CN107293792A - A kind of nonaqueous electrolytic solution and nickelic tertiary cathode material battery - Google Patents

A kind of nonaqueous electrolytic solution and nickelic tertiary cathode material battery Download PDF

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CN107293792A
CN107293792A CN201710718941.2A CN201710718941A CN107293792A CN 107293792 A CN107293792 A CN 107293792A CN 201710718941 A CN201710718941 A CN 201710718941A CN 107293792 A CN107293792 A CN 107293792A
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electrolyte
lithium
alkyl
compound
additive
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夏兰
陈政
余林颇
胡笛
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University of Nottingham Ningbo China
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University of Nottingham Ningbo China
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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
    • H01M10/05—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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides a kind of electrolyte, including lithium salts, organic solvent and additive A；The additive A includes the one or more in alkyl amine compound, silicon nitrogen compound and siloxane compound.The present invention starts with terms of the improvement of electrolyte, propose the nonaqueous electrolytic solution containing at least one of alkyl amine, the key classes of N containing Si compound (silicon nitrogen compound) and siloxane compound, the nonaqueous electrolytic solution that the present invention is provided has extremely low free acid content, it is applied in the lithium ion battery of nickelic tertiary cathode material, can effectively improve the cycle performance, high temperature cyclic performance and high-temperature storage performance of lithium ion battery.

Description

A kind of nonaqueous electrolytic solution and nickelic tertiary cathode material battery
Technical field
The present invention relates to technical field of lithium ion, it is related to a kind of electrolyte and lithium ion battery, more particularly to it is a kind of Nonaqueous electrolytic solution and nickelic tertiary cathode material battery.
Background technology
As " engine " part of electric automobile, the specific energy size of lithium-ion-power cell is to determine that pure electric drive is electronic The key factor of the course continuation mileage length that once charges of car, directly affects the technology development and penetration and promotion of electric automobile.When The specific energy of preceding lithium-ion-power cell is heavily dependent on the specific energy of positive electrode.By the electric discharge ratio for increasing positive pole Capacity is to improve one of effective way of battery specific energy.
In many positive electrodes, nickelic ternary anode material for lithium-ion batteries mainly includes nickle cobalt lithium manganate LiNi1-x- yCoxMnyO2(NCM)(0<x<1,0<y<1) with nickel cobalt lithium aluminate LiNi1-x-yCoxAlyO2(NCA)(0<x<1,0<y<1), because having Specific capacity is high, lower cost and the advantage such as security is excellent and be considered as the lithium-ion-power cell of great application prospect just Pole material, it has also become the main development direction of numerous electrokinetic cell enterprises.But with the nickelic ternary material of the increase of Ni contents Specific discharge capacity by 160mAh g-1Increase to 220mAh g-1More than, but its capability retention, heat endurance and high temperature storage Performance all decreases, and significantly limit its industrialization development application.Research is found, causes these problems of nickelic ternary material The reason for it is complicated, be broadly divided into material in itself with interface two large problems.The problem of material itself, has：During one is cyclic process Ni/Li mixings, produce phase transformation reaction, and then induce Stress-strain Effect, cause capacity attenuation during material circulation；Two be high Ni under de- lithium state4+Tend to reduction generation Ni3+, oxygen can be discharged in material, and the heat endurance of material is deteriorated.Separately On the one hand, interface problem refers to that electrode/electrolyte interface has unstability in actual electrochemical environment, easily by electrolyte In dissociate acid corrosion effect so that the problems such as causing battery capacity conservation rate low and high temperature poor performance.For nickelic ternary material (Ni content >=0.6), even in atmosphere, its material surface is easy to and the CO in air2And H2O reacts, in material Surface Creation Li2CO3And LiOH, Li2CO3It can cause to produce serious ballooning during high temperature storage, in LiOH and electrolyte LiPF6Reaction produces HF, and then directly influences the capability retention during material circulation.Certainly for other positive electrodes , also more or less there is above mentioned problem in battery.
In order to improve anode material for lithium-ion batteries, the cycle performance of particularly nickelic tertiary cathode material and thermally-stabilised Property, existing research is usual to be set about in terms of material modification ion doping, material surface cladding and exploitation electrolysis additive three, A large amount of exploratory research work are carried out.Pass through the elements such as Mg and F that adulterated in ternary material lattice；By in material surface Coat the suitable metal oxide of some thickness (such as Al2O3, ZnO etc.), fluoride (such as AlF3Deng) or some phosphate, thing Directly contacting between reason isolation active material and electrolyte, reduces generation of side reaction etc..But still exist incomplete Place.
In the last few years, exploitation also turned into an important research direction suitable for the electrolyte of nickelic ternary material.But Up to the present, the research direction on such material electrolyte is mainly to conventional LiPF6Base carbonates electrolyte enters Row is improved, and still, these measures are very limited to the improvement result of nickelic tertiary cathode material cycle performance, and cyclical stability is still It is so undesirable.
