CN105680096B - electrolyte and lithium ion battery including the electrolyte - Google Patents

electrolyte and lithium ion battery including the electrolyte Download PDF

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CN105680096B
CN105680096B CN201610017727.XA CN201610017727A CN105680096B CN 105680096 B CN105680096 B CN 105680096B CN 201610017727 A CN201610017727 A CN 201610017727A CN 105680096 B CN105680096 B CN 105680096B
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CN105680096A (en
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王耀辉
史松君
谢岚
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Dongguan Amperex Technology Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

This application involves a kind of electrolyte and including the lithium ion battery of the electrolyte, wherein electrolyte includes organic solvent, lithium salts and additive, the additive includes nitrogen heterocyclic ring boron trifluoride complex and silica phosphoric ester compound, and the nitrogen heterocyclic ring is selected from the heterocycle containing pyridyl group, the heterocycle containing pyridazinyl, the heterocycle containing pyrimidine radicals, the heterocycle containing pyrazinyl, the heterocycle containing pyrrole radicals, the heterocycle of pyrazolyl containing and at least one of heterocycle containing imidazole radicals.Electrolyte provided by the present application can improve the cycle performance of lithium ion battery at ambient and elevated temperatures due to including simultaneously the nitrogen heterocyclic ring boron trifluoride complex and silica phosphoric ester compound.

Description

Electrolyte and lithium ion battery including the electrolyte
Technical field
This application involves field of lithium more particularly to a kind of electrolyte and including the lithium ion battery of the electrolyte.
Background technology
Currently, the positive electrode active materials employed in lithium ion battery mainly have LiMn2O4, cobalt acid lithium, ternary material, LiFePO 4 etc. selects the charge cutoff voltage of the lithium ion battery of the above-mentioned positive electrode being previously mentioned in general No more than 4.2V, but with advances in technology and the continuous development in market, the energy density of lithium ion battery is promoted increasingly Seem important and urgent, it is a kind of promoted lithium ion battery energy density effective ways be exploitation high-voltage lithium ion batteries.
However, for example under the high voltage of 4.6V, conventional electrolyte can be caused in the positive electrode surface oxygenolysis of battery, The oxygenolysis of electrolyte itself can promote the deteriorative reaction of positive electrode active materials simultaneously, further influence the property of lithium ion battery Can, such as cycle performance.
Invention content
To solve the above-mentioned problems, the applicant has carried out sharp study, as a result, it has been found that：When in electrolyte while including containing Azacyclo--boron trifluoride complex and silica phosphoric ester compound, are capable of providing lithium ion battery at ambient and elevated temperatures Cycle performance, to complete the application.
The application's is designed to provide a kind of electrolyte, including organic solvent, lithium salts and additive, the additive packet Include nitrogen heterocyclic ring-boron trifluoride complex and silica phosphoric ester compound, wherein the nitrogen heterocyclic ring is selected from containing pyridyl group Heterocycle, the heterocycle containing pyridazinyl, the heterocycle containing pyrimidine radicals, the heterocycle containing pyrazinyl, heterocycle containing pyrrole radicals, pyrazolyl containing Heterocycle and at least one of heterocycle containing imidazole radicals.
The another object of the application is to provide a kind of lithium ion battery, include the positive plate containing positive electrode active materials, Negative plate, isolation film containing negative electrode active material and electrolyte provided herein.
In electrolyte provided by the present application, due to including nitrogen heterocyclic ring mentioned above-boron trifluoride ligand compound simultaneously Object and silica phosphoric ester compound, therefore the cycle performance of lithium ion battery at ambient and elevated temperatures can be improved.
Specific implementation mode
It is described in detail below by the application, will become more with these explanations with advantage the characteristics of the application It is clear, clear.
The application's is designed to provide a kind of electrolyte, including organic solvent, lithium salts and additive, the additive packet Include nitrogen heterocyclic ring-boron trifluoride complex and silica phosphoric ester compound, wherein the nitrogen heterocyclic ring is selected from containing pyridyl group Heterocycle, the heterocycle containing pyridazinyl, the heterocycle containing pyrimidine radicals, the heterocycle containing pyrazinyl, heterocycle containing pyrrole radicals, pyrazolyl containing Heterocycle and at least one of heterocycle containing imidazole radicals.
In above-mentioned electrolyte, " heterocycle containing pyridyl group, the heterocycle containing pyrimidine radicals, contains the heterocycle containing pyridazinyl described It is pyridyl group, pyridazinyl, phonetic in the heterocycle of pyrazinyl, the heterocycle containing pyrrole radicals, the heterocycle of pyrazolyl containing, the heterocycle containing imidazole radicals " Piperidinyl, pyrazinyl, pyrrole radicals, pyrazolyl, imidazole radicals can be replaced by other groups, such as can be by halogen atom, hydrogen atom, alkane The substituent groups such as base are replaced.
In above-mentioned electrolyte, the nitrogen heterocyclic ring-boron trifluoride complex refers to the nitrogen heterocyclic ring of above-mentioned raising The complex that organic molecule and boron trifluoride are formed, boron trifluoride are in anion, and nitrogen heterocyclic ring is in cation, entire azepine Ring-boron trifluoride complex is in electroneutral.
Preferably, the nitrogen heterocyclic ring-boron trifluoride complex be selected from following formula I, Formula II, formula III, formula IV, At least one of Formula V, Formula IV and Formula VII compound represented：
In above-mentioned Formulas I, Formula II, formula III, formula IV, Formula V, Formula IV and Formula VII, R11、R12、R13、R14、R15、R21、R22、 R23、R24、R31、R32、R33、R34、R41、R42、R43、R44、R51、R52、R53、R54、R61、R62、R63、R71、R72、R73Each independently For be 1~20 selected from hydrogen atom, halogen atom, carbon atom number alkyl, carbon atom number be 2~20 alkenyl, carbon atom number be 6~ The aryloxy group and above-mentioned carbon atom number that alkoxy that 26 aryl, carbon atom number are 1~20, carbon atom number are 6~26 are 1 The alcoxyl that aryl that alkenyl that~20 alkyl, carbon atom number are 2~20, carbon atom number are 6~26, carbon atom number are 1~20 Base, the aryloxy group that carbon atom number is 6~26 replace the one kind being formed by group by halogen atom, sulfonic group or sulfonyl, In, halogen atom F, Cl, Br, preferably F, Cl.In addition, alkyl mentioned above, alkenyl, aryl can also be by the groups containing pyridyl group Or the group substitution of thienyl-containing.
