CN107666011A - A kind of nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery - Google Patents

A kind of nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery Download PDF

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CN107666011A
CN107666011A CN201610615091.9A CN201610615091A CN107666011A CN 107666011 A CN107666011 A CN 107666011A CN 201610615091 A CN201610615091 A CN 201610615091A CN 107666011 A CN107666011 A CN 107666011A
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electrolytic solution
nonaqueous electrolytic
ester
acid
carbonate
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CN107666011B (en
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申大卫
钮博翔
费震宇
李林峰
聂云华
郑卓群
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Weihong Advanced Materials Co
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Microvast Power Systems Huzhou 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • 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
    • 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 present invention relates to a kind of nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery；More particularly to a kind of nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery using carboxylate as main solvent.A kind of nonaqueous electrolytic solution, including solvent, additive, the chain carboxylate of alkali metal salt and special construction；The chain carboxylate of the present invention can use in nonaqueous electrolytic solution as main solvent；And especially suitable for negative material it is the non-aqueous secondary batteries of alkali transition metal composite oxides or oxo transition metal/sulphur/nitride.

Description

A kind of nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery
Technical field
The present invention relates to a kind of nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery；More particularly to one kind based on carboxylate The nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery of solvent.
Background technology
Nonaqueous electrolytic solution secondary battery is commonly used to notebook computer, mobile phone, wearable device etc., has started at present big Measure and be used for electric automobile industry.Common nonaqueous electrolytic solution is LiPF6The system that mixed carbonic acid ester solvent is formed；Wherein, carbonic acid Ester solvent is mainly ethylene carbonate (EC), dimethyl carbonate (DMC) and the mixed solvent of methyl ethyl carbonate (EMC) composition.Carbon EC dielectric constants are big in acid esters solvent, and lithium salts can be made fully to dissolve or ionize, and are advantageous to improve the electrical conductivity of electrolyte；EC heat Stable high, being heated to more than 200 DEG C can just decompose；EC can form SEI films in carbon-based (particularly graphite) electrode surface, improve Battery efficiency, extend battery cycle life.EC viscositys are larger, fusing point height (m.p.36.4 DEG C), and low-viscosity, low melting point Linear carbonates (DMC, EMC, DEC etc.) be used in mixed way and can obtain excellent performance, to meet that the application of secondary cell will Ask.
Lithium secondary battery is developed so far, and negative material is still based on carbon-based material.It is lazy that carbonate solvent is suitable for chemistry The carbon-based material of property, therefore, carbonate solvent has irreplaceable status in non-aqueous secondary batteries industry.Recently, alkali gold Category compound transition metal oxide or transition metal oxide arouse people's interest as negative material, Li4Ti5O12It is mesh Preceding unique commercialized material.Its current potential is about 1.55V (vs.Li/Li+), lithium ion diffusion coefficient is 2 × 10-8cm2/ S, than The high an order of magnitude of common carbon-based material.Li4Ti5O12Charge and discharge platform is stable, and in the case of high rate charge-discharge, lithium ion is not Easily separated out in material surface, and Li4Ti5O12It is zero strain material, crystal is highly stable, although trickle change also occurs, But it is different from foregoing Carbon Materials (graphite), it can avoid producing due to stretching back and forth for electrode material in charge and discharge process Structure destroy, so as to having superior cycle performance.However, Li4Ti5O12(it is only~175mAh/ except theoretical specific capacity is low G) and outside the shortcomings such as full cell output voltage is low, also one the defects of influenceing its large-scale application " aerogenesis ".TiO2、NiO、 MoO2、MoO3、V2O5、Co3O4、CoO、Fe3O4、Fe2O3、FeO、Cu2O, the transition metal oxide such as CuO material is also always by people Pay attention to.In the process for finding preferable negative material, two kinds of materials based on v element arouse people's interest recently.China Patent (B of CN 101154725) discloses LiVO2Material and preparation method thereof, the week careful et al. (Adv.Energy of person of outstanding talent Mater.2013,3,428-432 it) first reported negative material Li of new generation3VO4.People are to lithium oxyvanadium compound material at present Research even concentrate on the modification of material in itself, yet there are no to full coverage and be related to and the compatibility of electrolyte/matching sex exploration. It is of the present invention researcher's test result indicates that carbonate solvent be not suitable for be applied to vanadium base negative material, exist in secondary cell The deficiencies of resistance is big, high rate performance is poor, circulation is unstable.Alkali transition metal composite oxides or transition metal oxide with Carbon material is different, during lithium ion repeatedly deintercalation along with transition metal valence state change, such as Ti4+With Ti3+、V5 +With V4+、V4+With V3+、Mo4+With Mo3+、Co3+With Co2+、Fe3+With Fe2+Between change.Carbon material, mainly it is made up of carbon, To organic solvent almost without oxidation or catalytic action, it is believed that be chemical inertness；Transition metal Ti, V, Mo etc., The transition metal of high-valence state has strong oxidizing property, even and lower valency, also catalytic decomposition or catalytic polymerization etc. Effect, situation are complicated.Molecular structure determines carbonate solvent, especially cyclic carbonate, and intolerant to catalysis, it is in active transition gold Metal surface, easily decompose, discharge gas, such as H2、CO2、CH4、C2H6Deng.Electrode surface aerogenesis, battery bulge, internal resistance rise (physical distance increases between both positive and negative polarity), causes degradation of cell performance.
Except the modification of material in itself, matching electrolyte is found, and overcomes the important hand of prior art bottleneck Section.The research staff of the present invention is directed to finding a kind of preferably nonaqueous electrolytic solution solvent always, to substitute carbonate solvent.Carboxylic Acid esters solvent dielectric constant is compared with high and viscosity is small, can be obviously improved the low temperature output characteristics of secondary cell (J.Electrochem.Soc.,157(12)A1361-A1374(2010)).It is however, generally mixed with carbonic ester and mixed When usage amount it is relatively fewer, i.e., carbonate solvent still accounts for leading.The carboxylate used includes methyl formate, ethyl acetate, fourth The small molecule solvents such as sour methyl esters, ethyl propionate and methyl propionate, boiling point is relatively low, and high-temperature behavior is barely satisfactory.In cyclic carboxylic esters Of greatest concern is gamma-butyrolacton, -43.5 DEG C of its fusing point, and boiling point is 204 DEG C, and liquid journey is wide, and the electrolyte for preparing formation also can The electrical conductivity suitable with carbonic ester is obtained, but in addition to being used in one-shot battery, is not yet realized in secondary cell field largely Using.Above-mentioned to show, application of the carboxylate solvent as main solvent in nonaqueous electrolytic solution secondary battery is remained in weak point.
The content of the invention
In order to solve the above technical problems, the present invention provides a kind of nonaqueous electrolytic solution, including solvent and alkali metal salt, its feature It is：The solvent includes the chain carboxylate of following structure：
Wherein, R is selected from alkyl；R ' is selected from the alkyl that carbon number is 1~8.
Conventional carbonate solvent typically has 5 kinds, ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC), by changing the composition of this 5 kinds of solvents, have nearly formed mesh Preceding commercialization electrolyte of lithium-ion secondary battery system.However, carbonic ester is the higher solvent of chemical latent active, such as DMC Be conventional methylating reagent, under catalytic action, give a methyl substituents, at the same discharge leaving group methoxyl group and CO2.By contrast, carboxylate alkylation ability much weaker, is typically seldom used as alkylating reagent.So far, carbonic ester is as lithium Ion secondary battery electrolyte solvent, there is irreplaceable status, be on the one hand the opposing party because its excellent electrochemical performance Face be because chemical inertness carbon-based material accounted for as negative active core-shell material it is leading.With alkali transition metal composite oxides with And rise of the transition metal oxide as negative active core-shell material, the nonaqueous electrolyte of main solvent, exposure are used as using carbonic ester Go out problems.Phenomena such as more side reaction, battery producing gas, short cycle life generally be present.
Compared to carbonate solvent, carboxylate solvent's species is various, and molecule structure change is various, can be configured to have various property The electrolyte of energy.Carboxylate, dielectric constant is compared with high and viscosity is small, and fusing point is lower than carbonic ester, adds a small amount of carboxylate, Ke Yigai The low-temperature characteristics of kind nonaqueous electrolyte, it is the solvent of the second class commercialization outside carbonate solvent.Nevertheless, carboxylate is also only Used as secondary solvent, carbonic ester is main solvent.And the carboxylate used to improve low-temperature characteristics, it is typically limited to first The small molecule solvents such as sour methyl esters, ethyl acetate, methyl butyrate, ethyl propionate and methyl propionate.Carboxylate species is various, and has There is industrialized production basic, price is cheaper than carbonic ester, and bigger space is provided for optimization electrolyte formula.Present invention research Personnel have found, the molecular structure of carboxylate solvent, electrolyte performance are influenceed very big.For example, butyl acetate and ethyl hexanoate, The ability difference for dissolving electrolytic salt is very big；For another example, the isomers of identical molecular weight, pivalic acid methyl esters and butyl acetate, prepare Into electrolyte viscosity differ greatly.
If alkyl substitutes on the carbon atom being connected in chain carboxylate of the present invention with R', the shape easily in electrochemical process Carboxylic acid ester molecule is promoted to decompose into two level or three-level carbonium ion；In addition, Carbocation stabilization：Three-level carbonium ion>Two Level carbonium ion>One-level carbonium ion, therefore, the more stable good leaving group of carbonium ion.Under electrochemical conditions, when When carbonyl in carboxylic acid ester molecule is by attack, to avoid alcoxyl from being broken (fracture of key between alkyl and oxygen), alkyl is preferably One-level alkyl.If in addition, there are other alkyl to substitute on carbon atom connected R', because space steric effect causes carboxylate solvent Viscosity is big (molecular motion velocity is slow), is configured to electrolyte injection battery, is unfavorable for the performance of battery high rate performance.The present invention is excellent The molecular structure of carboxylate is selected, is the important research content for developing carboxylic acid ester groups electrolyte.Such as test result of the embodiment of the present invention As can be seen that using carboxylate and the negative material graphite of the present invention of special construction of the present invention, mesocarbon, unformed Carbon, silica-base material, tin-based material, transition metal oxide, transient metal sulfide, alkali transition metal composite oxides are matched somebody with somebody Close, especially alkali transition metal composite oxides coordinate, and can obtain excellent battery combination property.