Therefore, the chemical property of lithium ion battery, the electricity of particularly nickelic ternary material lithium ion battery how to be improved Chemical property, it has also become one of this area front subject urgent problem to be solved.
The content of the invention
In view of this, the invention provides a kind of electrolyte and lithium ion battery, particularly a kind of nonaqueous electrolytic solution and height Nickel tertiary cathode material battery, the lithium ion battery of electrolyte provided using the present invention, can effectively improve cycle performance, High temperature cyclic performance and high-temperature storage performance etc..
The invention provides a kind of electrolyte, including lithium salts, organic solvent and additive A；
The additive A include alkyl amine compound, silicon nitrogen compound and one kind in siloxane compound or It is a variety of.
It is preferred that, percent by volume of the additive A in the electrolyte is 0.05%~10%；
Molar concentration of the lithium salts in the electrolyte is 0.1~20mol/L.
It is preferred that, the one kind of the alkyl amine compound in the alkyl amine compound shown in Formulas I structure Or it is a variety of,
Wherein, R1、R2And R3The independent straight chained alkyl or branched alkyl selected from C1~C6.
It is preferred that, one kind in two silicon aminated compounds shown in Formula II structure of the silicon nitrogen compound or It is a variety of, and/or, with the one or more in the silane glyoxaline compound shown in formula III structure,
Wherein, R4、R5、R6、R8、R9And R10Independent is selected from hydrogen atom, halogen, C1~C6 alkyl, C1~C6 alcoxyl The aromatic radical of base, C6~C20, R7It is independent selected from hydrogen atom, halogen, C1~C6 alkyl, C1~C6 alkoxy, C6~ C20 aromatic radical, alkali metal atom；
Wherein, R11、R12And R13It is independent selected from hydrogen atom, halogen, C1~C6 alkyl, C1~C6 alkoxy, C6~ C20 aromatic radical.
It is preferred that, the siloxane compound is in the linear siloxane class compound shown in formula IV structure One or more, and/or, with the one or more in the annular siloxane class compound shown in Formula V structure,
Wherein, R14、R15、R16And R17The independent alkyl selected from C1~C6, C1~C6 alkoxy, C6~C20 fragrance Base；
Wherein, R18、R19、R20、R21、R22And R23The independent straight chained alkyl or branched alkyl selected from C1~C6；
N is 1~6 integer.
It is preferred that, the lithium salts includes lithium hexafluoro phosphate, LiBF4, lithium perchlorate, di-oxalate lithium borate, difluoro grass Sour lithium borate, three oxalic acid lithium phosphates, difluoro dioxalic acid lithium phosphate, tetrafluoro oxalic acid lithium phosphate, two (trimethyl fluoride sulfonyl) imine lithiums With the one or more in double fluorine sulfimide lithiums；
The organic solvent includes the carbonate-based solvent of floride-free or fluorine substitution, the ether solvent of floride-free or fluorine substitution, nothing Fluorine or the carboxylic acid esters solvent of fluorine substitution, the phosphoric acid ester solvent of floride-free or fluorine substitution and one kind in ionic liquid class solvent or One or more in a variety of.
It is preferred that, the electrolyte also includes additive B；
The additive B includes Li2CO3、CaCO3、Al2O3、ZnO、MgO、BaO、AlF3、MgF2、AlOF、LiPF6、LiBF4 With one or more in LiBOB；
The mass percent that the additive B accounts for the electrolyte is 0.005%~10%.
It is preferred that, the electrolyte also includes addition of C；
The addition of C includes the sub- propyl ester of sulfuric acid, ethylene sulfite, propylene sulfite, 1- propyl group phosphoric acid cyclic anhydride, three (trimethyl silicane) phosphate, trimethyl phosphate, three (1,1,1,3,3,3- hexafluoro isopropyls) phosphates, fluoro ethylene carbonate Ester, methyl phenyl ethers anisole, vinylene carbonate, acid suppression vinyl acetate, propylene cyanogen, vinylethylene carbonate, 1,3- propane sultones, fourth two One kind or many in nitrile, 1,3- acrylic-sultones, divinylsulfone, dioxalic acid lithium borate and difluoro (oxalic acid) lithium borate Kind；
The mass percent that the addition of C accounts for the electrolyte is 0.005%~10%.
The invention provides a kind of lithium ion battery, including positive pole and electrolyte；
The electrolyte is the electrolyte described in above-mentioned technical proposal any one.
It is preferred that, the positive pole includes nickelic tertiary cathode material.