In above-mentioned Formulas I, Formula II, formula III, formula IV, Formula V, Formula IV and Formula VII, substituent group is as described below.
The alkyl that carbon atom number is 1~20, alkyl can be chain-like alkyl or naphthenic base, be located on the ring of naphthenic base Hydrogen can be replaced by alkyl, in the alkyl the preferred lower limiting value of carbon atom number be 2,3,4,5, preferred upper limit value be 3,4,5, 6,8,10,12,14,16,18.Preferably, select carbon atom number for 1~10 alkyl, it is further preferred that selection carbon atom number For 1~6 chain-like alkyl, carbon atom number is 3~8 naphthenic base, it is further preferred that select carbon atom number for 1~4 chain Shape alkyl, the naphthenic base that carbon atom number is 5~7.As the example of alkyl, can specifically enumerate：It is methyl, ethyl, n-propyl, different Propyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl, isopentyl, neopentyl, cyclopenta, cyclohexyl.
The alkenyl that carbon atom number is 2~20, can be cyclic alkenyl radical or chain alkenyl.In addition, in alkenyl double bond Number preferably 1.The preferred lower limiting value of carbon atom number is 3,4,5 in the alkenyl, and preferred upper limit value is 3,4,5,6,8,10, 12,14,16,18.Preferably, select carbon atom number for 2~10 alkenyl, it is further preferred that selecting carbon atom number for 2~6 Alkenyl, it is further preferred that select carbon atom number for 2~5 alkenyl.As the example of alkenyl, can specifically enumerate：Second Alkenyl, allyl, isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base.
Carbon atom number be 6~26 aryl, such as phenyl, benzene alkyl, at least contain there are one phenyl aryl such as xenyl, Condensed-nuclei aromatics base such as naphthalene, anthracene, phenanthrene, xenyl and condensed-nuclei aromatics base can also be replaced by alkyl or alkenyl.Preferably, it selects Select carbon atom number be 6~16 aryl, it is further preferred that select carbon atom number for 6~14 aryl, still more preferably Ground, select carbon atom number for 6~9 aryl.As the example of aryl, can specifically enumerate：Phenyl, benzyl, xenyl, to first Phenyl, o-tolyl, tolyl.
When containing oxygen atom in the alkyl that the aforementioned carbon atom number being previously mentioned is 1~20, alkoxy can be formed.It is preferred that Ground, select carbon atom number for 1~10 alkoxy, it is further preferred that select carbon atom number for 1~6 alkoxy, more into one Step preferably, select carbon atom number for 1~4 alkoxy.As the example of alkoxy, can specifically enumerate：Methoxyl group, ethoxy Base, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, cyclopentyloxy, ring Hexyloxy.
When containing oxygen atom in the aryl that the aforementioned carbon atom number being previously mentioned is 6~26, aryloxy group can be formed.It is preferred that Ground, select carbon atom number for 6~16 aryloxy group, it is further preferred that select carbon atom number for 6~14 aryloxy group, more into One step preferably, select carbon atom for 6~10 aryloxy group.As the example of aryloxy group, can specifically enumerate：Phenoxy group, benzyl Oxygroup, 4- methylphenoxies, 3,5- dimethyl phenoxies, 4- methylbenzyloxies, 3- methylbenzyloxies, 2,6- diisopropyl benzyloxies Base, 1- naphthoxys.
When alkenyl that alkyl that the carbon atom number being previously mentioned is 1~20, carbon atom number are 2~20, carbon atom number be 6~ After the aryloxy group that alkoxy that 26 aryl, carbon atom number are 1~20, carbon atom number are 6~26 is replaced by halogen atom, phase successively Halogenated alkenyl that halogenated alkyl that the formation carbon atom number answered is 1~20, carbon atom number are 2~20, carbon atom number are 6~26 The haloaryloxy that halogenated alkoxy that halogenated aryl, carbon atom number are 1~20, carbon atom number are 6~26, wherein halogen atom are F, Cl, Br, preferably F, Cl.In being formed by halo groups, halogen atom carries out part hydrogen atom or whole hydrogen atoms The number of substitution, halogen atom can be 1,2,3 or 4.
Preferably, select carbon atom number for 1~10 halogenated alkyl, carbon atom number be 2~10 halogenated alkenyl, carbon atom The haloaryloxy that the halogenated aryl for 6~16, the halogenated alkoxy that carbon atom number is 1~10, carbon atom number are 6~16 is counted, It is further preferred that select carbon atom number for 1~6 halogenated chain-like alkyl, carbon atom number be 3~8 halogenated cycloalkyl, carbon it is former Halogenated alkoxy that halogenated aryl that halogenated alkenyl that subnumber is 2~6, carbon atom number are 6~14, carbon atom number are 1~6, carbon The haloaryloxy that atomicity is 6~14, it is further preferred that selecting halogenated chain-like alkyl, carbon of the carbon atom number for 1~4 Halogenated aryl that halogenated alkenyl that halogenated cycloalkyl that atomicity is 5~7, carbon atom number are 2~5, carbon atom are 6~10, carbon The haloaryloxy that halogenated alkoxy that atomicity is 1~4, carbon atom are 6~10.