In chain carboxylate provided by the invention, the alkyl that carbon number is 1~20 may be selected in R, and R ' is selected from carbon number Band side chain or not branched alkyl for 1~8；Preferably, the R ' is selected from the alkyl that carbon number is 3~8.It is preferred that R is selected From the band side chain or not branched alkyl that carbon number is 1~7.It is preferred that in R and R ' group the total number of carbon atoms be more than or equal to 3 and Less than or equal to 10；Further preferred R is more than or equal to 4 and less than or equal to 8 with the total number of carbon atoms in R ' group.Before molecular weight is suitable Put, two level, three-level carboxylate are due to substituted base on the carbon of α positions, and due to steric effect, viscosity is larger, it is therefore preferable that one-level carboxylic Acid esters, i.e., there is no substituted radical on the carbon of α positions.The chain one-level carboxylate of the present invention, space steric effect is weak, and viscosity is small, can be with Improve advantage of the nonaqueous electrolyte in high magnification application field.Chain carboxylate structure provided by the invention is especially suitable for negative pole Material is the non-aqueous secondary batteries of alkali transition metal composite oxides or oxo transition metal/sulphur/nitride.The R with R ' while be not fluorine-containing alkyl.
The chain carboxylate of the present invention can use in nonaqueous electrolytic solution as main solvent；It is preferred that the chain carboxylate Volume is the 70%~100% of the total solvent volume；The volume of the further preferred chain carboxylate is total for the solvent The 85%~100% of volume；The volume of the preferably described chain carboxylate of a more step for the total solvent volume 90%~ 100%.As another embodiment, the volume of chain carboxylate of the invention is the 70% of the nonaqueous electrolytic solution cumulative volume ~95%.The volume of the further preferred chain carboxylate is the 85%~95% of the nonaqueous electrolytic solution cumulative volume.More one The volume of the step preferably chain carboxylate is the 90%~95% of the nonaqueous electrolytic solution cumulative volume.
As a kind of preferred embodiment, chain carboxylate of the present invention is selected from caprylic acid methyl esters, caprylic acid ethyl ester, just Methyl caproate, n-caproic acid ethyl ester, n-caproic acid propyl ester, n-caproic acid butyl ester, n-caproic acid isobutyl ester, pivalic acid methyl esters, pivalic acid ethyl ester, Pivalic acid propyl ester, pivalic acid butyl ester, pivalic acid isobutyl ester, pivalic acid n-pentyl ester, pivalic acid isopentyl ester, pivalic acid (2- methyl fourths Alcohol) ester, pivalic acid peopentyl ester, methyl butyrate, ethyl butyrate, propyl butyrate, butyric acid N-butyl, isobutyl isobutyrate (IBIB), butyric acid just Pentyl ester, isoamyl butyrate, butyric acid (2- methyl butanols) ester, butyric acid peopentyl ester, the just own ester of butyric acid, methyl isobutyrate, isobutyric acid second Ester, isobutyric acid n-propyl, isobutyric acid N-butyl, isobutyl isobutyrate, isobutyric acid n-pentyl ester, isoamyl isobutyrate, isobutyric acid (2- methyl butanols) ester, isobutyric acid peopentyl ester, the just own ester of isobutyric acid, ethyl propionate, n propyl propionate, n-butyl propionate, propionic acid Isobutyl ester, n-pentyl propionate, isoamyl propionate, propionic acid (2- methyl butanols) ester, propionic acid peopentyl ester, the just own ester of propionic acid, acetic acid are just Propyl ester, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, acetic acid (2- methyl butanols) ester, acetic acid new penta At least one of ester, n-hexyl acetate and acetic acid n-octyl.
Outside linear carboxylate, cyclic carboxylic esters, solvent of the present invention can also be contained in described nonaqueous electrolyte Also include cyclic carboxylic esters；The volume of the cyclic carboxylic esters is the 0~50% of total solvent volume.It is preferred that the cyclic carboxylic acids The volume of ester is the 0~30% of total solvent volume.Further preferably, the volume of the cyclic carboxylic esters is total solvent volume 10%~30%.Still more preferably, the cyclic carboxylic esters in gamma-butyrolacton, δ-valerolactone and 6-caprolactone at least It is a kind of.
In nonaqueous electrolytic solution of the present invention, the alkali metal salt is alkali metal lithium salts and/or alkali metal sodium salt；The alkali metal Lithium salts is selected from LiPF6、LiBF4、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiN(SO2F)2、LiPO2F2、LiCF3SO3、LiC (SO2CF3)3、LiPF3(CF3)3、LiPF3(C2F5)3、LiPF3(iso-C3F7)3、LiPF5(iso-C3F7)、LiB(C2O4)2、LiBF2 (C2O4) and Li2B12F12At least one of；The alkali metal sodium salt is selected from NaPF6、NaBF4、NaN(SO2CF3)2、NaN (SO2C2F5)2、NaN(SO2F)2、NaPO2F2、NaCF3SO3、NaC(SO2CF3)3、NaPF3(CF3)3、NaPF3(C2F5)3、NaPF3 (iso-C3F7)3、NaPF5(iso-C3F7)、NaBF2(C2O4) and Na2B12F12At least one of.It is preferred that the nonaqueous electrolytic solution In, the content of alkali metal salt is 0.5mol/L~3.0mol/L.Further preferably, in the nonaqueous electrolytic solution, alkali metal salt Content is 0.8mol/L~2.5mol/L.Still more preferably, in the nonaqueous electrolytic solution, the content of alkali metal salt is 0.9mol/L~1.5mol/L.
As a kind of embodiment, solvent of the present invention also includes carbonic ester, sulfite, sulphonic acid ester, sulfone, ether, organosilicon At least one of compound, organoboron compound, nitrile, ionic liquid and phosphazene compound.Preferably, the solvent also includes carbon Sour ethyl, fluoroethylene carbonate, propylene carbonate, butylene carbonate and carbonic acid Asia alkene ester, methyl carbonic acid propylene, ethyl Propene carbonate, methyl carbonic acid phenol ester, ethylene carbonate, halogenated ethylene carbonate, propene carbonate, butylene, carbon Dimethyl phthalate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethylene sulfite, propylene sulfite, sulfurous acid fourth Alkene ester, dimethyl sulfite, sulfurous acid diethyl ester, sulfolane, dimethyl sulfoxide, second methyl sulfoxide, 1,3- propane sulfonic acid ester, 1,4- fourths Sultones, dioxolanes, dimethoxy propane, dimethyldimethoxysil,ne, special valeronitrile, valeronitrile, 2,2- methyl pentane nitriles, Double (trimethyl fluoride sulfonyl) inferior amine salts of the fluorine phosphine nitrile of ethyoxyl five, the fluorine phosphine nitrile of phenoxy group five, N- methyl-N- butyl piperidines and N- first At least one of double (fluorine sulphonyl) inferior amine salts of base-N- propyl pyrroles alkane.Preferably, the carbonic ester includes cyclic carbonate and chain Shape carbonic ester；The cyclic carbonate be selected from ethylene carbonate, fluoroethylene carbonate, propylene carbonate, butylene carbonate and At least one of carbonic acid Asia alkene ester；The linear carbonate in dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate extremely Few one kind.
As a kind of embodiment, the nonaqueous electrolytic solution also includes additive, and additive of the present invention includes film forming At least one of additive, anti-overcharge additive, flame-retardant additive, conductive additive and wetting additive.Preferably, it is described into Film additive includes organic film former and/or inorganic film forming agent；The organic film former is selected from ionic liquid, sulfuric ester, sulfurous Acid esters, sulfone, sulfoxide, sulphonic acid ester, carbonic ester, halocarbonate, carboxylate, halogenated carboxylic ester, phosphate, halogenated phosphate, Asia At least one of phosphate, halo phosphite ester, unsaturated carbon acid ester containing double bond, nitrile, crown ether and organic boride；It is described inorganic Film forming agent is selected from LiBOB, LiODBF, NaBOB, NaODBF, Li2CO3、Na2CO3、K2CO3And NH4At least one of I.Further Preferably, the organic film former is selected from vinylene carbonate (VC), vinyl ethylene carbonate (VEC), phenyl-carbonic acid ethene Ester (PhEC), phenyl-carbonic acid vinylene (PhVC), Allyl methyl carbonate (AMC), pi-allyl ethyl carbonate ester (AEC), Ethylene sulfite (ES), propylene sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES), 1, 3-N-morpholinopropanesulfonic acid lactone (1,3-PS), acrylonitrile (AAN), chlorocarbonic acid vinyl acetate (ClEC), fluorinated ethylene carbonate (FEC), three Fluoropropylene carbonate (TFPC), bromo gamma-butyrolacton (BrGBL), fluoro gamma-butyrolacton (FGBL), glutaric anhydride (GA) and At least one of succinic anhydride (SA).
As a kind of embodiment, the anti-overcharge additive of the present invention adds including oxidationreduction to additive and/or electropolymerization Add agent.Preferably, the anti-overcharge additive includes at least one of following compound：
As a kind of embodiment, described flame-retardant additive is selected from phosphate, phosphonic amide, phosphite ester, fluorophosphate At least one of ester, fluorophosphite, ionic liquid and phosphine nitrile.Preferably, the flame-retardant additive is selected from following compound At least one of：
Wherein, the X1, X2, X3, X4, X5, X6Separately represent halogen or separately represent ORx；RxRepresent hydrogen Substituted or unsubstituted representative examples of saturated aliphatic base；Or RxRepresent the substituted or unsubstituted saturation aromatic series base of hydrogen.It is described The fatty group of saturation or the aromatic series base of saturation can also contain halogen atom, nitrogen-atoms, oxygen atom, sulphur atom, silicon atom Or boron atom.