The invention provides a kind of electrolyte, including lithium salts, organic solvent and additive A；The additive A includes alkyl One or more in aminated compounds, silicon nitrogen compound and siloxane compound.Compared with prior art, pin of the present invention The defect existed to existing anode material for lithium-ion batteries, the cycle performance of particularly nickelic tertiary cathode material and thermally-stabilised Property aspect the problem of, start with from the improvement of electrolyte in terms of, in particular for routine LiPF6Add in base carbonates electrolyte Enter a small amount of functional additive, occur oxidation Decomposition in all charging processes of head of battery by additive molecule, in positive pole material Material surface participates in forming stable positive pole interfacial film, the reaction of reduction active material and electrolyte, to improve the electrochemistry of material In terms of performance, in terms of improving cyclical stability it is not enough, improvement is limited the problem of.The invention is proposed Non- water power containing at least one of alkyl amine, the class of key containing Si-N compound (silicon nitrogen compound) and siloxane compound Liquid is solved, the nonaqueous electrolytic solution that the present invention is provided has extremely low free acid content, is applied to nickelic tertiary cathode material Lithium ion battery in, can effectively improve the cycle performance, high temperature cyclic performance and high-temperature storage performance of lithium ion battery.
Test result indicates that, lithium ion battery prepared by the electrolyte provided using the present invention has preferable normal temperature, height Warm cyclical stability and high-temperature storage performance, discharge and recharge 200 weeks at room temperature, the capability retention of battery is 65%~90%；It is high After warm discharge and recharge 100 weeks, the capability retention of battery is 51%~81%；After being stored 30 days under high temperature, open-circuit voltage OCV declines Rate is that the capability retention of 1.7%~11%, battery is 62%~89%.
Brief description of the drawings
Fig. 1 is the outside drawing of 1000mAh Soft Roll laminated batteries for being used in the embodiment of the present invention and comparative example test.
Embodiment
In order to further appreciate that the present invention, below in conjunction with the embodiment of the present invention, technical scheme is carried out clear Chu, it is fully described by, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments. Based on the embodiment in the present invention, it is all that those of ordinary skill in the art are obtained under the premise of creative work is not made Other embodiment, belongs to the scope of protection of the invention.
All raw materials of the present invention, originate to it and are not particularly limited, commercially buying or according to people in the art Known to member prepared by conventional method.
All raw materials of the present invention, its purity is not particularly limited, and present invention preferably employs analyze pure or lithium ion battery The conventional purity in field.
In the present invention, to the R1~R23The definition of specific group be not particularly limited, it is ripe with those skilled in the art The usual definition for the substituent known, group of the present invention can include the group replaced and/or unsubstituted in principle Group.
The invention provides a kind of electrolyte, including lithium salts, organic solvent and additive A；
The additive A include alkyl amine compound, silicon nitrogen compound and one kind in siloxane compound or It is a variety of.
The electrolyte is not particularly limited the present invention, is with lithium battery electrolytes well known to those skilled in the art Can, those skilled in the art can be selected and be adjusted according to applicable cases, properties of product and quality requirement, institute of the present invention State the preferred lithium ion battery nonaqueous electrolytic solution of electrolyte, more preferably tertiary cathode material electrolyte for lithium ion battery, most Preferably nickelic tertiary cathode material electrolyte for lithium ion battery.
The alkyl amine compound is not particularly limited the present invention, with alkyl amine well known to those skilled in the art Compound, those skilled in the art can be selected and be adjusted according to applicable cases, properties of product and quality requirement, Alkyl amine compound of the present invention preferably is selected from the one or more in the alkyl amine compound shown in Formulas I structure；
Wherein, R1、R2And R3The independent straight chained alkyl or branched alkyl selected from C1~C6.
R of the present invention1、R2And R3The independent straight chained alkyl or branched alkyl that preferably are selected from C1~C6, more preferably from C2~ C5 straight chained alkyl or branched alkyl, the more preferably straight chained alkyl or branched alkyl from C3~C4.
The silicon nitrogen compound is not particularly limited the present invention, with silicon nitrogen class chemical combination well known to those skilled in the art The compound of thing or the key containing Si-N, those skilled in the art can be according to applicable cases, properties of product and quality requirement Selected and adjusted, silicon nitrogen compound of the present invention preferably is selected from in two silicon aminated compounds shown in Formula II structure One or more, and/or, with the one or more in the silane glyoxaline compound shown in formula III structure, i.e., described silicon Nitrogen compound can be in two silicon aminated compounds shown in Formula II structure one or more, can also selected from tool There are the one or more in the silane glyoxaline compound shown in formula III structure, can also be simultaneously selected from Formula II structure institute In the two silicon aminated compounds shown one or more and with one kind in the silane glyoxaline compound shown in formula III structure Or it is a variety of.
Wherein, R4、R5、R6、R8、R9And R10Independent is selected from hydrogen atom, halogen, C1~C6 alkyl, C1~C6 alcoxyl The aromatic radical of base, C6~C20, R7It is independent selected from hydrogen atom, halogen, C1~C6 alkyl, C1~C6 alkoxy, C6~ C20 aromatic radical, alkali metal atom.