As the example of halo groups, can specifically enumerate：Trifluoromethyl (- CF3), 2- fluoro ethyls, 3- fluorine n-propyl, 2- Fluorine isopropyl, 4- fluorine normal-butyl, 3- fluorine sec-butyl, 5- fluorine n-pentyl, 4- fluorine isopentyl, 1- be fluoride-based, 3- fluorine allyl, 6- Fluoro- 4- hexenyls, o-fluorophenyl, p-fluorophenyl, fluorophenyl, 4- trifluoromethylphenyls, 2,6- difluoromethyls phenyl, the fluoro- 1- of 2- Naphthalene, fluoro-methoxy, 1- fluorine ethyoxyl, the fluoro- positive propoxies of 2-, the fluoro- isopropoxies of 1-, the fluoro- n-butoxies of 3-, 4- are fluoro- just Amoxy, 2,2- difluoromethyls propoxyl group, the fluoro- positive hexyloxies of 5-, 1,1,2- trifluoromethyl propoxyl group, the fluoro- n-heptyl oxygroups of 6-, The fluoro- n-octyl oxygroups of 7-, the fluoro- cyclopentyloxies of 3-, the fluoro- 2- methylcyclopentoxies of 4-, the fluoro- cyclohexyloxies of 3-, 3- fluorine cycloheptyls oxygroup, The fluoro- 2- methyl cycloheptyl oxygroups of 4-, 3- fluorine rings octyloxy, 4- fluorophenoxies, 3- fluorophenoxies, 2- fluorophenoxies, 3,5- difluorobenzenes Oxygroup, 2,6- difluoros phenoxy group, 2,3- difluoros phenoxy group, 2,6-, bis- fluoro- 4- methylphenoxies, 3- (2- fluoro ethyls) phenoxy group, 2- (1- fluoro ethyls) phenoxy group, 3,5- difluoros benzyloxy, 2- fluorine benzyloxy, the fluoro- 1- naphthoxys of 2-.In above-mentioned specific example In, F can be replaced by Cl and/or Br.
The aryl that carbon atom number is 1~20 alkyl, carbon atom number is 2~20 alkenyl, carbon atom number are 6~26 is by sulfonic acid It is corresponding to form sulfonic group alkyl, sulfonic group alkenyl, sulfonic group aryl, alkyl sulphonyl, alkenyl sulphur after base or sulfonyl substitution Acyl group, aryl sulfonyl.Sulfonic group can in abovementioned alkyl, alkenyl, aryl part hydrogen atom or whole hydrogen atom carry out Substitution, sulfonic number can be 1 or 2, likewise, sulfonyl can be former to the part hydrogen in abovementioned alkyl, alkenyl, aryl Son or whole hydrogen atoms are replaced, and the number of sulfonyl can be 1 or 2.
As containing sulfonyl example, can specifically enumerate：It is methyl sulphonyl, ethylsulfonyl, n-propyl sulfonyl, different Sulfonyl propyl base, normal-butyl sulfonyl, iso-butylsulfonyl, tert. butylsulfonyl, n-pentyl sulfonyl, isopentyl sulfonyl, Neopentyl sulfonyl, 2,3- dimethyl propyls sulfonyl, 1- ethyl propyls sulfonyl, n-hexyl sulfonyl, Cyclopentylsulfonyl, Cyclohexylsulfonyl, suberyl sulfonyl, cyclooctyl sulfonyl, n-heptyl sulfonyl, n-octyl sulfonyl, suberyl sulphonyl Base, cyclooctyl sulfonyl, acrylic sulfonyl, cyclobutenyl sulfonyl, pentenyl sulfonyl, hexenyl sulfonyl, heptenyl sulphur Acyl group, octenyl sulfonyl, phenyl sulfonyl, 4- Methyl benzenesulfonyl bases.
In addition contain sulfonic example, can specifically enumerate：Sulfonomethyl, 2- sulfonic groups ethyl, 3- sulfonic groups positive third Base, 4- sulfonic groups normal-butyl, sulfonic group tertiary butyl, 2- sulfonic groups n-pentyl, 3- sulfonic groups isopentyl, 6- sulfonic groups n-hexyl, 2- sulfonic acid cyclopentyl, 4- sulfonic acid butylcyclohexyl, sulfonic group acrylic, sulfonic group cyclobutenyl, sulfonic group pentenyl, sulfonic group oneself Alkenyl, sulfonic group heptenyl, sulfonic group octenyl, sulfonic group phenyl, 4- sulfonic acid methyl phenyl.
In addition, in above-mentioned Formulas I~Formula VII compound represented, R11、R12、R13、R14、R15At least one of be halogen Atom, halogen atom are preferably F or Cl, R21、R22、R23、R24At least one of be halogen atom, halogen atom is preferably F or Cl, R31、R32、R33、R34At least one of be halogen atom, halogen atom is preferably F or Cl, R41、R42、R43、R44At least one of For halogen atom, halogen atom is preferably F or Cl, R51、R52、R53、R54At least one of be halogen atom, halogen atom be preferably F or Cl, R61、R62、R63At least one of be halogen atom, preferably F or Cl, R71、R72、R73At least one of be halogen atom, halogen Atom is preferably F or Cl.
It is specific as follows shown as the example of nitrogen heterocyclic ring-boron trifluoride complex：
In this application, the nitrogen heterocyclic ring being previously mentioned-boron trifluoride complex can be according to existing conventional synthesis Method is synthesized, such as can refer to patent：CN200780033378.X.
In above-mentioned electrolyte, the silica phosphoric ester compound is in following formula VIII, Formula IX compound represented At least one：
In above-mentioned Formula VIII, Formula IX, R81、R82、R83、R84、R85、R86、R87、R88、R89、R91、R92、R93、R94、R95、 R96、R97、R98、R99Be each independently selected from hydrogen atom, halogen atom, carbon atom number be 1~10 alkyl, carbon atom number be 2~ The alkane that halogenated alkyl that aryl that 10 alkenyl, carbon atom number are 6~10, carbon atom number are 1~10, carbon atom number are 1~10 Halogenated alkyl that aryloxy group that oxygroup, carbon atom number are 6~10, carbon atom number are 1~10, carbon atom number be 6~10 it is halogenated One kind in the haloaryloxy that the halogenated alkoxy and carbon atom number that aryl, carbon atom number are 1~10 are 6~10, In, halogen atom F, Cl, Br, preferably F, Cl, and R81、R82、R83、R84、R85、R86、R87、R88And R89All same, R91、 R92、R93、R94、R95、R96、R97、R98And R99All same.