As a kind of embodiment, conductive additive of the present invention includes cationic ligand compound, anion ligand chemical combination At least one of thing and neutral ligand compound；Preferably, the conductive additive be selected from amine, crown ether, cryptand compound, At least one of fluoro-alkyl boride, alkyl boron compounds and azepine ether.
As a kind of embodiment, present invention wetting additive is selected from tertiary ammonium surfactant, containing aryl or long chain hydrocarbons At least one of carbonate products of base.Preferably, the wetting additive is selected from methyl benzol carbonate and/or double octyl groups Carbonic ester.
As a kind of embodiment, the quality of the additive is the 0~15.0% of the nonaqueous electrolytic solution quality；It is preferred that Ground, the quality of the additive are the 0~5.0% of the nonaqueous electrolytic solution quality；It is further preferred that the matter of the additive Measure as the 0~3.0% of the nonaqueous electrolytic solution quality.Preferably, the quality of the additive is the nonaqueous electrolytic solution quality 1.0%~10.0%.
The present invention also provides a kind of nonaqueous electrolytic solution secondary battery, including positive pole, negative pole, barrier film and above-mentioned non-aqueous solution electrolysis Liquid.
As a kind of embodiment, the positive electrode is selected from lithium nickel cobalt manganese oxide, sodium nickel cobalt manganese combined oxidation Thing, sodium nickel/cobalt composite oxide, lithium nickel cobalt aluminium composite oxide, li-mn-ni compound oxide, olivine-type Lithium Phosphor Oxide, lithium At least one of cobalt/cobalt oxide, sodium cobalt/cobalt oxide, lithium manganese oxide, sodium manganese oxide and sodium titanium ni compound oxide.
As a kind of embodiment, the negative material is selected from graphite, mesocarbon, agraphitic carbon, silica-base material, tinbase At least one of material, transition metal oxide, transient metal sulfide and alkali transition metal composite oxides.It is preferred that Ground, the negative material are selected from TiO2、TiS2、NiO、MoO2、MoO3、V2O5、Co3O4、CoO、Fe3O4、Fe2O3、FeO、Cu2O and At least one of CuO.
Preferably, the negative material is alkali transition metal composite oxides；It is further preferred that negative material selects From lithium titanium oxygen compound and/or lithium oxyvanadium compound.It is further preferred that the negative material is selected from lithium titanium oxygen compound And/or modified lithium titanium oxygen compound；The modification includes doping and/or cladding.Modified lithium titanium oxygen compound can be carbon The Li of coating modification4Ti5O12.It is preferred that the quality of the carbon coating part is the 0.1%~10.0% of negative material gross mass.Change Property lithium titanium oxygen compound can also be metallic element doping Li4Ti5O12And/or the Li of metallic element cladding4Ti5O12.Specifically The method of doping or cladding is not restricted driving, and the method as described in the embodiment of the present invention or other can reach effect same Prior art.
As a kind of embodiment, it is described doping or cladding include using Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Ga, At least one of In, Ge, Sn, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd, Sb and Sm Metallic element is to Li4Ti5O12It is modified processing.Preferably, the metallic element is with metal oxide after adulterating or coat Form and Li4Ti5O12With reference to；The quality of the metal oxide is the 0.1%~49.0% of the negative material gross mass. For example, from metal element Ti to Li4Ti5O12After being coated, TiO is formed2With Li4Ti5O12With reference to covering amount now is By TiO2Calculate, i.e. TiO2Quality be the negative material gross mass 0.1%~49.0%.
As a kind of embodiment, the titanium-based oxide that the present invention is used as negative material also includes TiO2-P2O5、TiO2- V2O5、TiO2-P2O5-SnO2And TiO2-P2O5- CuO etc..
As a kind of embodiment, negative material of the present invention changes except lithium titanium oxygen compound or doping/cladding The lithium titanium oxygen compound of property, also comprising carbon material.Described carbon material include graphite, mesocarbon, soft carbon, hard carbon, graphene, Gas-phase growth of carbon fibre and carbon black.The mass ratio of lithium titanium oxygen compound and carbon material is (98:2)~(51:49)；It is preferred that (90: 10)~(70:30).
As a kind of embodiment, the metal sulfide that the present invention is used as negative material includes TiS2、MoS2、FeS、FeS2 Deng metal nitride such as LixCoyN(0<x<4,0<y<0.5)。
As a kind of embodiment, the barrier film is selected from polyolefin fusion drawn barrier film；Or the barrier film is selected from and gathered to benzene At least one of naphthalate, Kynoar, aramid fiber and polyamide are the barrier film of base material；Or the barrier film is selected from height The barrier film of polyolefin is coated with softening point porous matrix material；Or the barrier film is selected from inorganic solid electrolyte barrier film；It is or described Barrier film is selected from organic solid-state electrolyte membrance；Or the barrier film is selected from what inorganic solid electrolyte was combined with organic solid-state electrolyte Composite diaphragm.The porous matrix material of the high softening-point refers to that softening point is higher than 150 DEG C of porous matrix material.
Nonaqueous electrolytic solution secondary battery of the present invention, except the active matter using heretofore described positive electrode Outside matter, the active material of negative material, barrier film and nonaqueous electrolytic solution, binding agent, conductive agent etc. are not construed as limiting, it is constructed It is not construed as limiting, its process for machining and manufacturing is also not especially limited.
Brief description of the drawings
Fig. 1 is circulating battery curve in the embodiment of the present invention 4；
Fig. 2 is circulating battery curve in the embodiment of the present invention 11；
Fig. 3 is the embodiment of the present invention 15 and initial charge curve comparison figure in comparative example 7.
Embodiment
Following specific embodiment expands detailed description to the present invention, but the present invention is not restricted to following implementation Example.
The present invention is not construed as limiting to lithium rechargeable battery structure, can be cylindrical type, square or coin shape, flexible package or Box hat or aluminum hull.Polyolefin is used using stacking aluminum plastic film flexible-packed battery, design capacity 10Ah, barrier film in the embodiment of the present invention Class fusion drawn barrier film, also have using coin half cell (2025 type).
The positive electrode of 10Ah secondary cells uses the LiNi of high nickel content0.5Co0.2Mn0.3O2(NCM523), cobalt acid lithium LiCoO2And LiMn2O4 LiMn2O4；Negative material uses the material enumerated in each embodiment.
As the conductive agent in electrode plates, such as carbon can be used, can be that amorphous carbon can also be crystalline state carbon, including Charcoal, coke, bone black, sugar charcoal, activated carbon, carbon black, coke, graphitized intermediate-phase carbon microballon (MCMB), soft carbon, hard carbon and stone Ink etc.；Divide from microstructure, described carbon can be CNT, graphite flake, fullerene, graphene etc.；From microcosmic Divide on pattern, described carbon can be carbon fiber, carbon pipe, carbon ball etc..Graphene, VGCF, second are used in the embodiment of the present invention One or more in acetylene black and KS-6.Binding agent plays a part of positive active material particle being connected, including hydrophilic Property polymer is carboxymethyl cellulose (CMC), methylcellulose (MC), cellulose acetate-phthalate (CAP), hydroxypropyl Methylcellulose (HPMC), HPMCP (HPMCP), polyvinyl alcohol (PVA), polyethylene glycol oxide Etc. and hydrophobic polymer material such as polytetrafluoroethylene (PTFE) (PTFE), tetrafluoroethene perfluoroalkyl vinyl ether copolymer (PEO) (FEP), the fluorine resin such as Kynoar (PVDF), polyethylene-TFE copolymer (ETFE) and vinyl acetate copolymerization The rubber such as thing, styrene-butadiene block copolymer (SBR), acrylic acid modified SBR resins (SBR systems latex), acacia gum Class.PVDF is used in the embodiment of the present invention.
When evaluating material and electrolyte property using button cell, by negative material, conductive agent acetylene black and binding agent Kynoar (PVDF) in mass ratio 80:10:10 mixing, and add solvent N-methyl pyrilidone and slurry is made.By slurry On the aluminium foil or copper foil for being 20 μm coated on thickness, then in 120 DEG C of vacuum drying, the circle that diameter is about 14mm is struck out Piece, electrode is made.Using metal lithium sheet as to electrode.Barrier film is porous polyethylene membrane, 20 μm of thickness, in the hand of Ar gas shieldeds 2025 type button cells are assembled into casing.The preparation condition and cell testing results being related in the specific embodiment of the invention are shown in Table 1 and table 2.
Embodiment 1
Electrolyte quota
Prepare the non-water mixed solvent of pivalic acid methyl esters (MTE, chain three-level carboxylate) and propene carbonate (PC), volume Than 70:30, it is slowly added to electrolytic salt LiPF6And cooled down, form the nonaqueous electrolytic solution that concentration is 1.3mol/L.
Battery makes
10Ah is laminated aluminum plastic film flexible-packed battery, and positive electrode uses LiNi0.5Co0.2Mn0.3O2(NCM523), negative pole material Material uses lithium titanium oxygen compound Li4Ti5O12(LTO) battery energy density about 85Wh/kg when, normal temperature 1C discharges.
Battery performance test
(1) under normal temperature condition, by the discharge and recharge in 1.50V~2.80V voltage ranges of above-mentioned flexible-packed battery, constant current is filled Electric multiplying power is 6C, constant-current discharge multiplying power 3C, investigates its high magnification output characteristics and charge and discharge cycles stability.
(2) it is fully charged that above-mentioned flexible-packed battery is pressed to 1C multiplying powers in 1.50V~2.80V voltage ranges, then at 60 DEG C Under environment temperature, shelve 30 days, observation battery whether aerogenesis, bulge.