R of the present invention4、R5、R6、R8、R9And R10It is independent preferably be selected from hydrogen atom, halogen, C1~C6 alkyl, C1~ C6 alkoxy, C6~C20 aromatic radical, more preferably from hydrogen atom, halogen, C2~C5 alkyl, C2~C5 alkoxy, C8 ~C16 aromatic radical, more preferably from hydrogen atom, halogen, C3~C4 alkyl, C3~C4 alkoxy, C10~C14 fragrance Base, is specifically as follows hydrogen atom, halogen, C1~C3 alkyl, C1~C3 alkoxy, C6~C8 aromatic radical.
R of the present invention7It is independent preferably be selected from hydrogen atom, halogen, C1~C6 alkyl, C1~C6 alkoxy, C6~ C20 aromatic radical, alkali metal atom, more preferably from hydrogen atom, halogen, C2~C5 alkyl, C2~C5 alkoxy, C8~ C16 aromatic radical, alkali metal atom, more preferably from hydrogen atom, halogen, C3~C4 alkyl, C3~C4 alkoxy, C10~ C14 aromatic radical, alkali metal atom, be specifically as follows hydrogen atom, halogen, C1~C3 alkyl, C1~C3 alkoxy, C6~ C8 aromatic radical, alkali metal atom.
Wherein, R11、R12And R13It is independent selected from hydrogen atom, halogen, C1~C6 alkyl, C1~C6 alkoxy, C6~ C20 aromatic radical.
R of the present invention11、R12And R13Independent preferably is selected from hydrogen atom, halogen, C1~C6 alkyl, C1~C6 alcoxyl The aromatic radical of base, C6~C20, more preferably from hydrogen atom, halogen, C2~C5 alkyl, C2~C5 alkoxy, C8~C16 Aromatic radical, more preferably from hydrogen atom, halogen, C3~C4 alkyl, C3~C4 alkoxy, C10~C14 aromatic radical, specifically Can be hydrogen atom, halogen, C1~C3 alkyl, C1~C3 alkoxy, C6~C8 aromatic radical.
The siloxane compound is not particularly limited the present invention, with type siloxane well known to those skilled in the art Compound, those skilled in the art can be selected and be adjusted according to applicable cases, properties of product and quality requirement, Siloxane compound of the present invention preferably be selected from one kind in the linear siloxane class compound shown in formula IV structure or It is a variety of, and/or, with the one or more in the annular siloxane class compound shown in Formula V structure, i.e., described type siloxane Compound can be in the linear siloxane class compound shown in formula IV structure one or more, can also be selected from having The one or more in annular siloxane class compound shown in Formula V structure, can also be simultaneously selected from shown in formula IV structure Linear siloxane class compound in one or more and with one in the annular siloxane class compound shown in Formula V structure Plant or a variety of.
Wherein, R14、R15、R16And R17The independent alkyl selected from C1~C6, C1~C6 alkoxy, C6~C20 fragrance Base.
R of the present invention14、R15、R16And R17The independent alkyl selected from C1~C6, C1~C6 alkoxy, C6~C20 Aromatic radical, alkoxy, the C8~C16 aromatic radical of alkyl, C2~C5 more preferably from C2~C5, more preferably from C3~C4's Alkyl, C3~C4 alkoxy, C10~C14 aromatic radical, are specifically as follows C1~C6 straight chained alkyl or branched alkyl, It can be C1~C4 straight chained alkyl or branched alkyl, or be C1~C2 straight chained alkyl or branched alkyl.
Wherein, R18、R19、R20、R21、R22And R23The independent straight chained alkyl or branched alkyl selected from C1~C6；
N is 1~6 integer.
R of the present invention18、R19、R20、R21、R22And R23The independent straight chained alkyl or branched alkyl that preferably are selected from C1~C6, More preferably from C2~C5 straight chained alkyl or branched alkyl, the more preferably straight chained alkyl or branched alkyl from C3~C4 can also For C1~C4 straight chained alkyl or branched alkyl, or it is C1~C2 straight chained alkyl or branched alkyl.N of the present invention is preferred For 1~6 integer, more preferably 2~5 integer, more preferably 3~4 integer, be specifically as follows 1~4 integer, or For 1~2 integer.
The concrete structure of the additive A is not particularly limited the present invention, and those skilled in the art can be according to application Situation, properties of product and quality requirement are selected and adjusted within the above range, and the present invention is further optimisation technique side Case, the concrete structure formula of the additive A can be following 1~formula of formula 9：
The addition of the additive A is not particularly limited the present invention, is added with routine well known to those skilled in the art Enter amount, those skilled in the art can be selected and be adjusted according to applicable cases, properties of product and quality requirement, this It is preferably 0.05%~10% to invent percent by volume of the additive A in the electrolyte, more preferably 0.1%~ 8%, more preferably 0.5%~6%, more preferably 1%~5%.