In above-mentioned Formula VIII, Formula IX, substituent group is as described below.
The alkyl that carbon atom number is 1~10, alkyl can be chain-like alkyl or naphthenic base, be located on the ring of naphthenic base Hydrogen can be replaced by alkyl, in the alkyl the preferred lower limiting value of carbon atom number be 2,3,4,5, preferred upper limit value be 3,4,5, 6,8,9.Preferably, select carbon atom number for 1~6 chain-like alkyl, the naphthenic base that carbon atom number is 3~8, further preferably Ground selects carbon atom number for 1~4 chain-like alkyl, the naphthenic base that carbon atom number is 5~7.As the example of alkyl, specifically may be used To enumerate：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl, isopentyl, new penta Base, cyclopenta, cyclohexyl.
The alkenyl that carbon atom number is 2~10, can be cyclic alkenyl radical or chain alkenyl.In addition, in alkenyl double bond Number preferably 1.The preferred lower limiting value of carbon atom number is 3,4,5 in the alkenyl, and preferred upper limit value is 3,4,5,6,8,9. Preferably, select carbon atom number for 2~6 alkenyl, it is further preferred that select carbon atom number for 2~5 alkenyl.As alkene The example of base can specifically be enumerated：Vinyl, allyl, isopropenyl, pentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene Base.
The aryl that carbon atom number is 6~10, such as phenyl, benzene alkyl, condensed-nuclei aromatics base such as naphthalene, xenyl and condensed ring Aryl can also be replaced by alkyl or alkenyl.The preferred lower limiting value of carbon atom number is 7,8 in the aryl, the preferred upper limit Value is 8,9.Preferably, select carbon atom number for 6~9 aryl.As the example of aryl, can specifically enumerate：Phenyl, benzyl Base, xenyl, p-methylphenyl, o-tolyl, tolyl.
When containing oxygen atom in the alkyl that the aforementioned carbon atom number being previously mentioned is 1~10, alkoxy can be formed.It is preferred that Ground, select carbon atom number for 1~6 alkoxy, it is further preferred that select carbon atom number for 1~4 alkoxy.As alkane The example of oxygroup can specifically be enumerated：Methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, uncle Butoxy, n-pentyloxy, isoamoxy, cyclopentyloxy, cyclohexyloxy.
When containing oxygen atom in the aryl that the aforementioned carbon atom number being previously mentioned is 6~10, aryloxy group can be formed.It is preferred that Ground, select carbon atom for 6~9 aryloxy group.As the example of aryloxy group, can specifically enumerate：Phenoxy group, benzyloxy, 4- first Phenoxyl, 3,5- dimethyl phenoxies, 4- methylbenzyloxies, 3- methylbenzyloxies, 2,6- diisopropyls benzyloxy, 1- naphthalene oxygen Base.
When alkenyl that alkyl that the carbon atom number being previously mentioned is 1~10, carbon atom number are 2~10, carbon atom number be 6~ After the aryloxy group that alkoxy that 10 aryl, carbon atom number are 1~10, carbon atom number are 6~10 is replaced by halogen atom, phase successively Halogenated alkenyl that halogenated alkyl that the formation carbon atom number answered is 1~10, carbon atom number are 2~10, carbon atom number are 6~10 The haloaryloxy that halogenated alkoxy that halogenated aryl, carbon atom number are 1~10, carbon atom number are 6~10, wherein halogen atom are F, Cl, Br, preferably F, Cl.In being formed by halo groups, halogen atom carries out part hydrogen atom or whole hydrogen atoms The number of substitution, halogen atom can be 1,2,3 or 4.
Preferably, select carbon atom number for 1~6 halogenated chain-like alkyl, carbon atom number be 3~8 halogenated cycloalkyl, carbon Halogenated alkoxy that halogenated aryl that halogenated alkenyl that atomicity is 2~6, carbon atom number are 6~9, carbon atom number are 1~6, carbon The haloaryloxy that atomicity is 6~9, it is further preferred that selecting halogenated chain-like alkyl, carbon atom of the carbon atom number for 1~4 Count the halogenated aryl, carbon atom number that the halogenated cycloalkyl for 5~7, the halogenated alkenyl that carbon atom number is 2~5, carbon atom are 6~8 For 1~4 halogenated alkoxy, carbon atom be 6~8 haloaryloxy.
As the example of halo groups, can specifically enumerate：Trifluoromethyl (- CF3), 2- fluoro ethyls, 3- fluorine n-propyl, 2- Fluorine isopropyl, 4- fluorine normal-butyl, 3- fluorine sec-butyl, 5- fluorine n-pentyl, 4- fluorine isopentyl, 1- be fluoride-based, 3- fluorine allyl, 6- Fluoro- 4- hexenyls, o-fluorophenyl, p-fluorophenyl, fluorophenyl, 4- trifluoromethylphenyls, 2,6- difluoromethyls phenyl, the fluoro- 1- of 2- Naphthalene, fluoro-methoxy, 1- fluorine ethyoxyl, the fluoro- positive propoxies of 2-, the fluoro- isopropoxies of 1-, the fluoro- n-butoxies of 3-, 4- are fluoro- just Amoxy, 2,2- difluoromethyls propoxyl group, the fluoro- positive hexyloxies of 5-, 1,1,2- trifluoromethyl propoxyl group, the fluoro- n-heptyl oxygroups of 6-, The fluoro- n-octyl oxygroups of 7-, the fluoro- cyclopentyloxies of 3-, the fluoro- 2- methylcyclopentoxies of 4-, the fluoro- cyclohexyloxies of 3-, 3- fluorine cycloheptyls oxygroup, The fluoro- 2- methyl cycloheptyl oxygroups of 4-, 3- fluorine rings octyloxy, 4- fluorophenoxies, 3- fluorophenoxies, 2- fluorophenoxies, 3,5- difluorobenzenes Oxygroup, 2,6- difluoros phenoxy group, 2,3- difluoros phenoxy group, 2,6-, bis- fluoro- 4- methylphenoxies, 3- (2- fluoro ethyls) phenoxy group, 2- (1- fluoro ethyls) phenoxy group, 3,5- difluoros benzyloxy, 2- fluorine benzyloxy, the fluoro- 1- naphthoxys of 2-.In above-mentioned specific example In, F can be replaced by Cl and/or Br.