Embodiment 2
Electrolyte quota
Prepare pivalic acid ethyl ester (ETE, chain three-level carboxylate), methylpropionate (MP, chain one-level carboxylate) and carbon The non-water mixed solvent of vinyl acetate (EC), volume ratio 50:30:20, film for additive vinylene carbonate (VC) is then added, Its content is the content 1.0wt% of nonaqueous electrolytic solution quality.It is slowly added to electrolytic salt LiPF6And cooled down, form concentration For 1.2mol/L nonaqueous electrolytic solution.
Secondary cell makes and battery performance test is the same as embodiment 1.
Embodiment 3
Electrolyte quota
Butyl acetate (BA, chain one-level carboxylate) is prepared to mix with the non-aqueous of gamma-butyrolacton (γ-BL, cyclic carboxylic esters) Bonding solvent, volume ratio 90:10, it is slowly added to electrolytic salt LiPF6And cooled down, form the non-water power that concentration is 1.2mol/L Solve liquid.
Secondary cell makes and battery performance test is the same as embodiment 1.
Embodiment 4
Electrolyte quota
Prepare isobutyl acetate (IBA, chain one-level carboxylate), pivalic acid methyl esters (MTE, chain three-level carboxylate) with The non-water mixed solvent of gamma-butyrolacton (γ-BL, cyclic carboxylic esters), volume ratio 70:20:10, it is slowly added to electrolytic salt LiPF6And cooled down, form the nonaqueous electrolytic solution that concentration is 1.2mol/L.
Secondary cell makes and battery performance test is the same as embodiment 1.
Embodiment 5
Electrolyte quota
Prepare the non-water mixed solvent of propyl isobutyrate (PIB, chain two level carboxylate) and propene carbonate (PC), volume Than 70:30, then add film for additive vinylene carbonate (VC) and PS (1,3-PS), its content point Not Wei nonaqueous electrolytic solution quality 2.0wt% and 1.5wt%.It is slowly added to electrolytic salt LiPF6And cooled down, form concentration For 0.9mol/L nonaqueous electrolytic solution.
Secondary cell is made with embodiment 1.
Battery performance test with embodiment 1, unlike, constant-current charge multiplying power is 3C, constant-current discharge multiplying power 3C.
Embodiment 6
Electrolyte quota
Prepare ethyl hexanoate (EH, chain one-level carboxylate), ethyl propionate (EP, chain one-level carboxylate) and γ-fourth The non-water mixed solvent of lactone (γ-BL, cyclic carboxylic esters), volume ratio 70:10:20, then add film for additive vinyl Ethylene carbonate (VEC), its content are the 1.0wt% of nonaqueous electrolytic solution quality.It is slowly added to electrolytic salt LiPF6And LiBF4And Cooled down, both mol ratios 9:1, form the nonaqueous electrolytic solution that concentration is 1.2mol/L.
Secondary cell is made with embodiment 1.
Battery performance test with embodiment 1, unlike, constant-current charge multiplying power is 3C, constant-current discharge multiplying power 3C.
Embodiment 7
Electrolyte quota
Hexyl acetate (HA, chain one-level carboxylate) is prepared to mix with the non-aqueous of gamma-butyrolacton (γ-BL, cyclic carboxylic esters) Bonding solvent, volume ratio 80:20, additive succinonitrile (BDN) is then added, its content is the 2.0wt% of nonaqueous electrolytic solution quality. It is slowly added to electrolytic salt LiPF6And cooled down, form the nonaqueous electrolytic solution that concentration is 1.2mol/L.
Battery makes
10Ah is laminated aluminum plastic film flexible-packed battery, and positive electrode uses LiCoO2(LCO), negative material uses lithium titanyl Compound Li4Ti5O12, battery energy density about 85Wh/kg when normal temperature 1C discharges.
Battery performance test with embodiment 1, unlike, constant-current charge multiplying power is 3C, constant-current discharge multiplying power 3C.
Embodiment 8
Electrolyte quota
Prepare isobutyl acetate (IBA, chain one-level carboxylate) solvent, account for solvent volume 100%, then add additive LiBOB (di-oxalate lithium borate), its content are the 0.5wt% of nonaqueous electrolytic solution quality.It is slowly added to electrolytic salt LiPF6And add With cooling, the nonaqueous electrolytic solution that concentration is 1.2mol/L is formed.
Battery makes
10Ah is laminated aluminum plastic film flexible-packed battery, and positive electrode uses LiMn2O4(LMO), negative material uses lithium titanyl Compound Li4Ti5O12, battery energy density about 75Wh/kg when normal temperature 1C discharges.
Battery performance test
Under normal temperature condition, by the discharge and recharge in 1.50V~2.80V voltage ranges of above-mentioned flexible-packed battery, constant-current charge Multiplying power is 3C, constant-current discharge multiplying power 3C, investigates its high magnification output characteristics and charge and discharge cycles stability.
Embodiment 9
Electrolyte quota
Prepare the non-aqueous mixing of pentyl acetate (PA, chain one-level carboxylate) and δ-valerolactone (δ-PL, cyclic carboxylic esters) Solvent, volume ratio 70:30, it is slowly added to electrolytic salt LiPF6And cooled down, form the non-aqueous solution electrolysis that concentration is 1.2mol/L Liquid.
Battery makes
10Ah is laminated aluminum plastic film flexible-packed battery, and positive electrode uses LiNi0.5Co0.2Mn0.3O2And LiMn (NCM523)2O4 (LMO) composite, negative material use the lithium titanium oxygen compound Li of carbon coating4Ti5O12/ C, carbon content about 2.0wt%.Normal temperature Battery energy density about 82Wh/kg when 1C discharges.
Li4Ti5O12The preparation of/C-material：By lithium, titanium mol ratio Li:Ti=4:5 weigh Li source compound LiOH respectively H2O and titanium source compound TiO2, and weigh chelating agent and carbon-source cpd glucose (its quality is adds material gross mass 10%), it is respectively added slowly into deionized water, the mass ratio for adding material and solvent medium is 40:60.Then stirring 4 is small When.Well mixed slurry is transferred to spray drying system, by the spherical precursor powder obtained after spray drying prior to 450 DEG C roasting 4 hours, then in 800 DEG C be calcined 10 hours, calcination atmosphere is nitrogen.After roasting terminates, cooling, smash, sieving.
Battery performance test
Under normal temperature condition, by the discharge and recharge in 1.50V~2.80V voltage ranges of above-mentioned flexible-packed battery, constant-current charge Multiplying power is 3C, constant-current discharge multiplying power 3C, investigates its high magnification output characteristics and charge and discharge cycles stability.
Embodiment 10
Electrolyte quota
Preparation pivalic acid methyl esters (MTE, chain three-level carboxylate), ethyl propionate (EP, chain one-level carboxylate) and ε- The non-water mixed solvent of caprolactone (cyclic carboxylic esters, ε-HL), volume ratio 30:60:10.Then (the trimethyl of additive three is added Silane) borate (TMSB), its content is the 1.0wt% of nonaqueous electrolytic solution quality.It is slowly added to electrolytic salt LiPF6And it is subject to Cooling, form the nonaqueous electrolytic solution that concentration is 1.2mol/L.
Battery makes
10Ah is laminated aluminum plastic film flexible-packed battery, and positive electrode uses LiNi0.5Co0.2Mn0.3O2(NCM523), negative pole material Material uses the lithium titanium oxygen compound Li of carbon coating4Ti5O12/ C, carbon content about 2.0wt%.Battery energy density when normal temperature 1C discharges About 85Wh/kg.
Battery performance test is the same as embodiment 1.
Embodiment 11
Electrolyte quota
Prepare pivalic acid methyl esters (MTE, chain three-level carboxylate), butyl acetate (BA, chain one-level carboxylate) and carbon The non-water mixed solvent of acid propylene ester (PC), volume ratio 10:80:10.Then additive succinic anhydride (SA) is added, its content is The 1.0wt% of nonaqueous electrolytic solution quality.It is slowly added to electrolytic salt LiPF6And cooled down, it is 1.3mol/L's to form concentration Nonaqueous electrolytic solution.
Battery makes
10Ah is laminated aluminum plastic film flexible-packed battery, and positive electrode uses LiNi0.5Co0.2Mn0.3O2(NCM523), negative pole material Material uses the lithium titanium oxygen compound Li of carbon coating4Ti5O12/ C, carbon content about 5.0wt%.Battery energy density when normal temperature 1C discharges About 83Wh/kg.
Battery performance test is the same as embodiment 1.
Embodiment 12
Electrolyte quota
Preparation butyl isobutyrate (BIB, chain two level carboxylate), isobutyl acetate (IBA, chain one-level carboxylate), γ- The non-water mixed solvent of butyrolactone (γ-BL, cyclic carboxylic esters) and propene carbonate (PC), volume ratio 30:45:20:5.So It is respectively nonaqueous electrolytic solution quality to add additive succinonitrile (DBN) and vinylene carbonate (VC), its content afterwards 2.0wt%.It is slowly added to electrolytic salt LiPF6And cooled down, form the nonaqueous electrolytic solution that concentration is 1.2mol/L.
Button cell makes
Button cell (2025 type), active material use zirconium doped lithium titanate, and with carbon coating, covering amount 2.0wt% (Li4Ti4.95Zr0.05O12(LTZO)/C), lithium metal is used to electrode.
Li4Ti4.95Zr0.05O12The preparation of/C (2.0wt%) material：By lithium, titanium, zirconium mol ratio Li:Ti:Zr=4:4.95: 0.05 weighs Li source compound LiOHH respectively2O and titanium source compound TiO2And zirconium source compound nanoscale ZrO2, and weigh Chelating agent and carbon-source cpd glucose (its quality is the 10% of addition material gross mass), are respectively added slowly to deionization In water, the mass ratio for adding material and solvent medium is 40:60.Then stir 4 hours.Well mixed slurry is transferred to spray Mist drying system, the spherical precursor powder obtained after spray drying is calcined 4 hours prior to 450 DEG C, then in 800 DEG C of roastings 10 hours, calcination atmosphere was nitrogen.After roasting terminates, cooling, smash, sieving.