The lithium salts is not particularly limited the present invention, with lithium battery electrolytes lithium salts well known to those skilled in the art , those skilled in the art can be selected and be adjusted according to applicable cases, properties of product and quality requirement, of the invention The lithium salts preferably includes lithium hexafluoro phosphate, LiBF4, lithium perchlorate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, three Oxalic acid lithium phosphate, difluoro dioxalic acid lithium phosphate, tetrafluoro oxalic acid lithium phosphate, two (trimethyl fluoride sulfonyl) imine lithiums and double fluorine sulphonyl are sub- One or more in amine lithium, more preferably lithium hexafluoro phosphate, LiBF4, lithium perchlorate, di-oxalate lithium borate, difluoro grass Sour lithium borate, three oxalic acid lithium phosphates, difluoro dioxalic acid lithium phosphate, tetrafluoro oxalic acid lithium phosphate, two (trimethyl fluoride sulfonyl) imine lithiums Or double fluorine sulfimide lithiums.
The addition of the lithium salts is not particularly limited the present invention, is added with conventional lithium salts well known to those skilled in the art Enter amount, those skilled in the art can be selected and be adjusted according to applicable cases, properties of product and quality requirement, this It is preferably 0.1~20mol/L to invent molar concentration of the lithium salts in the electrolyte, more preferably 0.5~5mol/L, more Preferably 0.6~2.5mol/L, more preferably 0.8~1.5mol/L.
The organic solvent is not particularly limited the present invention, is used with lithium battery electrolytes well known to those skilled in the art Organic solvent, those skilled in the art can be selected and be adjusted according to applicable cases, properties of product and quality requirement Whole, the ethers that organic solvent of the present invention preferably includes the carbonate-based solvent of floride-free or fluorine substitution, floride-free or fluorine replaces is molten In agent, the carboxylic acid esters solvent of free-floride or fluorine substitution, the phosphoric acid ester solvent and ionic liquid class solvent of the substitution of floride-free or fluorine One or more in one or more, the more preferably carbonate-based solvent of floride-free or fluorine substitution, the ether of floride-free or fluorine substitution Class solvent, the carboxylic acid esters solvent of floride-free or fluorine substitution, the phosphoric acid ester solvent or ionic liquid class solvent of the substitution of floride-free or fluorine, Can be ethylene carbonate+dimethyl carbonate, fluorinated ethylene carbonate+dimethyl carbonate+methyl ethyl carbonate+hexafluoro isopropyl first Base ether, fluoro carbonic ester+trifluoroacetic acid methyl esters, trimethyl phosphate+fluorinated ethylene carbonate or N- methyl-N- butylpiperidins- Bis trifluoromethyl sulfonamide PP14TFSI ionic liquids+hexafluoro isopropyl methyl ether, specific proportioning can be ethylene carbonate+carbon Dimethyl phthalate (3:7, v/v), fluorinated ethylene carbonate+dimethyl carbonate+methyl ethyl carbonate+hexafluoro isopropyl methyl ether (2:3: 1:4, v/v/v/v), fluoro carbonic ester+trifluoroacetic acid methyl esters (3:7, v/v), trimethyl phosphate+fluorinated ethylene carbonate (9: 1, v/v) or N- methyl-N- butylpiperidins-bis trifluoromethyl sulfonamide PP14TFSI ionic liquids+hexafluoro isopropyl methyl ether (9:1,v/v)。
Performance of the invention further to improve lithium battery, particularly when lithium salts is the lithium salts centered on N atoms, be The corrosion of Al collectors is prevented, the electrolyte preferably also includes additive B, more preferably the Al collection liquid surfaces can be made blunt The additive B of change.
The specifically chosen of the additive B is not particularly limited the present invention, with lithium well known to those skilled in the art electricity Pond electrolyte typical additives, those skilled in the art can enter according to applicable cases, properties of product and quality requirement Row selection and adjustment, additive B of the present invention preferably include Li2CO3、CaCO3、Al2O3、ZnO、MgO、BaO、AlF3、MgF2、 AlOF、LiPF6、LiBF4With one or more in LiBOB, more preferably Li2CO3、CaCO3、Al2O3、ZnO、MgO、BaO、AlF3、 MgF2、AlOF、LiPF6、LiBF4Or LiBOB.
The addition of the additive B is not particularly limited the present invention, is added with routine well known to those skilled in the art Enter amount, those skilled in the art can be selected and be adjusted according to applicable cases, properties of product and quality requirement, this Invent the additive B account for the electrolyte mass percent be preferably 0.005%~10%, more preferably 0.01%~ 8%, more preferably 0.05%~6%, more preferably 0.1%~4%, more preferably 0.5%~2%.
The present invention is further improves the performance of lithium battery, and stable positive pole interfacial film and negative pole SEI films, the electrolyte are excellent Choosing also includes addition of C.