As the example of silica phosphoric ester compound, can specifically enumerate：
In this application, the silica phosphoric ester compound being previously mentioned can be synthesized according to existing conventional synthetic method, Such as it can refer to document：US5830600.
It has been investigated that when in electrolyte simultaneously including nitrogen heterocyclic ring mentioned above-boron trifluoride complex and When silica phosphoric ester compound, under the common synergistic effect of the two, being respectively formed on the positive and negative plate surface of lithium ion battery can The SEI films of electrolyte decomposition are prevented, especially form the small and fine and close solid electrolyte interface (SEI) of impedance on negative plate surface Film；In addition, due to containing nitrogen heterocyclic ring-boron trifluoride complex and silica phosphoric ester compound in electrolyte simultaneously, may be used also To adsorb the substances such as oxygen and lithia in anode；Additionally it is possible to neutralize the acidic materials generated in electrolyte, such as PF5、 HF、CO2Deng effectively reducing corrosion of these acidic materials to SEI films；It is possible thereby to learn, under the synergistic effect of the two, greatly The big cycle performance for improving lithium ion battery, such as lithium ion battery have under 4.6V high voltages and at 25 DEG C and 45 DEG C There is excellent cycle performance；At the same time, the high temperature safety of electrolyte and storage performance are also significantly improved.
In above-mentioned electrolyte, the content of the nitrogen heterocyclic ring-boron trifluoride complex is the total weight of electrolyte 0.05%~10%, the content of the nitrogen heterocyclic ring-boron trifluoride complex is preferably the total weight of electrolyte 0.1%~4%, the content of the silica phosphoric ester compound is the 0.1%~10% of the total weight of electrolyte, the silica phosphide The content of compound is the 1%~4% of the total weight of electrolyte.
If in the electrolytic solution, nitrogen heterocyclic ring-boron trifluoride complex content is excessive, then can cause in positive and negative plate Surface forms thicker SEI films, reduces the conductive performance of lithium ion, deteriorates the cyclicity of lithium ion battery at ambient and elevated temperatures Energy；And the content of silica phosphoric ester compound is excessive, also can form SEI films that are very thick and stablizing on positive and negative plate surface, makes The impedance of positive and negative plate greatly increases, reduce the conductive performance of lithium ion, deteriorate lithium ion battery at ambient and elevated temperatures Cycle performance.
If in the electrolytic solution, nitrogen heterocyclic ring-boron trifluoride complex content is too small, lithium-ion electric cannot be effectively improved The cycle performance of pond at ambient and elevated temperatures, cycle performance especially under high pressure；And the content mistake of silica phosphoric ester compound It is small, it can not equally improve the cycle performance of lithium ion battery at ambient and elevated temperatures, cycle performance especially under high pressure.
In above-mentioned electrolyte, the organic solvent can be non-aqueous organic solvent, and the organic solvent is preferably carbon atom Number is 1~8 and the compound containing at least one ester group.
As the example of organic solvent, can enumerate：Ethylene carbonate, propene carbonate, butylene, fluoro carbonic acid second Enester, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, Isosorbide-5-Nitrae-fourth Lactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl butyrate.
In above-mentioned electrolyte, the lithium salts can be organic lithium salt or inorganic lithium salt, specifically, the lithium salts In can contain fluorine element, boron element, at least one of P elements.Preferably, the lithium salts is selected from lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), tetrafluoro oxalic acid lithium phosphate (LiTFOP)、LiN(SO2RF)2、LiN(SO2F)(SO2RF), double trifluoromethanesulfonimide lithium LiN (CF3SO2)2It (is abbreviated as LiTFSI), bis- (fluorine sulphonyl) imine lithium Li (N (SO2F)2) (being abbreviated as LiFSI), di-oxalate lithium borate LiB (C2O4)2It (is abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF2(C2O4At least one of) (being abbreviated as LiDFOB), wherein substituent RF=- CnF2n+1Saturation perfluoroalkyl, n be 1~10 integer, preferably 1~4 integer, and 2n+1 be more than zero integer.It is especially excellent It is selected as LiPF6And/or LiN (SO2RF)2.A concentration of 0.5M~2M (the M=mol L of the lithium salts in the electrolytic solution-1)。
In this application, the preparation method of electrolyte selects conventional method, such as by organic solvent, lithium salts and can add Agent is added to be uniformly mixed.
The another object of the application is the provision of lithium ion battery, and the lithium ion battery includes electrolyte, containing just The positive plate of pole active material, negative plate and isolation film containing negative electrode active material.
In above-mentioned lithium ion battery, the positive plate further includes binder and conductive agent, will include positive-active material The anode sizing agent of material, binder and conductive agent is coated on plus plate current-collecting body, and positive plate is obtained after anode sizing agent drying.Equally , by include negative electrode active material, binder and conductive agent negative electrode slurry be coated in negative current collector on, wait for negative electrode slurry Negative plate is obtained after drying.