Battery performance test
Normal temperature, by above-mentioned soft button cell discharge and recharge in 1.0~2.5V voltage ranges, constant-current charge multiplying power is 0.2C, Constant-current discharge multiplying power 0.2C, investigates its specific capacity and cyclical stability.
Embodiment 13
Electrolyte quota
Prepare isobutyl acetate (IBA, chain one-level carboxylate), gamma-butyrolacton (γ-BL, cyclic carboxylic esters) and fluorine For the non-water mixed solvent of vinyl acetate (F-EC), volume ratio 65:20:15.Then additive vinylene carbonate (VC) is added, is contained Measure as the 2.0wt% of nonaqueous electrolytic solution quality.It is slowly added to electrolytic salt LiPF6And LiBF4And cooled down, both moles Than 8:2, form the nonaqueous electrolytic solution that concentration is 1.1mol/L.Button cell makes
Button cell (2025 type), active material use caesium doped lithium titanate, and with carbon coating, covering amount 2.0wt% (Li3.98Cs0.02Ti5O12(LCTO)/C), lithium metal is used to electrode.
Li3.98Cs0.02Ti5O12The preparation of/C (2.0wt%) material：By lithium, caesium, titanium mol ratio Li:Cs:Ti=3.98: 0.02:5 weigh Li source compound LiOHH respectively2O, caesium source compound cesium carbonate and titanium source compound TiO2, and weigh chela Mixture and carbon-source cpd glucose (its quality is the 10% of addition material gross mass), are respectively added slowly to deionized water In, the mass ratio for adding material and solvent medium is 40:60.Then stir 4 hours.Well mixed slurry is transferred to spraying Drying system, the spherical precursor powder obtained after spray drying is calcined 4 hours prior to 480 DEG C, is then calcined 16 in 780 DEG C Hour, calcination atmosphere is nitrogen.After roasting terminates, cooling, smash, sieving.
Battery performance test is the same as embodiment 12.
Embodiment 14
Electrolyte quota
Prepare ethyl caprilate (EO, chain one-level carboxylate), pivalic acid ethyl ester (ETE, chain three-level carboxylate) and γ-fourth The non-water mixed solvent of lactone (γ-BL, cyclic carboxylic esters), volume ratio 45:45:10.It is slowly added to electrolytic salt LiPF6And add With cooling, the nonaqueous electrolytic solution that concentration is 1.2mol/L is formed.
Button cell makes
Button cell (2025 type), the TiO that active material is about 500nm using average grain diameter2, metal is used to electrode Lithium.
Battery performance test
Battery testing condition：Normal temperature, by above-mentioned soft button cell discharge and recharge in 0.1~2.5V voltage ranges, constant current is filled Electric multiplying power is 0.1C, constant-current discharge multiplying power 0.1C, investigates its charging and discharging curve and first charge-discharge efficiency.
Embodiment 15
Electrolyte quota
Prepare pivalic acid methyl esters (MTE, chain three-level carboxylate), pivalic acid ethyl ester (ETE, chain three-level carboxylate), carbon The non-water mixed solvent of vinyl acetate (EC) and dimethyl carbonate (DMC), volume ratio 35:35:20:10.Then addition is added Agent PS (1,3-PS), content are the 2.0wt% of nonaqueous electrolytic solution quality.It is slowly added to electrolytic salt LiPF6 Form the nonaqueous electrolytic solution that concentration is 1.1mol/L.
Button cell makes
Button cell (2025 type), the vanadium oxide (V that active material is about 300nm using average grain diameter2O5, at sand milling Reason), lithium metal is used to electrode.
Battery performance test
Battery testing condition：Normal temperature, by above-mentioned soft button cell discharge and recharge in 0.1~2.5V voltage ranges, constant current is filled Electric multiplying power is 0.1C, constant-current discharge multiplying power 0.1C, investigates its charging and discharging curve and first charge-discharge efficiency.
Embodiment 16
Electrolyte quota
Prepare the non-water mixed solvent of hexyl acetate (HA, chain one-level carboxylate) and propene carbonate (PC), volume ratio 85:15.Then additive vinylene carbonate (VC) is added, content is the 2.0wt% of nonaqueous electrolytic solution quality.It is slowly added to electricity Solve matter salt LiPF6With LiTFSI and cooled down, both mol ratios 8.5:1.5, form the non-water power that concentration is 1.2mol/L Solve liquid.
Button cell makes
Button cell (2025 type), active material use lithium titanium oxygen compound Li4Ti5O12With the composite wood of graphene (G) Material, the content of graphene is 3.0wt%, and lithium metal is used to electrode.
Li4Ti5O12With the preparation of the composite of graphene：By lithium, titanium mol ratio Li:Ti=4:5 weigh lithium source respectively Compound L iOHH2O and titanium source compound TiO2, and a certain amount of grapheme material is weighed, it is respectively added slowly to deionization In water, to ensure that graphene dispersion is uniform, 1,2- ethylene glycol and a small amount of hexadecyltrimethylammonium chloride are added, adds material Gross mass and solvent medium mass ratio be 40:60.Then stir 4 hours.It is dry that well mixed slurry is transferred to spraying Drying system, the spherical precursor powder obtained after spray drying is calcined 4 hours prior to 480 DEG C, it is then small in 800 DEG C of roastings 8 When, calcination atmosphere is nitrogen.After roasting terminates, cooling, smash, sieving.
Battery performance test
Battery testing condition：Normal temperature, by above-mentioned soft button cell discharge and recharge in 1.0~2.5V voltage ranges, constant current is filled Electric multiplying power is 0.2C, constant-current discharge multiplying power 0.2C, investigates its charging and discharging curve and charge and discharge cycles stability.
Embodiment 17
Electrolyte quota
Prepare ethyl hexanoate (EH, chain one-level carboxylate), ethyl propionate (EP, chain one-level carboxylate) and γ-fourth The non-water mixed solvent of lactone (γ-BL, cyclic carboxylic esters), volume ratio 20:70:10.Then it is sub- to add film for additive carbonic acid Vinyl acetate (VC) and flame-retardant additive three (trifluoroethyl) phosphate (TFP), content are respectively nonaqueous electrolytic solution quality 2.0wt% and 5.0wt%.It is slowly added to electrolytic salt LiPF6And cooled down, form the non-aqueous solution electrolysis that concentration is 1.5mol/L Liquid.
Button cell makes
Button cell (2025 type), active material use lithium titanium oxygen compound Li4Ti5O12With the composite wood of hard carbon (HC) Material, both mass ratioes are 90:10, lithium metal is used to electrode.
Battery performance test
Battery testing condition：Normal temperature, by above-mentioned soft button cell discharge and recharge in 0.1~2.5V voltage ranges, constant current is filled Electric multiplying power is 0.2C, constant-current discharge multiplying power 0.2C, investigates its charging and discharging curve and charge and discharge cycles stability.
Embodiment 18
Electrolyte quota
Prepare isobutyl acetate (IBA, chain one-level carboxylate), ethylene carbonate (EC) and diethyl carbonate (DEC) Non- water mixed solvent, volume ratio 70:20:10.Then the fluorine phosphine nitrile (EPZ) of flame-retardant additive ethyoxyl five is added, its content is The 10.0wt% of nonaqueous electrolytic solution quality.It is slowly added to electrolytic salt LiPF6And cooled down, it is 1.1mol/L's to form concentration Nonaqueous electrolytic solution.
Battery makes
10Ah is laminated aluminum plastic film flexible-packed battery, and positive electrode uses LiNi0.5Co0.2Mn0.3O2(NCM523), negative pole material The lithium titanium oxygen compound Li that material is adulterated using zirconium4Ti4.9Zr0.1O12(LTZO).Battery energy density about 85Wh/ when normal temperature 1C discharges kg。
Battery performance test
Under normal temperature condition, by the discharge and recharge in 1.5~2.8V voltage ranges of above-mentioned flexible-packed battery, constant-current charge multiplying power For 3C, constant-current discharge multiplying power 3C, its high magnification output characteristics and charge and discharge cycles stability are investigated.
Embodiment 19
Electrolyte quota
Prepare butyl acetate (BA, chain one-level carboxylate), propene carbonate (PC) and N- Methyl-N-propyl pyrrolidines Double (trifluoro sulphonyl) inferior amine salt (PP1,3TFSI non-water mixed solvent), volume ratio 70:15:15.It is slowly added to electrolytic salt LiPF6With LiTFSI and cooled down, both mol ratios 7:3, form the nonaqueous electrolytic solution that concentration is 0.9mol/L.
Battery is made with embodiment 18.
Battery performance test
Under normal temperature condition, by the discharge and recharge in 1.5~2.8V voltage ranges of above-mentioned flexible-packed battery, constant-current charge multiplying power For 2C, constant-current discharge multiplying power 2C, its high magnification output characteristics and charge and discharge cycles stability are investigated.
Embodiment 20
Electrolyte quota
Prepare butyl butyrate (BB, chain one-level carboxylate), hexyl acetate (HA, chain one-level carboxylate) and pivalic acid The non-water mixed solvent of methyl esters (MTE, chain three-level carboxylate), volume ratio 30:30:40.Then anti-overcharge additive ring is added Hexyl benzene (HB), its content are the 2.0wt% of nonaqueous electrolytic solution quality.It is slowly added to electrolytic salt LiPF6And cooled down, shape Into the nonaqueous electrolytic solution that concentration is 1.2mol/L.