The specifically chosen of the addition of C is not particularly limited the present invention, with lithium well known to those skilled in the art electricity Pond electrolyte typical additives, those skilled in the art can enter according to applicable cases, properties of product and quality requirement Row selection and adjustment, addition of C of the present invention preferably include the sub- propyl ester of sulfuric acid, ethylene sulfite, propylene sulfite, 1- Propyl group phosphoric acid cyclic anhydride, three (trimethyl silicane) phosphates, trimethyl phosphate, three (1,1,1,3,3,3- hexafluoro isopropyls) phosphoric acid Ester, fluorinated ethylene carbonate, methyl phenyl ethers anisole, vinylene carbonate, acid suppression vinyl acetate, propylene cyanogen, vinylethylene carbonate, 1,3- third Sultone, succinonitrile, 1,3- acrylic-sultones, divinylsulfone, dioxalic acid lithium borate and difluoro (oxalic acid) boric acid One or more in lithium, more preferably sulfuric acid Asia propyl ester, ethylene sulfite, propylene sulfite, 1- propyl group phosphoric acid cyclic anhydride, Three (trimethyl silicane) phosphates, trimethyl phosphate, three (1,1,1,3,3,3- hexafluoro isopropyls) phosphates, fluoro ethylene carbonate Ester, methyl phenyl ethers anisole, vinylene carbonate, acid suppression vinyl acetate, propylene cyanogen, vinylethylene carbonate, 1,3- propane sultones, fourth two Nitrile, 1,3- acrylic-sultones, divinylsulfone, dioxalic acid lithium borate or difluoro (oxalic acid) lithium borate.
The addition of the addition of C is not particularly limited the present invention, is added with routine well known to those skilled in the art Enter amount, those skilled in the art can be selected and be adjusted according to applicable cases, properties of product and quality requirement, this It is preferably 0.005%~10% to invent the addition of C and account for the mass percent of the electrolyte, more preferably 0.01%~ 8%, more preferably 0.05%~6%, more preferably 0.1%~4%, more preferably 0.5%~2%.
The content of the free acid of the electrolyte is not particularly limited the present invention, and those skilled in the art can be according to should Selected and adjusted with situation, properties of product and quality requirement, the present invention further aligns to improve the performance of lithium battery Pole material is optimized, and the content of the free acid of the electrolyte, which is preferably less than, is equal to 50ppm, is more preferably less than equal to 40ppm, more preferably less than equal to 30ppm.
The present invention is poor for the acid-resistant corrosion of nickelic ternary material, even in atmosphere, high-nickel material surface is very Easily with the CO in air2And H2O, which reacts, generates Li2CO3And LiOH, these accessory substances easily with LiPF6Base carbonic ester electricity Solve liquid reaction, Li2CO3It can cause to produce serious ballooning during high temperature storage, the LiOH and LiPF in electrolyte6Reaction production Raw HF, and then directly influence the capability retention during material circulation, and current LiPF6Base carbonic ester electrolyte holds again The free acids such as HF are also easy to produce, especially HF is more also easy to produce under high temperature, is acidified electrolyte, so as to cause the acidizing corrosion of electrode material And the drastically deterioration of battery performance, and whether positive electrode Surface coating or electrolysis additive, its effect is all Directly contacting between material and electrolyte is reduced, material surface prevents the corrosion of the free acids such as HF, but can not hinder completely Only in electrolyte HF etc. generation inherent shortcoming.
The present invention is from drawbacks described above, next a kind of non-aqueous eletrolyte especially set out, and creative use additive A should Class additive A and H2A small amount of water and a small amount of HF etc. are free in O free acids such as (and/or) HF reactions, effectively capture electrolyte Acid, substantially reduces the content of free acid in electrolyte, so that the acidizing corrosion of electrode material is prevented, stable electrolyte/electrode Interface, the cyclical stability of final maintenance electrode material.
Present invention also offers a kind of lithium ion battery, including positive pole and electrolyte；The electrolyte is above-mentioned technical side Electrolyte described in case any one.
The positive electrode or lithium ion battery are not particularly limited the present invention, with lithium well known to those skilled in the art Cell positive material and lithium ion battery, those skilled in the art can be according to applicable cases, properties of product and quality It is required that being selected and being adjusted, positive electrode of the present invention is preferably tertiary cathode material, i.e., described lithium ion battery is preferred For tertiary cathode material lithium ion battery, more preferably nickelic tertiary cathode material, i.e., described lithium ion battery is more preferably height Nickel tertiary cathode material lithium ion battery.
Other compositions or parameter of the lithium ion battery are not particularly limited the present invention, ripe with those skilled in the art The conventional composition or parameter for the lithium ion battery known, those skilled in the art can according to applicable cases, properties of product with And quality requirement is selected and adjusted, lithium ion battery of the present invention preferably also includes negative pole, barrier film, battery case etc. Deng.