Preferably, the positive electrode active materials are selected from cobalt acid lithium LiCoO2, cobalt nickel lithium manganate ternary material, ferrous phosphate Lithium, LiFePO4 (LiFePO4), LiMn2O4 (LiMnO2At least one of), such as cobalt acid lithium and lithium-nickel-manganese-cobalt ternary material Mixture can be used as positive electrode active materials.As the example of cobalt nickel lithium manganate ternary material, can specifically enumerate：LiNi1/3Co1/ 3Mn1/3O2, nickle cobalt lithium manganate LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2。
Preferably, the negative electrode active material is graphite and/or silicon.
In above-mentioned lithium ion battery, the specific type of lithium battery diaphragm is not exposed to specific limitation, can be existing Any diaphragm material used in lithium ion battery, such as polyethylene, polypropylene, Kynoar and their MULTILAYER COMPOSITE Film, but it is not limited only to these.
Embodiment
The application is further described below by way of specific example.But these examples are only exemplary, not to this The protection domain of application constitutes any restrictions.
In following embodiments, comparative example and test example, reagent, material and the instrument used be not such as special Explanation, be conventional reagent, conventional material and conventional instrument, it is commercially available, wherein involved reagent can also lead to Conventional synthesis process synthesis is crossed to obtain.
In following embodiments, comparative example and test example, used reagent is as follows：
Additive：
Nitrogen heterocyclic ring-boron trifluoride complex：1~the compound of compound 7 being previously mentioned.
Silica phosphoric ester compound：The silica phosphide 1 being previously mentioned.
Lithium salts：Lithium hexafluoro phosphate (LiPF6)。
Organic solvent：Ethylene carbonate (EC), methyl ethyl carbonate (EMC).
Positive electrode active materials：Lithium-nickel-manganese-cobalt ternary material (LiNi1/3Co1/3Mn1/3O2)。
Isolation film：Using PE porous polymer films as isolation film.
The preparation of 6 lithium ion battery of Examples 1 to 3 (following abbreviation batteries) 1~36
Battery 1~36 is prepared by the following method：
(1) prepared by negative plate
Negative electrode active material graphite, conductive agent acetylene black, binder butadiene-styrene rubber, thickener sodium carboxymethylcellulose are pressed It is graphite: acetylene black: butadiene-styrene rubber: sodium carboxymethylcellulose=95: mixed at 2: 2: 1 according to weight ratio, deionized water is added Afterwards, it is thoroughly mixed, forms uniform negative electrode slurry；This slurry is coated on negative current collector copper foil, then dries, is cold Pressure, obtains negative plate.
(2) prepared by positive plate
By weight by positive electrode active materials lithium-nickel-manganese-cobalt ternary material, conductive agent acetylene black, binder polyvinylidene fluoride Than for lithium-nickel-manganese-cobalt ternary material: acetylene black: Solvents N-methyl pyrrolidines is added in polyvinylidene fluoride=96: mixed at 2: 2 Ketone after being thoroughly mixed, forms uniform anode sizing agent；This slurry is coated on plus plate current-collecting body aluminium foil, then dry, Cold pressing, obtains positive plate.
(3) prepared by electrolyte
Electrolyte 1~36 is prepared by the following method：
In the argon gas atmosphere glove box of water content ＜ 10ppm, EC, EMC are carried out according to weight ratio for EC: EMC=3: 7 After mixing, mixed solvent is obtained, then the lithium salts LiPF that will fully dry6It is dissolved in above-mentioned in the mixed solvent, is then added thereto Enter nitrogen heterocyclic ring-boron trifluoride complex and silica phosphoric ester compound, after stirring evenly, obtains electrolyte, wherein LiPF6 A concentration of 1mol/L.
(4) preparation of battery
Battery 1~36 is prepared by the following method：
Positive plate, isolation film, negative plate are folded in order, the work of isolation is played between so that isolation film is in positive/negative plate With then winding obtains naked battery core；Naked battery core is placed in outer packing foil, after the above-mentioned electrolyte prepared is injected into drying Battery in, then pass through the processes such as Vacuum Package, standing, chemical conversion, shaping, obtain battery.
It is above-mentioned prepare battery during, it is used in selected electrolyte, each electrolyte in each battery The type of nitrogen heterocyclic ring-boron trifluoride complex and its content of content and silica phosphoric ester compound, such as institute in following table 1 Show.
In following table 1, the content of nitrogen heterocyclic ring-boron trifluoride complex and the content of silica phosphoric ester compound It is the weight percent that the total weight based on electrolyte is calculated.
Table 1
1~21 lithium ion battery of comparative example (following abbreviation batteries) 1#~21#Preparation
Comparative example 1~21
Battery 1#~21#Prepared by the following method：
The preparation of battery 1 in embodiment 1 is repeated, wherein in the preparation of electrolyte, changes nitrogen heterocyclic ring-boron trifluoride and matches Type, the content of position compound, and/or change the content of silica phosphoric ester compound, remaining condition is constant.
It is above-mentioned prepare battery during, it is used in selected electrolyte, each electrolyte in each battery The type of nitrogen heterocyclic ring-boron trifluoride complex and its content of content and silica phosphoric ester compound, such as institute in following table 2 Show.
In following table 2, the content of nitrogen heterocyclic ring-boron trifluoride complex and the content of silica phosphoric ester compound It is the weight percent that the total weight based on electrolyte is calculated.
Table 2
Note：In table 2, "-" expression is not added with any kind of substance.
Test case
(1) survey of electrochemical impedance spectroscopy (ElectrochemicalImpedance Spectroscopy, be abbreviated as EIS) Examination
The battery being prepared in embodiment and comparative example carries out following tests：
At 25 DEG C, by with the constant current of 0.5C to battery discharge to 3.0V, then extremely with 0.5C constant current discharges Then 3.85V charges to electric current to battery with the constant voltage of 3.85V and is less than 0.05C, the capacity of battery, which reaches, at this time completely fills appearance Then the 50% of amount uses VMP3 electrochemical workstations, carry out EIS tests to battery under 25 DEG C of constant temperatures, obtain electricity Lotus transfger impedance Rct, test result is as follows shown in table 3.
