CN106252724A - Additive, preparation method thereof and lithium ion battery containing additive - Google Patents

Additive, preparation method thereof and lithium ion battery containing additive Download PDF

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Publication number
CN106252724A
CN106252724A CN201610751307.4A CN201610751307A CN106252724A CN 106252724 A CN106252724 A CN 106252724A CN 201610751307 A CN201610751307 A CN 201610751307A CN 106252724 A CN106252724 A CN 106252724A
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additive
lithium ion
ion battery
unsubstituted
battery
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CN201610751307.4A
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Inventor
余林峰
蒋治亿
许金梅
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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Priority to CN201610751307.4A priority Critical patent/CN106252724A/en
Publication of CN106252724A publication Critical patent/CN106252724A/en
Priority to PCT/CN2017/093186 priority patent/WO2018040763A1/en
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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
    • H01M10/052—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
    • H01M10/0567—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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The application relates to an additive, in particular to at least one additive selected from compounds shown in a formula I. The application also relates to a preparation method of the additive and a lithium ion battery containing the additive. The additive disclosed by the application is beneficial to forming a stable SEI film on the surface of an electrode of a lithium ion battery, preventing the co-intercalation of solvent molecules and inhibiting the further reaction of a negative electrode and an electrolyte. And a surface film can be formed on the surface of the electrode to isolate air, so that a stronger flame-retardant effect is exerted, and the rate capability, the cycle performance and the safety of the battery are improved.