The invention provides a kind of nonaqueous electrolytic solution and nickelic tertiary cathode material battery, improvement of the present invention from electrolyte Aspect is started with, creative that alkyl amine compound, the class of key containing Si-N compound (silicon nitrogen class chemical combination are added in nonaqueous electrolytic solution At least one of thing) and siloxane compound, the nonaqueous electrolytic solution that the present invention is provided has extremely low free acid content, by it Applied in the lithium ion battery of nickelic tertiary cathode material, can effectively to improve cycle performance, the height of lithium ion battery Warm cycle performance and high-temperature storage performance.
Test result indicates that, lithium ion battery prepared by the electrolyte provided using the present invention has preferable normal temperature, height Charge and discharge cycles 200 weeks at warm cyclical stability and high-temperature storage performance, 25 DEG C of room temperature, the capability retention of battery for 65%~ 90%；Charge and discharge cycles are after 100 weeks at 60 DEG C of high temperature, and the capability retention of battery is 51%~81%；Stored 30 days at 55 DEG C Afterwards, open-circuit voltage OCV rates of descent are that the capability retention of 1.7%~11%, battery is 62%~89%.However, assembling is existing The lithium ion battery of conventional carbonic ester electrolyte, the charge and discharge cycles 200 weeks at 25 DEG C of room temperature, the capability retention of battery is only 23%~54%；Charge and discharge cycles are after 100 weeks at 60 DEG C of high temperature, and the capability retention of battery is only 16%~32%；At 55 DEG C After storage 30 days, the capability retention that open-circuit voltage OCV rates of descent are only 18%~34%, battery is 51%~60%.
In order to further illustrate the present invention, a kind of electrolyte and lithium-ion electric provided with reference to embodiments the present invention Pond is described in detail, but it is to be understood that these embodiments are implemented lower premised on technical solution of the present invention, give Go out detailed embodiment and specific operating process, simply to further illustrate the features and advantages of the present invention, rather than Limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following embodiments.
Reagent used in following examples of the present invention is commercial goods.
There is the species of additive A used in following examples：
Embodiment 1~10
Organic solvent is selected from the mixed liquor that carbonate-based solvent is ethylene carbonate EC and dimethyl carbonate DMC, its volume Than for 3：7.
Lithium salts is respectively selected from LiPF6With the lithium salts LiTFSI centered on N atoms, it is 1mol L to make its molar concentration-1。
It is preferably LiPF that additive A, which is selected from above-mentioned formula 1~9, additive B,6(mass percent is 2%), addition of C are preferred For 1,3- propane sultones, (PS, mass percent is 1%), to finally obtain lithium-ion battery electrolytes.
Comparative example 1~2
Using conventional electrolyte for lithium ion battery, organic solvent be selected from carbonate-based solvent be ethylene carbonate EC with Dimethyl carbonate DMC mixed liquor, its volume ratio is 3：7.
Lithium salts is respectively selected from LiPF6With the lithium salts LiTFSI centered on N atoms, it is 1mol L to make its molar concentration-1。
Embodiment 11
To the embodiment of the present invention 1~10 and the parallel performance detection of electrolyte progress shown in comparative example 1~2,
Referring to Fig. 1, Fig. 1 is the outer of the 1000mAh Soft Roll laminated batteries that are used in the embodiment of the present invention and comparative example testing See figure.
The lithium-ion battery electrolytes of above-mentioned preparation are injected separately into 1000mAh Soft Roll laminated batteries.Tested.
Just extremely nickelic ternary material NCM nickle cobalt lithium manganates (811), negative pole is Delanium, and barrier film is Celgard 2075。
Test condition：Charging/discharging voltage interval is 2.5~4.3V；
Normal-temperature circulating performance：Charge and discharge cycles 200 times under 30 DEG C of normal temperature 1C multiplying powers；
High-temperature behavior is tested：The charge and discharge cycles 100 times under 60 DEG C of high temperature 1C multiplying powers；
High-temperature storage performance：Mesuring battary under full state of charge is placed in 55 DEG C and stored 30 days, after test battery storage Open-circuit voltage OCV rates of descent and capability retention.
Referring to table 1, table 1 is electrolyte prescription and performance test knot in lithium ion battery prepared by the embodiment of the present invention 11 Really
Table 1
It was found from the test data of table 1, followed using the room temperature of the nickelic tertiary cathode battery of the electrolyte of additive A, high temperature Ring performance and high-temperature storage performance are significantly better than that the battery of the comparative example 1 without additive.When lithium salts is former with N in electrolyte During lithium salts centered on son, compared with comparative example 2, additive A, B, C combination can significantly improve the properties of battery.