(2) the normal-temperature circulating performance test of battery
The battery being prepared in embodiment and comparative example carries out following tests：
At 25 DEG C, 4.6V is first charged to battery with the constant current of 1C, further extremely with 4.6V constant-potential charges Electric current is 0.025C, and then with the constant current of 1C by battery discharge to 3.0V, this is a charge and discharge cycles process, this Discharge capacity is the discharge capacity of the 1st cycle.Battery carries out multiple cyclic charging and discharging test in a manner described, and detection obtains the The discharge capacity of 100 cycles, and it is calculate by the following formula the circulation volume conservation rate for obtaining battery.In addition, test result is as follows Shown in table 3.
Capacity retention ratio (%) after the cycle of battery 100 times=[discharge capacity/1st time cycle of the 100th cycle is put Capacitance] × 100%
(3) the high temperature cyclic performance test of battery
The battery being prepared in embodiment and comparative example carries out following tests：
At 45 DEG C, 4.6V is first charged to battery with the constant current of 1C, further extremely with 4.6V constant-potential charges Electric current is 0.025C, and then with the constant current of 1C by battery discharge to 3.0V, this is a charge and discharge cycles process, this Discharge capacity is the discharge capacity of the 1st cycle.Battery carries out multiple cyclic charging and discharging test in a manner described, and detection obtains the The discharge capacity of 100 cycles, and it is calculate by the following formula the capacity retention ratio after the cycle for obtaining battery.In addition, test result As shown in Table 3 below.
Capacity retention ratio (%) after the cycle of battery 100 times=[discharge capacity/1st time cycle of the 100th cycle is put Capacitance] × 100%
Table 3
Related data from above-mentioned table 3, is analyzed as follows：
(1) test result analysis of EIS
By to battery 2#, battery 3#And battery 4 and battery 1#Test obtaining as a result, it is known that only adding silica phosphorus Ester compounds, Rct values are smaller；Only addition nitrogen heterocyclic ring-boron trifluoride complex, Rct values are bigger；When in electrolyte When containing silica phosphoric ester compound and nitrogen heterocyclic ring-boron trifluoride complex simultaneously, it is borontrifluoride more only to add nitrogen heterocyclic ring- The case where boron complex, Rct values are smaller.
By the test result comparison of obtained battery, it is known that when the additive amount of silica phosphoric ester compound is excessive, Rct Value is also larger；Likewise, if the content of nitrogen heterocyclic ring-boron trifluoride complex is excessive, Rct values are also larger.
(2) test result analysis of cycle performance
Capacity retention ratio after the cycle obtained by battery 1~36 and battery 1#Capacity retention ratio after obtained cycle can To find out, nitrogen heterocyclic ring-boron trifluoride complex and silica phosphoric ester compound are contained in electrolyte, battery has higher Capacity retention ratio, battery have excellent cycle performance under high temperature and room temperature.
By battery 1#~9#Capacity retention ratio after obtained cycle, it is known that electrolyte 1#In not any add without being added Add agent so that organic solvent can generate more side reaction in pole piece, cause the capacity retention ratio of battery low.
In battery 2#With battery 3#In, nitrogen heterocyclic ring-boron trifluoride ligand compound is added in respective electrolyte respectively Object, silica phosphoric ester compound can't effectively prevent the pair between active material and electrolyte anti-due to being formed by SEI films It answers, to make the cycle performance of battery substantially cannot improve.
Due in battery 4#, battery 5#With battery 7#In, nitrogen heterocyclic ring-boron trifluoride complex and/or silica phosphide The weight percentage of compound is very little, is formed by the characteristics of SEI films cannot have both compactness and stability, can not be effectively The side reaction between active material and electrolyte is prevented, makes cycle performance of the battery under high temperature and room temperature that cannot effectively change It is kind.
In battery 6#, battery 8#, battery 9#In, nitrogen heterocyclic ring-boron trifluoride complex and/or silica phosphide chemical combination Object content is excessive, excessive nitrogen heterocyclic ring-boron trifluoride complex and silica phosphoric ester compound residual in the electrolytic solution, after Continue and reacted in pole piece, interface impedance is caused to become larger, deteriorates cycle performance of the battery under high temperature and room temperature.
In battery 1~8, the content of silica phosphoric ester compound is 2%, and the nitrogen-containing hetero that content is 0.05%~10% is added Ring-boron trifluoride complex can form SEI films that are fine and close, stablizing, prevent the pair between active material and electrolyte anti- It answers, there is higher capacity retention ratio after so that battery is recycled under high temperature and room temperature.
In battery 4 and battery 9~14, the content of nitrogen heterocyclic ring-boron trifluoride complex is 2%, and addition contains Amount is 0.1%~10% silica phosphoric ester compound, can form SEI films that are fine and close, stablizing, prevent active material and electrolyte Between side reaction, after so that battery is recycled under high temperature and room temperature have higher capacity retention ratio.Likewise, to battery 15~ Capacity retention ratio after 36 cycles is analyzed, and has analysis result same as described above.
In from the above as can be seen that in the electrolyte nitrogen heterocyclic ring-boron trifluoride complex and silica simultaneously When phosphoric ester compound, the capacity retention ratio after battery recycles under high temperature and room temperature is improved, battery has under high temperature and room temperature Excellent cycle performance.
In summary：In the electrolytic solution, when the content of nitrogen heterocyclic ring-boron trifluoride complex is too small or it is excessive with And when silica phosphoric ester compound content is too small or excessive, fine and close, stablize, the preferable SEI films of interface performance cannot be all formed, The battery of the good cycle under high temperature and room temperature can not be obtained simultaneously.When electrolyte contains 0.05%~10% nitrogen-containing hetero Ring-boron trifluoride complex and 0.1%~10% silica phosphoric ester compound, especially contain containing 0.1%~4.0% Azacyclo--boron trifluoride complex and 1%~4% silica phosphoric ester compound, cycle of the battery under high temperature and room temperature Performance is more excellent.
