beneficial effects of the invention are as follows：The present invention is by introducing new lithium ion battery functional additive and applied to non-aqueous It, can be with shape when battery made of the nonaqueous lithium ion battery electrolyte is being melted into for the first time in lithium-ion battery electrolytes and battery The SEI film high into dense uniform, lithium-ion-conducting, makes homogeneous current distribution of the battery during charge and discharge, makes lithium ion Ionic conductivity increases, and then the capacity for the first time for improving lithium ion battery plays, and normal-temperature circulating performance and high rate performance, high temperature follow Ring performance and storage performance, low temperature performance and high rate performance.
Certainly, in order to obtain the promotion of other functions of battery, art technology can be also added in electrolyte of the present invention Any conventional additive well known to personnel, such as carbon dioxide (CO2), carbon disulfide (CS2), vinylene carbonate (VC), sub- second It is one or more kinds of in alkenyl ethylene carbonate (VEC), fluorinated ethylene carbonate (FEC), ethylene sulfite (ES) Mixture, this is decided according to the actual requirements.
The present invention is further described with reference to specific embodiment.
Embodiment 1：
1st, prepared by electrolyte：Electrolyte is prepared in BRAUN glove boxes, the nitrogen that purity is 99.999% is full of in glove box Gas, in≤5ppm, temperature is room temperature for moisture control in glove box.It is EC by mass ratio:DMC:DEC=3:3:4 dicyandiamide solution It is uniformly mixed, sealing is put into refrigerator after it is cooled to 8 DEG C, is transferred in glove box, then adds in LiPF in two batches6It fills Divide mixing, form the nonaqueous electrolytic solution for the lithium ion battery that lithium salts molar concentration is 1mol/L, add in above-mentioned nonaqueous electrolytic solution Entering calgon makes it obtain containing the non-aqueous of the calgon that the molar concentration in non-aqueous organic solvent is 0.01% Electrolyte uniformly after mixing, obtains nonaqueous lithium ion battery electrolyte.
2nd, the preparation of lithium ion cell positive：By nickel cobalt aluminium ternary material NCA (LiNi0.8Co0.15Al0.05O2), conductive agent SuperP, bonding agent PVDF in mass ratio 96:2.0:2.0 are uniformly mixed the lithium ion battery anode glue size that certain viscosity is made, It is coated in current collector aluminum foil, coating weight 0.0194g/cm2, it is cold-pressed after being dried at 85 DEG C；Then carry out trimming, Cut-parts, slitting, when 85 DEG C of drying 4 are small under vacuum after slitting, the lithium ion battery met the requirements is being made just in soldering polar ear Pole.
3rd, the preparation of lithium ion battery negative electrode：By Delanium and conductive agent SuperP, thickener CMC, bonding agent SBR (SBR emulsion) in mass ratio 90:2.0:2.0:Slurry is made in 6.0 ratio, be coated on copper foil of affluxion body and It is dried at 85 DEG C, coating weight 0.0089g/cm2；Trimming, cut-parts, slitting are carried out, 110 DEG C of drying under vacuum after slitting 4 it is small when, the negative electrode of lithium ion battery met the requirements is made in soldering polar ear.
4th, the preparation of lithium ion battery：The lithium ion cell positive, cathode pole piece and isolation that will be prepared according to previous process Film is fabricated to thickness as 4.2mm by lamination process, and width 34mm, length is the lithium ion battery of 82mm, true at 75 DEG C When sky baking 10 is small, injection such as preceding nonaqueous lithium ion battery electrolyte.Stand 24 it is small when after, with the constant electricity of 0.lC (160mA) Then current charge drops to 0.05C (80mA) to 4.2V with 4.2V constant-voltage charges to electric current；Then discharged with 0.lC (160mA) To 3.0V, charge and discharge are repeated 2 times, battery is finally charged to by 3.8V with 0.lC (160mA) again, battery is completed and makes.
In the present invention, the preparation method of embodiment 2~8 and comparative example 1~7 is carried out according to the preparation method of embodiment 1.
As shown in table 1 to table 4, the indices and performance test of the embodiment of the present invention and comparative example are as shown in Table.
Table 1：The battery positive and negative electrode and solvent material and solvent ratios contrast table that comparative example 1~7, Examples 1 to 8 use.