A kind of nonaqueous electrolytic solution and nickelic tertiary cathode material battery provided above the present invention has carried out detailed Jie Continue, specific case used herein is set forth to the principle and embodiment of the present invention, the explanation of above example is only It is to be used to help understand method and its core concept of the invention, including best mode, and also causes any skill of this area Art personnel can put into practice the present invention, including manufacture and the method using any device or system, and any combination of implementation.Should Point out, for those skilled in the art, under the premise without departing from the principles of the invention, can also be to this hair Bright to carry out some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.It is of the invention special Profit protection scope be defined by the claims, and may include those skilled in the art it is conceivable that other embodiment.Such as Really these other embodiments have the structural element for being similar to claim character express, or if they include wanting with right Equivalent structural elements of the character express asked without essence difference, then these other embodiments should also be included in the model of claim In enclosing.

Claims (10)

1. a kind of electrolyte, it is characterised in that including lithium salts, organic solvent and additive A；
The additive A includes the one or more in alkyl amine compound, silicon nitrogen compound and siloxane compound.
2. electrolyte according to claim 1, it is characterised in that volume hundred of the additive A in the electrolyte Divide than being 0.05%~10%；
Molar concentration of the lithium salts in the electrolyte is 0.1~20mol/L.
3. electrolyte according to claim 1, it is characterised in that the alkyl amine compound, which is selected from, has Formulas I structure One or more in shown alkyl amine compound,
Wherein, R1、R2And R3The independent straight chained alkyl or branched alkyl selected from C1~C6.
4. electrolyte according to claim 1, it is characterised in that the silicon nitrogen compound, which is selected from, has Formula II structure institute One or more in the two silicon aminated compounds shown, and/or, with the silane glyoxaline compound shown in formula III structure One or more,
Wherein, R4、R5、R6、R8、R9And R10Independent is selected from hydrogen atom, halogen, C1~C6 alkyl, C1~C6 alkoxy, C6 ~C20 aromatic radical, R7Independent is selected from hydrogen atom, halogen, C1~C6 alkyl, C1~C6 alkoxy, C6~C20 virtue Perfume base, alkali metal atom；
Wherein, R11、R12And R13Independent is selected from hydrogen atom, halogen, C1~C6 alkyl, C1~C6 alkoxy, C6~C20 Aromatic radical.
5. electrolyte according to claim 1, it is characterised in that the siloxane compound, which is selected from, has formula IV structure One or more in shown linear siloxane class compound, and/or, with the annular siloxane class shown in Formula V structure One or more in compound,
Wherein, R14、R15、R16And R17The independent alkyl selected from C1~C6, C1~C6 alkoxy, C6~C20 aromatic radical；
Wherein, R18、R19、R20、R21、R22And R23The independent straight chained alkyl or branched alkyl selected from C1~C6；
N is 1~6 integer.
6. electrolyte according to claim 1, it is characterised in that the lithium salts include lithium hexafluoro phosphate, LiBF4, Lithium perchlorate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, three oxalic acid lithium phosphates, difluoro dioxalic acid lithium phosphate, tetrafluoro oxalic acid phosphorus One or more in sour lithium, two (trimethyl fluoride sulfonyl) imine lithiums and double fluorine sulfimide lithiums；
The organic solvent include the carbonate-based solvent of floride-free or fluorine substitution, the ether solvent of floride-free or fluorine substitution, it is floride-free or One or more in phosphoric acid ester solvent and ionic liquid class solvent that carboxylic acid esters solvent, the floride-free or fluorine of fluorine substitution replace In one or more.
7. the electrolyte according to claim 1~6 any one, it is characterised in that the electrolyte also includes additive B；
The additive B includes Li2CO3、CaCO3、Al2O3、ZnO、MgO、BaO、AlF3、MgF2、AlOF、LiPF6、LiBF4With It is one or more in LiBOB；
The mass percent that the additive B accounts for the electrolyte is 0.005%~10%.
8. the electrolyte according to claim 1~6 any one, it is characterised in that the electrolyte also includes additive C；
The addition of C includes the sub- propyl ester of sulfuric acid, ethylene sulfite, propylene sulfite, 1- propyl group phosphoric acid cyclic anhydride, three (three Methyl silicon) phosphate, trimethyl phosphate, three (1,1,1,3,3,3- hexafluoro isopropyls) phosphates, fluorinated ethylene carbonate, benzene Methyl ether, vinylene carbonate, acid suppression vinyl acetate, propylene cyanogen, vinylethylene carbonate, 1,3- propane sultones, succinonitrile, 1, One or more in 3- acrylic-sultones, divinylsulfone, dioxalic acid lithium borate and difluoro (oxalic acid) lithium borate；
The mass percent that the addition of C accounts for the electrolyte is 0.005%~10%.
9. a kind of lithium ion battery, it is characterised in that including positive pole and electrolyte；
The electrolyte is the electrolyte described in claim 1~8 any one.
10. lithium ion battery according to claim 9, it is characterised in that the positive pole includes nickelic tertiary cathode material Material.
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Application publication date: 20171024