Battery makes
10Ah is laminated aluminum plastic film flexible-packed battery, and positive electrode uses LiNi0.5Co0.2Mn0.3O2(NCM523), negative pole material The lithium titanium oxygen compound Li that material is adulterated using nickel4Ti4.9Ni0.1O12(LTNO).Battery energy density about 85Wh/ when normal temperature 1C discharges kg。
Battery performance test
Under normal temperature condition, by the discharge and recharge in 1.5~2.8V voltage ranges of above-mentioned flexible-packed battery, constant-current charge multiplying power For 2C, constant-current discharge multiplying power 2C, its high magnification output characteristics and charge and discharge cycles stability are investigated.
Embodiment 21
Electrolyte quota
Prepare hexyl acetate (HA, chain one-level carboxylate), ethyl propionate (EP, chain one-level carboxylate) and γ-fourth The non-water mixed solvent of lactone (γ-BL, cyclic carboxylic esters), volume ratio 70:10:20.Then it is sub- to add film for additive carbonic acid Vinyl acetate (VC), its content are the 1.0wt% of nonaqueous electrolytic solution quality.It is slowly added to electrolytic salt LiFSI and is cooled down, shape Into the nonaqueous electrolytic solution that concentration is 2.0mol/L.
Battery makes
10Ah is laminated aluminum plastic film flexible-packed battery, and positive electrode uses LiNi0.5Co0.2Mn0.3O2(NCM523), negative pole material Material uses the lithium titanium oxygen compound Li of natrium doping3.8Na0.2Ti5O12(LNTO).Battery energy density about 85Wh/ when normal temperature 1C discharges kg。
Battery performance test
Under normal temperature condition, by the discharge and recharge in 1.5~2.8V voltage ranges of above-mentioned flexible-packed battery, constant-current charge multiplying power For 2C, constant-current discharge multiplying power 2C, its high magnification output characteristics and charge and discharge cycles stability are investigated.
Embodiment 22
Electrolyte quota
Prepare the non-of isobutyl acetate (IBA, chain one-level carboxylate), ethyl caprilate (EO) and propene carbonate (PC) Water mixed solvent, volume ratio 70:20:10.Then film for additive vinylene carbonate (VC) is added, its content is non-aqueous solution electrolysis The 1.0wt% of liquid quality.It is slowly added to electrolytic salt LiPF6And cooled down, form the non-aqueous solution electrolysis that concentration is 1.2mol/L Liquid.
Button cell makes
Button cell (2025 type), active material use titanium disulfide TiS2, lithium metal is used to electrode.Battery performance is surveyed Examination
Battery testing condition：Normal temperature, by above-mentioned soft button cell discharge and recharge in 0.1~2.5V voltage ranges, constant current is filled Electric multiplying power is 0.1C, constant-current discharge multiplying power 0.1C, investigates its first charge-discharge curve and first charge-discharge efficiency.
Comparative example 1
Electrolyte quota
Non- water mixed solvent with preparing dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and propene carbonate (PC), Volume ratio 33:33:34.It is slowly added to electrolytic salt LiPF6And cooled down, form the non-aqueous solution electrolysis that concentration is 1.2mol/L Liquid.
Secondary cell makes and battery performance test is the same as embodiment 1.
Comparative example 2
Electrolyte quota
Non- water mixed solvent with preparing dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethylene carbonate (EC), Volume ratio 33:33:34.Then film for additive vinylene carbonate (VC) is added, its content is nonaqueous electrolytic solution quality 1.0wt%.It is slowly added to electrolytic salt LiPF6And cooled down, form the nonaqueous electrolytic solution that concentration is 1.2mol/L.
Secondary cell makes and battery performance test is the same as embodiment 1.
Comparative example 3
Electrolyte quota
Prepare the non-aqueous of ethyl acetate (EA), methyl propionate (MP), ethylene carbonate (EC) and methyl ethyl carbonate (EMC) Mixed solvent, volume ratio 30:40:20:10.Then film for additive vinylene carbonate (VC) is added, its content is non-water power Solve the 1.0wt% of liquid quality.It is slowly added to electrolytic salt LiPF6And cooled down, form the non-water power that concentration is 1.2mol/L Solve liquid.
Secondary cell is made with embodiment 1.
Battery performance test
Under the conditions of 45 DEG C, by the discharge and recharge in 1.50V~2.80V voltage ranges of above-mentioned flexible-packed battery, constant-current charge Multiplying power is 3C, constant-current discharge multiplying power 3C, investigates its high magnification output characteristics and charge and discharge cycles stability.
Comparative example 4
Electrolyte quota
Prepare isobutyl acetate (IBA, chain one-level carboxylate), methyl ethyl carbonate (EMC) and ethylene carbonate (EC) Non- water mixed solvent, volume ratio 60:20:20.Then film for additive vinylene carbonate (VC) is added, content is non-water power Solve the 2.0wt% of liquid quality.It is slowly added to electrolytic salt LiPF6Form the nonaqueous electrolytic solution that concentration is 1.2mol/L.
Secondary cell makes and battery performance test is the same as embodiment 10.
Comparative example 5
Electrolyte quota
Prepare the non-of hexyl acetate (HE, chain one-level carboxylate), diethyl carbonate (DEC) and propene carbonate (PC) Water mixed solvent, volume ratio 30:40:30.It is slowly added to electrolytic salt LiPF6Form the non-aqueous solution electrolysis that concentration is 1.15mol/L Liquid.
Secondary cell makes and battery performance test is the same as embodiment 10.
Comparative example 6
Electrolyte quota
The non-water mixed solvent of methyl ethyl carbonate (EMC), diethyl carbonate (DEC) and ethylene carbonate (EC) is prepared, Volume ratio 33:33:34.Then additive vinylene carbonate (VC) is added, content is the 2.0wt% of nonaqueous electrolytic solution quality. It is slowly added to electrolytic salt LiPF6And cooled down, form the nonaqueous electrolytic solution that concentration is 1.2mol/L.
Button cell is made with battery performance test with embodiment 13.
Comparative example 7
The non-water mixed solvent of methyl ethyl carbonate (EMC), dimethyl carbonate (DMC) and ethylene carbonate (EC) is prepared, Volume ratio 33:33:34.Then additive PS (1,3-PS) is added, content is nonaqueous electrolytic solution quality 2.0wt%.It is slowly added to electrolytic salt LiPF6And cooled down, form the nonaqueous electrolytic solution that concentration is 1.2mol/L.
Button cell is made with battery performance test with embodiment 15.
Embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6, embodiment 10, implementation from table 2 Example 11 is understood with comparative example 1, comparative example 2, comparative example 4, the test result of comparative example 5, when non-water power When solution matter main solvent is selected from carboxylate solvent and accounts for total solvent volume more than 70%, for using lithium titanium oxygen compound as negative material Secondary cell, battery producing gas may be significantly suppression.Carboxylate solvent's content is higher, and suppression aerogenesis effect is more obvious, when When carboxylate solvent accounts for total solvent volume 100%, aerogenesis is completely suppressed.Comparative example 3 then illustrates, when largely using small During carboxylic acids ester (the total number of carbon atoms is less than 5 in molecule), the cycle performance of battery at high temperature can deteriorate.Fig. 3 explanations, when Applied to metal oxide negative material such as V2O5When, the nonaqueous electrolytic solution using carboxylate as main solvent also shows to compare carbonic acid The more excellent performance of ester group nonaqueous electrolytic solution, be embodied in first charge-discharge efficiency it is higher, ratio
Capacity plays higher.
Table 1
Table 2

Claims (51)

1. a kind of nonaqueous electrolytic solution, including solvent and alkali metal salt, it is characterised in that：The solvent includes the chain of following structure Carboxylate：
Wherein, R is selected from alkyl；R ' is selected from the alkyl that carbon number is 1~8.
2. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that：The R ' is selected from the alkyl that carbon number is 3~8.
3. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that：The total number of carbon atoms sum contained in the R and R ' is big In equal to 3 and less than or equal to 10.
4. nonaqueous electrolytic solution as claimed in claim 3, it is characterised in that：The total number of carbon atoms sum contained in the R and R ' is big In equal to 4 and less than or equal to 8.
5. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that：The R and R ' while be not fluorine-containing alkyl.
6. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that：The volume of the chain carboxylate is that the solvent is overall Long-pending 70%~100%.
7. nonaqueous electrolytic solution as claimed in claim 6, it is characterised in that：The volume of the chain carboxylate is that the solvent is overall Long-pending 85%~100%.
8. nonaqueous electrolytic solution as claimed in claim 7, it is characterised in that：The volume of the chain carboxylate is that the solvent is overall Long-pending 90%~100%.
9. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that：The volume of the chain carboxylate is the non-aqueous solution electrolysis The 70%~95% of liquid cumulative volume.
10. nonaqueous electrolytic solution as claimed in claim 9, it is characterised in that：The volume of the chain carboxylate is the non-water power Solve the 85%~95% of liquid cumulative volume.
11. nonaqueous electrolytic solution as claimed in claim 10, it is characterised in that：The volume of the chain carboxylate is the non-water power Solve the 90%~95% of liquid cumulative volume.
12. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that：The chain carboxylate is selected from caprylic acid methyl esters, just pungent Acetoacetic ester, methyl hexyl, n-caproic acid ethyl ester, n-caproic acid propyl ester, n-caproic acid butyl ester, n-caproic acid isobutyl ester, pivalic acid methyl esters, spy Ethyl valerate, pivalic acid propyl ester, pivalic acid butyl ester, pivalic acid isobutyl ester, pivalic acid n-pentyl ester, pivalic acid isopentyl ester, pivalic acid (2- methyl butanols) ester, pivalic acid peopentyl ester, methyl butyrate, ethyl butyrate, propyl butyrate, butyric acid N-butyl, butyric acid isobutyl Ester, n-pentyl butytate, isoamyl butyrate, butyric acid (2- methyl butanols) ester, butyric acid peopentyl ester, the just own ester of butyric acid, isobutyric acid first Ester, ethyl isobutyrate, isobutyric acid n-propyl, isobutyric acid N-butyl, isobutyl isobutyrate, isobutyric acid n-pentyl ester, isobutyric acid isoamyl Ester, isobutyric acid (2- methyl butanols) ester, isobutyric acid peopentyl ester, the just own ester of isobutyric acid, ethyl propionate, n propyl propionate, propionic acid are just Butyl ester, isobutyl propionate, n-pentyl propionate, isoamyl propionate, propionic acid (2- methyl butanols) ester, propionic acid peopentyl ester, propionic acid just oneself Ester, n-propyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, acetic acid (2- methyl butanols) At least one of ester, acetic acid peopentyl ester, n-hexyl acetate and acetic acid n-octyl.
13. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that：The solvent also includes cyclic carboxylic esters；The ring-type The volume of carboxylate is the 0~50% of total solvent volume.
14. nonaqueous electrolytic solution as claimed in claim 13, it is characterised in that：The volume of the cyclic carboxylic esters is total solvent volume 0~30%.
15. nonaqueous electrolytic solution as claimed in claim 14, it is characterised in that：The volume of the cyclic carboxylic esters is total solvent volume 10%~30%.
16. nonaqueous electrolytic solution as claimed in claim 13, it is characterised in that：The cyclic carboxylic esters are selected from gamma-butyrolacton, δ-penta At least one of lactone and 6-caprolactone.
17. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that：The alkali metal salt is alkali metal lithium salts and/or alkali gold Belong to sodium salt；The alkali metal lithium salts is selected from LiPF6、LiBF4、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiN(SO2F)2、 LiPO2F2、LiCF3SO3、LiC(SO2CF3)3、LiPF3(CF3)3、LiPF3(C2F5)3、LiPF3(iso-C3F7)3、LiPF5(iso- C3F7)、LiB(C2O4)2、LiBF2(C2O4) and Li2B12F12At least one of；The alkali metal sodium salt is selected from NaPF6、NaBF4、 NaN(SO2CF3)2、NaN(SO2C2F5)2、NaN(SO2F)2、NaPO2F2、NaCF3SO3、NaC(SO2CF3)3、NaPF3(CF3)3、 NaPF3(C2F5)3、NaPF3(iso-C3F7)3、NaPF5(iso-C3F7)、NaBF2(C2O4) and Na2B12F12At least one of.
18. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that：In the nonaqueous electrolytic solution, the content of alkali metal salt is 0.5mol/L~3.0mol/L.
19. nonaqueous electrolytic solution as claimed in claim 18, it is characterised in that：In the nonaqueous electrolytic solution, the content of alkali metal salt For 0.8mol/L~2.5mol/L.
20. nonaqueous electrolytic solution as claimed in claim 19, it is characterised in that：In the nonaqueous electrolytic solution, the content of alkali metal salt For 0.9mol/L~1.5mol/L.
21. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that：The solvent also includes carbonic ester, sulfite, sulphur At least one of acid esters, sulfone, ether, organo-silicon compound, organoboron compound, nitrile, ionic liquid and phosphazene compound.
22. nonaqueous electrolytic solution as claimed in claim 21, it is characterised in that：The solvent also includes ethylene carbonate, fluoro carbon Sour ethyl, propylene carbonate, butylene carbonate and carbonic acid Asia alkene ester, methyl carbonic acid propylene, ethyl carbonate propylene, methyl Carbonic acid phenol ester, ethylene carbonate, halogenated ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, carbonic acid two Ethyl ester, methyl ethyl carbonate, methyl propyl carbonate, ethylene sulfite, propylene sulfite, butylene sulfite, sulfurous acid diformazan Ester, sulfurous acid diethyl ester, sulfolane, dimethyl sulfoxide, second methyl sulfoxide, 1,3- propane sulfonic acid ester, 1,4- butyl sultones, dioxy penta Ring, dimethoxy propane, dimethyldimethoxysil,ne, special valeronitrile, valeronitrile, 2,2- methyl pentane nitriles, the fluorine phosphine nitrile of ethyoxyl five, Double (trimethyl fluoride sulfonyl) inferior amine salts of the fluorine phosphine nitrile of phenoxy group five, N- methyl-N- butyl piperidines and N- Methyl-N-propyls pyrrolidines are double At least one of (fluorine sulphonyl) inferior amine salt.
23. nonaqueous electrolytic solution as claimed in claim 21, it is characterised in that：The carbonic ester includes cyclic carbonate and chain carbon Acid esters；The cyclic carbonate is selected from ethylene carbonate, fluoroethylene carbonate, propylene carbonate, butylene carbonate and carbonic acid At least one of sub- alkene ester；The linear carbonate is at least one in dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate Kind.
24. nonaqueous electrolytic solution as claimed in claim 1, it is characterised in that：The nonaqueous electrolytic solution also includes additive；It is described to add Agent is added to include at least one of film for additive, anti-overcharge additive, flame-retardant additive, conductive additive and wetting additive.
25. nonaqueous electrolytic solution as claimed in claim 24, it is characterised in that：The film for additive include organic film former and/ Or inorganic film forming agent；The organic film former is selected from ionic liquid, sulfuric ester, sulfite, sulfone, sulfoxide, sulphonic acid ester, carbonic acid Ester, halocarbonate, carboxylate, halogenated carboxylic ester, phosphate, halogenated phosphate, phosphite ester, halo phosphite ester, containing double At least one of key unsaturated carbon acid ester, nitrile, crown ether and organic boride；The inorganic film forming agent be selected from LiBOB, LiODBF, NaBOB、NaODBF、Li2CO3、Na2CO3、K2CO3And NH4At least one of I.
26. nonaqueous electrolytic solution as claimed in claim 25, it is characterised in that：The organic film former is selected from vinylene carbonate (VC), vinyl ethylene carbonate (VEC), phenyl-carbonic acid vinyl acetate (PhEC), phenyl-carbonic acid vinylene (PhVC), allyl Ylmethyl carbonic ester (AMC), pi-allyl ethyl carbonate ester (AEC), ethylene sulfite (ES), propylene sulfite (PS), two Methyl sulfite (DMS), diethyl sulfite (DES), 1,3- propane sultones (1,3-PS), acrylonitrile (AAN), chloro Ethylene carbonate (ClEC), fluorinated ethylene carbonate (FEC), three fluoropropylene carbonates (TFPC), bromo gamma-butyrolacton (BrGBL), at least one of fluoro gamma-butyrolacton (FGBL), glutaric anhydride (GA) and succinic anhydride (SA).
27. nonaqueous electrolytic solution as claimed in claim 24, it is characterised in that：The anti-overcharge additive includes oxidationreduction pair Additive and/or electropolymerization additive.
28. nonaqueous electrolytic solution as claimed in claim 27, it is characterised in that：The anti-overcharge additive is included in following compound It is at least one：
29. nonaqueous electrolytic solution as claimed in claim 24, it is characterised in that：The flame-retardant additive be selected from phosphate, phosphonic amide, At least one of phosphite ester, fluorophosphate ester, fluorophosphite, ionic liquid and phosphine nitrile.
30. nonaqueous electrolytic solution as claimed in claim 29, it is characterised in that：The flame-retardant additive in following compound extremely Few one kind：
Wherein, the X1, X2, X3, X4, X5, X6Separately represent halogen or separately represent ORx；RxHydrogen is represented to be taken Generation or unsubstituted representative examples of saturated aliphatic base；Or RxRepresent the substituted or unsubstituted saturation aromatic series base of hydrogen.
31. nonaqueous electrolytic solution as claimed in claim 24, it is characterised in that：The conductive additive includes cationic ligand chemical combination At least one of thing, anion ligand compound and neutral ligand compound.
32. nonaqueous electrolytic solution as claimed in claim 31, it is characterised in that：The conductive additive is selected from amine, crown ether, cave-shaped matched somebody with somebody At least one of body compound, fluoro-alkyl boride, alkyl boron compounds and azepine ether.
33. nonaqueous electrolytic solution as claimed in claim 24, it is characterised in that：The wetting additive is selected from quaternary amines surface-active At least one of agent, carbonate products containing aryl or long chain hydrocarbon groups.
34. nonaqueous electrolytic solution as claimed in claim 33, it is characterised in that：The wetting additive is selected from methyl benzol carbonate And/or double octyl group carbonic esters.
35. nonaqueous electrolytic solution as claimed in claim 24, it is characterised in that：The quality of the additive is the nonaqueous electrolytic solution The 0~15.0% of quality.
36. nonaqueous electrolytic solution as claimed in claim 35, it is characterised in that：The quality of the additive is the nonaqueous electrolytic solution The 0~5.0% of quality.
37. nonaqueous electrolytic solution as claimed in claim 36, it is characterised in that：The quality of the additive is the nonaqueous electrolytic solution The 0~3.0% of quality.
38. nonaqueous electrolytic solution as claimed in claim 35, it is characterised in that：The quality of the additive is the nonaqueous electrolytic solution The 1.0%~10.0% of quality.
39. a kind of nonaqueous electrolytic solution secondary battery, including the nonaqueous electrolytic solution described in positive pole, negative pole, barrier film and claim 1.
40. nonaqueous electrolytic solution secondary battery as claimed in claim 39, it is characterised in that：The positive electrode is selected from lithium nickel cobalt Manganese composite oxide, sodium cobalt-nickel-manganese oxide compound, sodium nickel/cobalt composite oxide, lithium nickel cobalt aluminium composite oxide, lithium manganese nickel are answered Close oxide, olivine-type Lithium Phosphor Oxide, lithium and cobalt oxides, sodium cobalt/cobalt oxide, lithium manganese oxide, sodium manganese oxide and sodium titanium At least one of ni compound oxide.
41. nonaqueous electrolytic solution secondary battery as claimed in claim 39, it is characterised in that：The negative material be selected from graphite, Mesocarbon, agraphitic carbon, silica-base material, tin-based material, transition metal oxide, transient metal sulfide and alkali transition At least one of composite oxide of metal.