Wherein, NCA：Nickel cobalt aluminium ternary material；LMO：LiMn2O4；LFP：LiFePO4；LCO：Cobalt acid lithium.
Table 2：The LiPF that comparative example 1~7, Examples 1 to 8 use6Concentration, additive and additive amount contrast table.
Table 3：Comparative example 1~7, the efficiency for the first time of Examples 1 to 8 acquisition, 500 weeks capacity are kept, -40 DEG C _ 0.2C electric discharges The contrast table of function.
Table 4：Comparative example 1~7, Examples 1 to 8 obtain 2C multiplying power dischargings, 60 DEG C cycle 100 weeks, 60 DEG C of 7 days thickness it is swollen Swollen rate, 60 DEG C of 7 days capacity retention ratios, 60 DEG C of 7 days capacity recovery rates, 0 DEG C of analysis functions contrast table such as lithium situation.
By Experimental Comparison, it can be deduced that：It is with the addition of the nonaqueous lithium ion battery electrolyte of functional additive of the present invention, energy The enough efficiency for the first time for significantly improving lithium ion battery；Due to its can promote electrolyte film forming more it is thin evenly, so as to The normal-temperature circulating performance of battery and room temperature multiplying power discharging property are obviously improved, and high temperature cyclic performance can be improved；From low temperature Test data comparison is as can be seen that it can be obviously improved low temperature analysis lithium situation, and low temperature performance also obtains greatly Improve.
The explanation for several embodiments that the above embodiment of the present invention, which is inventor, carries out the present invention, functional additive Can also be other additives, such as calcium pyrophosphate, pyrophosphoric acid rubidium, tripolyphosphate calcium, tripolyphosphate barium, it can reach this Invention effect.
The above embodiment of the present invention is described in detail the present invention, but is not meant to that the present invention is limited only to this A little examples.In the case where not departing from the technology of the present invention principle, make improvements and deform in the claims in the present invention and skill Within art, should also it belong to the scope of protection of the present invention.

Claims (9)

1. a kind of nonaqueous lithium ion battery electrolyte, which is characterized in that added containing electrolytic salt, non-aqueous organic solvent and function Agent, it is (K) that functional additive, which is selected from chemical formula,m+4Pm+2O3m+7,(L)n/2+2Pn+2O3n+7Or (K)s(PO3)sIn a kind of chemical combination The combination of object or multiple several compounds；
Wherein, K is the alkali metal element outside the first main group dehydrogenation in the periodic table of elements；L is in the periodic table of elements Alkali earth metal of second main group in addition to beryllium；
(K)m+4Pm+2O3m+7In include anionic group P as shown in structural formula (1)m+2O3m+7 (m+4)-, wherein, m is 0 or just whole Number；
(L)n/2+2Pn+2O3n+7In include anionic group P as shown in structural formula (2)n+2O3n+7 (n+4)-, wherein, n is 0 or just Even number；
(K)s(PO3)sIn include anionic group (PO as shown in structural formula (2)3)s s-, wherein, s is 3 or the integer more than 3；
(1)
(2)
(3)
2. functional additives for Li-ion battery electrolytes according to claim 1, which is characterized in that the function addition Agent is calcium pyrophosphate, pyrophosphoric acid rubidium, pyrophosphoric acid caesium, sodium tripolyphosphate, pyrophosphoric acid lithium, sodium pyrophosphate, magnesium pyrophosphate, pyrophosphoric acid Potassium, tripolyphosphate calcium, potassium tripolyphosphate, tripolyphosphate lithium.One kind in tripolyphosphate barium, hexa metaphosphoric acid rubidium or calgon Or the combination of plural number kind.
3. functional additives for Li-ion battery electrolytes according to claim 1, which is characterized in that the function of stating adds It is 0.01%~1% to add molar concentration of the agent in non-aqueous organic solvent.
4. functional additives for Li-ion battery electrolytes according to claim 1, which is characterized in that described non-aqueous organic molten Agent is ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, acetic acid first It is one or more kinds of in ester, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate or butyl propionate Mixture.