The announcement of book according to the above description, the application those skilled in the art can also carry out the above embodiment Change and modification appropriate.Therefore, the application is not limited to specific implementation mode disclosed and described above, to the application's Some modifications and changes should also be as falling into the protection domain of claims hereof.

Claims (10)

1. a kind of electrolyte, which is characterized in that including organic solvent, lithium salts and additive, the additive includes nitrogen heterocyclic ring- Boron trifluoride complex and silica phosphoric ester compound, wherein the nitrogen heterocyclic ring be selected from containing pyridyl group heterocycle, containing rattling away The heterocycle of piperazine base, the heterocycle containing pyrimidine radicals, the heterocycle containing pyrazinyl, the heterocycle containing pyrrole radicals, pyrazolyl containing heterocycle and contain miaow At least one of heterocycle of oxazolyl.
2. electrolyte according to claim 1, which is characterized in that the nitrogen heterocyclic ring-boron trifluoride complex is Selected from least one of following formula I, formula II, formula III, formula IV, VII compound represented of formula V, formula VI and formula：
Wherein, R11、R12、R13、R14、R15、R21、R22、R23、R24、R31、R32、R33、R34、R41、R42、R43、R44、R51、R52、R53、 R54、R61、R62、R63、R71、R72、R73It is each independently selected from hydrogen atom, halogen atom, the alkyl that carbon atom number is 1~20, carbon Alkoxy that aryl that alkenyl that atomicity is 2~20, carbon atom number are 6~26, carbon atom number are 1~20, carbon atom number 6 Alkenyl that alkyl that~26 aryloxy group and above-mentioned carbon atom number are 1~20, carbon atom number are 2~20, carbon atom number 6 The aryloxy group that alkoxy that~26 aryl, carbon atom number are 1~20, carbon atom number are 6~26 is by halogen atom, sulfonic group or sulphur Acyl group substitution is formed by one kind in group, wherein halogen atom F, Cl, Br, and
R11、R12、R13、R14、R15At least one of be halogen atom, R21、R22、R23、R24At least one of be halogen atom, R31、 R32、R33、R34At least one of be halogen atom, R41、R42、R43、R44At least one of be halogen atom, R51、R52、R53、R54 At least one of be halogen atom, R61、R62、R63At least one of be halogen atom, R71、R72、R73At least one of be halogen Atom, wherein the halogen atom is F, Cl.
3. electrolyte according to claim 2, which is characterized in that R11、R12、R13、R14、R15、R21、R22、R23、R24、R31、 R32、R33、R34、R41、R42、R43、R44、R51、R52、R53、R54、R61、R62、R63、R71、R72、R73It is each independently selected from F, carbon Alkenyl that naphthenic base that chain-like alkyl that atomicity is 1~4, carbon atom number are 5~7, carbon atom number are 2~5, carbon atom number are Aryloxy group that alkoxy that 6~9 aryl, carbon atom number are 1~4, carbon atom are 6~10, carbon atom number be 1~4 it is halogenated Halogenated alkenyl that halogenated cycloalkyl that chain-like alkyl, carbon atom number are 5~7, carbon atom number are 2~5, carbon atom are 6~10 One kind in the haloaryloxy that the halogenated alkoxy and carbon atom that halogenated aryl, carbon atom number are 1~4 are 6~10.
4. electrolyte according to claim 1, which is characterized in that the nitrogen heterocyclic ring-boron trifluoride complex is Selected from least one of following complexes：
5. electrolyte according to claim 1, which is characterized in that the silica phosphoric ester compound be selected from following formula VIII, At least one of Ⅸ compound represented of formula：
Wherein, R81、R82、R83、R84、R85、R86、R87、R88、R89、R91、R92、R93、R94、R95、R96、R97、R98、R99It is respectively independent Ground be selected from hydrogen atom, halogen atom, carbon atom number be 1~10 alkyl, carbon atom number be 2~10 alkenyl, carbon atom number 6 Alkoxy that halogenated alkyl that~10 aryl, carbon atom number are 1~10, carbon atom number are 1~10, carbon atom number are 6~10 Aryloxy group, carbon atom number be 1~10 halogenated alkyl, carbon atom number be 6~10 halogenated aryl, carbon atom number be 1~10 Halogenated alkoxy and carbon atom number be 6~10 haloaryloxy in one kind, wherein halogen atom F, Cl, Br, and R81、R82、R83、R84、R85、R86、R87、R88And R89All same, R91、R92、R93、R94、R95、R96、R97、R98And R99Homogeneously Together.
6. electrolyte according to claim 1, which is characterized in that the silica phosphoric ester compound is selected from following compounds At least one of：
7. electrolyte according to claim 1, which is characterized in that the nitrogen heterocyclic ring-boron trifluoride complex Content is the 0.05%~10% of the total weight of electrolyte, and/or,
The content of the silica phosphoric ester compound is the 0.1%~10% of the total weight of electrolyte.
8. electrolyte according to claim 1, which is characterized in that the organic solvent is selected from ethylene carbonate, carbonic acid Acrylic ester, butylene, fluorinated ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, Methyl propyl carbonate, ethyl propyl carbonic acid ester, 1,4- butyrolactone, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate and butyric acid At least one of ethyl ester.
9. electrolyte according to claim 1, which is characterized in that
The lithium salts be selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro oxalic acid lithium phosphate, LiN(SO2RF)2、LiN(SO2F)(SO2RF), double trifluoromethanesulfonimide lithiums, bis- (fluorine sulphonyl) imine lithiums, double oxalic acid boric acid At least one of lithium, difluorine oxalic acid boracic acid lithium, wherein RF=-CnF2n+1, n be 1~10 integer；And/or
A concentration of 0.5mol L of the lithium salts in the electrolytic solution-1~2mol L-1。
10. a kind of lithium ion battery, which is characterized in that include the positive plate containing positive electrode active materials, contain negative electrode active material Negative plate, isolation film and the electrolyte according to any one of claims 1 to 9 of material.
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