42. nonaqueous electrolytic solution secondary battery as claimed in claim 41, it is characterised in that：The negative material is selected from TiO2、 TiS2、NiO、MoO2、MoO3、V2O5、Co3O4、CoO、Fe3O4、Fe2O3、FeO、Cu2At least one of O and CuO.
43. nonaqueous electrolytic solution secondary battery as claimed in claim 41, it is characterised in that：The negative material is alkali metal mistake Cross composite oxide of metal.
44. nonaqueous electrolytic solution secondary battery as claimed in claim 43, it is characterised in that：The negative material is selected from lithium titanyl Compound and/or lithium oxyvanadium compound.
45. nonaqueous electrolytic solution secondary battery as claimed in claim 43, it is characterised in that：The negative material is selected from lithium titanyl Compound and/or the lithium titanium oxygen compound of modification；The modification includes doping and/or cladding.
46. nonaqueous electrolytic solution secondary battery as claimed in claim 45, it is characterised in that：The negative material is carbon coating Li4Ti5O12。
47. nonaqueous electrolytic solution secondary battery as claimed in claim 46, it is characterised in that：The quality of the carbon coating part is The 0.1~10.0% of negative material gross mass.
48. nonaqueous electrolytic solution secondary battery as claimed in claim 44, it is characterised in that：The negative material is metallic element The Li of doping4Ti5O12And/or the Li of metallic element cladding4Ti5O12。
49. nonaqueous electrolytic solution secondary battery as claimed in claim 48, it is characterised in that：The doping includes using Na、K、Rb、Cs、Mg、Ca、Sr、Ba、Al、Ga、In、Ge、Sn、Ti、V、Cr、Fe、Mn、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、 At least one of Cd, W, La, Ce, Nd, Sb and Sm metallic element are to Li4Ti5O12It is modified processing.
50. nonaqueous electrolytic solution secondary battery as claimed in claim 48, it is characterised in that：The gold after doping or cladding Belong to element in the form of metal oxide and Li4Ti5O12With reference to；The quality of the metal oxide is the total matter of the negative material The 0.1%~49.0% of amount.
51. nonaqueous electrolytic solution secondary battery as claimed in claim 39, it is characterised in that：The barrier film melts selected from polyolefin Tensile membrane；Or the barrier film is selected from least one of polyethylene terephthalate, Kynoar, aramid fiber and polyamide For the barrier film of base material；Or the barrier film is selected from the barrier film that polyolefin is coated with high softening-point porous matrix material；Or the barrier film Selected from inorganic solid electrolyte barrier film；Or the barrier film is selected from organic solid-state electrolyte membrance；Or the barrier film is selected from inorganic solid The composite diaphragm that state electrolyte is combined with organic solid-state electrolyte.
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108682842A (en) * 2018-03-23 2018-10-19 格林美（无锡）能源材料有限公司 A kind of Y doping CaMnO3Tertiary cathode material of cladding and preparation method thereof
CN109244545A (en) * 2018-11-28 2019-01-18 宝鸡智乾信息科技有限公司 Novel lithium-ion battery electrolyte and lithium ion battery
CN111153939A (en) * 2020-02-16 2020-05-15 成都市水泷头化工科技有限公司 Modified cyclic phosphazene flame retardant additive for lithium battery electrolyte and preparation method thereof
WO2020186913A1 (en) * 2019-03-18 2020-09-24 Ningde Amperex Technology Limited Electrochemical device and electronic device including same
US11183688B2 (en) 2017-12-29 2021-11-23 Cornell University Porous Fe3O4/S composites for Li/S batteries
CN113809395A (en) * 2021-08-30 2021-12-17 大连中比动力电池有限公司 Electrolyte for lithium battery and lithium battery with same
CN113809398A (en) * 2021-08-12 2021-12-17 东莞市创明电池技术有限公司 Electrolyte additive, electrolyte and sodium secondary battery
CN114256506A (en) * 2020-09-21 2022-03-29 合肥国轩高科动力能源有限公司 Film forming additive for power type lithium ion battery electrolyte, application and battery
CN114421013A (en) * 2022-03-11 2022-04-29 宁德新能源科技有限公司 Electrochemical device and electronic device
CN114614018A (en) * 2022-03-25 2022-06-10 宁波梅山保税港区锂泰企业管理合伙企业(有限合伙) Lithium ion battery negative electrode material, preparation method thereof and lithium ion secondary battery
CN115332638A (en) * 2022-10-14 2022-11-11 宁德新能源科技有限公司 Electrolyte, electrochemical device and electronic device
TWI803648B (en) * 2018-06-12 2023-06-01 南韓商Ｌｇ化學股份有限公司 Separator for electrochemical device including inorganic coating layer and method for manufacturing the same
CN116525949A (en) * 2023-06-26 2023-08-01 蔚来电池科技(安徽)有限公司 Secondary battery and device

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101803101A (en) * 2007-09-19 2010-08-11 株式会社Lg化学 Non-aqueous electrolyte lithium secondary battery
CN103078141A (en) * 2013-01-25 2013-05-01 宁德新能源科技有限公司 Lithium-ion secondary battery and electrolyte thereof
CN104241688A (en) * 2013-06-24 2014-12-24 微宏动力系统（湖州）有限公司 Lithium ion battery electrolyte and lithium ion battery
CN104900917A (en) * 2015-07-09 2015-09-09 上海动力储能电池系统工程技术有限公司 Electrolyte for lithium titanate lithium ion battery
CN104966822A (en) * 2015-06-16 2015-10-07 东莞市翔丰华电池材料有限公司 Multilayer coated lithium titanate cathode material of lithium ion battery and preparation method of multilayer coated lithium titanate cathode material
CN105449187A (en) * 2015-12-20 2016-03-30 华南理工大学 Preparation method of high-performance co-doped lithium titanate electrode material
CN105811010A (en) * 2014-12-29 2016-07-27 张家港市国泰华荣化工新材料有限公司 Lithium battery

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101803101A (en) * 2007-09-19 2010-08-11 株式会社Lg化学 Non-aqueous electrolyte lithium secondary battery
CN103078141A (en) * 2013-01-25 2013-05-01 宁德新能源科技有限公司 Lithium-ion secondary battery and electrolyte thereof
CN104241688A (en) * 2013-06-24 2014-12-24 微宏动力系统（湖州）有限公司 Lithium ion battery electrolyte and lithium ion battery
CN105811010A (en) * 2014-12-29 2016-07-27 张家港市国泰华荣化工新材料有限公司 Lithium battery
CN104966822A (en) * 2015-06-16 2015-10-07 东莞市翔丰华电池材料有限公司 Multilayer coated lithium titanate cathode material of lithium ion battery and preparation method of multilayer coated lithium titanate cathode material
CN104900917A (en) * 2015-07-09 2015-09-09 上海动力储能电池系统工程技术有限公司 Electrolyte for lithium titanate lithium ion battery
CN105449187A (en) * 2015-12-20 2016-03-30 华南理工大学 Preparation method of high-performance co-doped lithium titanate electrode material

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11183688B2 (en) 2017-12-29 2021-11-23 Cornell University Porous Fe3O4/S composites for Li/S batteries
CN108682842B (en) * 2018-03-23 2021-03-30 格林美（无锡）能源材料有限公司 Y-doped CaMnO3Coated ternary positive electrode material and preparation method thereof
CN108682842A (en) * 2018-03-23 2018-10-19 格林美（无锡）能源材料有限公司 A kind of Y doping CaMnO3Tertiary cathode material of cladding and preparation method thereof
TWI803648B (en) * 2018-06-12 2023-06-01 南韓商Ｌｇ化學股份有限公司 Separator for electrochemical device including inorganic coating layer and method for manufacturing the same
US11728542B2 (en) 2018-06-12 2023-08-15 Lg Chem, Ltd. Separator for electrochemical device comprising inorganic coating layer and method for manufacturing the same
CN109244545A (en) * 2018-11-28 2019-01-18 宝鸡智乾信息科技有限公司 Novel lithium-ion battery electrolyte and lithium ion battery
WO2020186913A1 (en) * 2019-03-18 2020-09-24 Ningde Amperex Technology Limited Electrochemical device and electronic device including same
CN111153939A (en) * 2020-02-16 2020-05-15 成都市水泷头化工科技有限公司 Modified cyclic phosphazene flame retardant additive for lithium battery electrolyte and preparation method thereof
CN111153939B (en) * 2020-02-16 2021-02-02 双登集团股份有限公司 Modified cyclic phosphazene flame retardant additive for lithium battery electrolyte and preparation method thereof
CN114256506A (en) * 2020-09-21 2022-03-29 合肥国轩高科动力能源有限公司 Film forming additive for power type lithium ion battery electrolyte, application and battery
CN113809398A (en) * 2021-08-12 2021-12-17 东莞市创明电池技术有限公司 Electrolyte additive, electrolyte and sodium secondary battery
CN113809398B (en) * 2021-08-12 2024-04-05 东莞市创明电池技术有限公司 Electrolyte additive, electrolyte and sodium secondary battery
CN113809395A (en) * 2021-08-30 2021-12-17 大连中比动力电池有限公司 Electrolyte for lithium battery and lithium battery with same
CN114421013B (en) * 2022-03-11 2022-07-12 宁德新能源科技有限公司 Electrochemical device and electronic device
CN114421013A (en) * 2022-03-11 2022-04-29 宁德新能源科技有限公司 Electrochemical device and electronic device
CN114614018A (en) * 2022-03-25 2022-06-10 宁波梅山保税港区锂泰企业管理合伙企业(有限合伙) Lithium ion battery negative electrode material, preparation method thereof and lithium ion secondary battery
CN115332638A (en) * 2022-10-14 2022-11-11 宁德新能源科技有限公司 Electrolyte, electrochemical device and electronic device
CN116525949A (en) * 2023-06-26 2023-08-01 蔚来电池科技(安徽)有限公司 Secondary battery and device

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