5. functional additives for Li-ion battery electrolytes according to claim 1, which is characterized in that the electrolytic salt is LiPF6、LiBF4、LiClO4、LiBOB、LiDFOB、LiFAP、LiAsF6、LiSbF6、LiCF3S03、LiN(SO2CF3)2、LiN (SO2C2F5)2、LiN(SO2CF3)2、LiN(SO2C4F9)2、LiC(SO2CF3)3、LiPF3(C3F7)3、LiB(CF3)4、LiBF3 (C2F5)、LiPO2F2, LiDMSI, LiTESI, LiHPSI or LiPF4C2O4In one or more kinds of mixtures.
6. functional additives for Li-ion battery electrolytes according to claim 1, which is characterized in that the electrolytic salt exists Molar concentration in non-aqueous organic solvent is 0.5~2.5mol/L.
7. a kind of lithium ion battery, including anode, cathode, membrane and electrolyte, which is characterized in that the electrolyte will for right Seek the nonaqueous lithium ion battery electrolyte described in 1.
8. lithium ion battery according to claim 7, which is characterized in that the material of the cathode includes Delanium, day Right graphite, Si cathode and its alloy, Sn cathode and its alloy, lithium anode and its alloy, metal oxide MOx, metal nitrogen Compound, LixMyOzOr Li4Ti5-xMxO12In one or more kinds of mixtures；The metal oxide MOxIn M be： Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ge or Sn, x are the number of oxygen atom；The LixMyOzIn M be：Ti、V、Cr、Fe、 Co, Ni, Cu, Zn, Ge or Sn, the value of x, y, z meet the requirement for forming chemical molecular formula；The Li4Ti5-xMxO12In M be Mg, Al, Ba, Sr or Ta, 0≤x≤1.
9. lithium ion battery according to claim 7, which is characterized in that the material of the anode is included in following component One or more kinds of mixtures：Li4-xMxTi5O12, wherein M be Mg, Al, Ba, Sr or Ta, 0≤x≤1；MnO2；V2O5； LiV3O8；LiMC1xMC21-xPO4, wherein MC1 or MC2 are Fe, Mn, Ni, Co, Cr or Ti, 0≤x≤1；Li3V2-xMx(PO4)3, Middle M be Cr, Co, Fe, Mg, Y, Ti, Nb or Ce, 0≤x≤1；LiVPO4F；LiMC1xMC21-xO2, wherein MC1 or MC2 be Fe, Mn, Ni, Co, Cr, Ti, Mg or Al, 0≤x≤1；LiMC1xMC2yMC31-x-yO2, wherein MC1, MC2 or MC3 for Fe, Mn, Ni, Co, Cr, Ti, Mg or Al, 0≤x≤1,0≤y≤1；LiMn2-yXyO4, wherein X be Cr, Al or Fe, 0≤y≤1；LiNi0.5- yXyMn1.5O4, wherein X be Fe, Cr, Zn, Al, Mg, Ga, V or Cu, 0≤y<0.5；LiMC1yMC2zMC31-y-zO2, wherein MC1, MC2 or MC3 be Mn, Ni, Co, Cr, Fe or their mixture, x=0.3~0.5, y≤0.5, z≤0.5；xLi2MnO3·(1- x)LiMC1yMC2zMC31-y-zO2, wherein MC1, MC2 or MC3 be Mn, Ni, Co, Cr, Fe or their mixture, x=0.3~ 0.5, y≤0.5, z≤0.5；Li2MSiO4, wherein M is Mn, Fe or Co；Li2MSO4, wherein M is Mn, Fe or Co；LiMSO4F, Middle M is Fe, Mn or Co；Li2-x(Fe1-yMny)P2O7, wherein 0≤x≤2,0≤y≤1；LiMn2O4；LiFePO4；LiCoO2； LiNi0.8Co0.15Al0.05O2；LiNi1/3Mn1/3Co1/3O2；LiNi0.5Mn0.3Co0.2O2；LiNi0.4Mn0.4Co0.2O2； LiNi0.5Mn1.5O4；xLi2MnO3·(1-x)LiNi1/3Mn1/3Co1/3O2, wherein, 0≤x≤1；Or LiCoPO4；It is above-described In positive electrode, wherein：LiCoO2；LiNi0.8Co0.15Al0.05O2；LiNi1/3Mn1/3Co1/3O2；LiNi0.5Mn0.3Co0.2O2； LiNi0.4Mn0.4Co0.2O2；LiNi0.5Mn1.5O4；LiCoPO4And xLi2MnO3·(1-x)LiNi1/3Mn1/3Co1/3O2, wherein, 0≤ x≤1。
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