Description

A kind of additive, its preparation method and the lithium ion battery containing described additive
Technical field
The application relates to field of lithium ion battery material, specifically, relates to a kind of additive, its preparation method and containing State the lithium ion battery of additive.
Background technology
In lithium ion battery, add a small amount of Cucumber, the performance of battery can be significantly improved, these a small amount of materials It is referred to as additive.Additive has become the focus in current Study on Li-ion batteries field.
In lithium ion battery charge and discharge process, there are a series of electrochemical reactions with electrolyte in electrode material, generates Cover the passivation layer in electrode material surface, i.e. solid electrolyte interface (SEI) film.Add in lithium ion battery is a small amount of Additive preferentially can react at electrode surface, improves SEI membrane component and structure.Excellent SEI film allows lithium ion freely Passing through, solvent molecule cannot pass through, and stops the further reaction of electrolyte and electrode material, and then improves the high rate performance of battery And cycle performance.
Lithium ion battery is when overcharging or be heated, and inside battery easily occurs the irreversible oxidation of electrolyte to decompose or heat point Solve, produce a large amount of imflammable gas, easily burn, and set off an explosion.The combustion reaction of electrolyte is typically hydroxyl free radical The chain reaction participated in, therefore adds additive in lithium ion battery, and additive discharges free radical in time-division solution of being heated, with The hydroperoxyl radical of capture high reaction activity, can effectively reduce the combustibility of electrolyte, promotes the safety of lithium ion battery.
In consideration of it, special, the application is proposed.
Summary of the invention
The primary goal of the invention of the application is to propose a kind of additive.
Second goal of the invention of the application is to propose the preparation method of described additive.
3rd goal of the invention of the application is to propose the lithium ion battery containing described additive.
In order to complete the purpose of the application, the technical scheme of employing is:
The application relates to a kind of lithium ion battery additive, described additive in compound shown in formula I at least A kind of:
Wherein, described R1And R2It is each independently selected from substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6 ～C26Aryl, substituted or unsubstituted C5～C22Heterocyclic base, substituent group is halogen；It is preferably C1～C8Alkyl, more preferably C1~ C3Alkyl.
Preferably, the structural formula of described additive such as Formulas I1Shown in:
The application further relates to the method preparing described additive, and described method at least includes lithium iodide and as shown in Formula II Phosphotriester prepares compound shown in formula I by substitution reaction,
Wherein, R3Selected from substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C26Aryl, replace or not Substituted C5～C22Heterocyclic base, substituent group is halogen.
Preferably, described reaction is carried out in inert gas atmosphere, and reaction temperature is 20 DEG C～30 DEG C, and the response time is 22 ～26 hours, lithium iodide is 0.9～1.1:0.9～1.1 with the mol ratio of triethyl phosphate.
Preferably, in inert gas atmosphere, in solvent, add lithium iodide and triethyl phosphate reacts, obtain formula I1Shown additive.
Preferably, described solvent is acetone, and lithium iodide is 1:1 with the mol ratio of triethyl phosphate, and reaction temperature is room temperature, Time is 24 hours.
The application further relates to a kind of lithium ion battery, and described lithium ion battery includes positive plate, negative plate, barrier film and electricity Solve liquid, containing electrolyte, organic solvent and additive described herein in described electrolyte.
Preferably, described additive mass content in the electrolytic solution is 0.1～0.5%.
The technical scheme of the application at least has a following beneficial effect:
The additive that the application relates to contributes to forming stable SEI film at the electrode surface of lithium ion battery, stops molten The common embedding of agent molecule, suppression negative pole reacts with the further of electrolyte.Meanwhile, the addition of additive can improve SEI film Pattern and composition, promote and participate in component LixPOyFzFormation, reduce SEI membrane impedance, reduce polarization, reduce the disappearing of lithium ion Consumption.Due to the additive of the application improvement result to SEI film, add the lithium ion battery high rate performance of this additive, circulation Performance gets a promotion.
In lithium ion battery, electrolyte, in the case of being heated, is susceptible to the chain reaction of hydroxyl free radical.Pass through Acupuncture experiment embodies the safety of the application additive.Further, the additive of the application vaporizes decomposition when being heated, release Going out phosphorous free radical, this phosphorous free radical has the ability of hydroperoxyl radical in capture system, thus terminates the continuation of chain reaction Carry out, stop burning or the blast of organic solvent, promote the safety of lithium ion battery.
The additive of the present invention adds in lithium ion battery, and when Mars or burning occurs in battery, phosphorus compound decomposes raw Become the noninflammability liquid film of phosphoric acid.Meanwhile, phosphoric acid is dehydrated generation Metaphosphoric acid further, and Metaphosphoric acid is polymerized the poly-inclined phosphorus of generation further Acid.In this process, the cover layer that not only phosphoric acid generates plays blanketing effect, and the poly-Metaphosphoric acid owing to generating is strong Acid, is the strongest dehydrant, makes polymer be dehydrated and carbonization, changes the pattern of polymer combustion process and formed on its surface Skin covering of the surface is to completely cut off air, thus plays higher flame retardant effect, promotes the safety of lithium ion battery.
Detailed description of the invention
Below in conjunction with specific embodiment, the application is expanded on further.Should be understood that these embodiments are merely to illustrate the application Rather than restriction scope of the present application.
The application relates to a kind of lithium ion battery additive, described additive in compound shown in formula I at least A kind of:
Wherein, R1And R2It is each independently selected from substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C26 Aryl, substituted or unsubstituted C5～C22Heterocyclic base, substituent group is halogen.
As a kind of improvement of the application lithium ion battery additive, R1And R2It is each independently selected from C1～C8Alkyl, more It is preferably C1～C3Alkyl.
As a kind of improvement of the application lithium ion battery additive, R1And R2For identical substituent group.
In the structure above of the application:
For substituted or unsubstituted C1～C12Alkyl, alkyl can be chain-like alkyl, it is possible to for cycloalkyl, be positioned at cycloalkyl Ring hydrogen can be replaced by alkyl, in described alkyl, the preferred lower limit of carbon number is 1,2,3,4, preferred higher limit is 3,4,5,6,8,10,12.Preferably, the alkyl selecting carbon number to be 1～8, it is further preferred that selecting carbon number is 1 ～the chain-like alkyl of 6, carbon number is the cycloalkyl of 3～8, it is further preferred that the chain selecting carbon number to be 1～3 Alkyl.As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding Base, the tert-butyl group, n-pentyl, isopentyl, neopentyl, hexyl, 2-Methyl pentyl, 3-Methyl pentyl, 1,1,2-trimethyl-the third Base, 3,3 ,-dimethyl-butyl, heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl, different heptyl, octyl group, nonyl Base, decyl.
For the aryl that carbon number is 6～26, it is preferable that the aryl selecting carbon number to be 6～16, further preferably Ground, the aryl selecting carbon number to be 6～14, it is further preferred that the aryl selecting carbon number to be 6～9.As aryl Example, specifically can enumerate: phenyl, benzyl, xenyl, p-methylphenyl, o-tolyl, a tolyl.
Carbon number is the heterocyclic base of 5～22, is selected from: furyl, thienyl, pyrrole radicals, thiazolyl, imidazole radicals, pyrrole Piperidinyl, pyrazinyl, pyrimidine radicals, pyridazinyl, indyl, quinolyl etc..
As a kind of improvement of the application lithium ion battery additive, work as R1And R2During for ethyl, the structure of described additive Formula such as Formulas I1Shown in:
Shown additive molecule is phosphate ester structure.Wherein, two phosphorus oxygen keys of phosphate ester are connected with two ethyls respectively Connecing, the 3rd phosphorus oxygen key becomes salt with lithium ion.
As a kind of improvement of the application lithium ion battery additive, the secondary cell additive of the application be further selected from At least one in lower compound:
In order to realize second purpose of the application, the additive of the application is anti-by replacing with phosphotriester by lithium iodide Should prepare, reaction equation is as follows:
Wherein, R3Selected from substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C26Aryl, replace or not Substituted C5～C22Heterocyclic base, substituent group is halogen.
Preferably, R1、R2、R3For identical substituent group.
The additive of the application, can use said method to be prepared by changing the chemical structural formula of initial feed.
As a kind of improvement of the application preparation method, the actual conditions of reaction is: reaction is entered in inert gas atmosphere OK, reaction temperature is 20 DEG C～30 DEG C, and the response time is 22～26 hours, preferably 24 hours, lithium iodide and triethyl phosphate Mol ratio is 0.9～1.1:0.9～1.1.
As a kind of improvement of the application preparation method, described such as Formulas I1The preparation method of shown additive, at least includes:
In inert gas atmosphere, in solvent, add lithium iodide and triethyl phosphate reacts, obtain Formulas I1Shown in Compound, its reaction equation is as follows:
Wherein, solvent is acetone, and the mol ratio of lithium iodide and triethyl phosphate is 1:1, and reaction temperature is room temperature, and the time is 24 hours.
In order to realize the 3rd purpose of the application, the application provides a kind of lithium ion battery, and lithium ion battery contains positive pole Sheet, negative plate, isolating membrane and electrolyte, containing additive provided herein in electrolyte.
As a kind of improvement of the application lithium ion battery, additive mass content in the electrolytic solution be 0.2～ 0.5%.As additive level is too low, then the electrode surface at lithium ion battery is not effectively form stable SEI film, it is impossible to Suppression negative pole reacts with the further of electrolyte effectively.Meanwhile, the addition of additive is too low, pattern and the composition to SEI film Improve effect the most notable, it is impossible to be effectively reduced SEI membrane impedance.Too low additive level, for the improvement of battery security Effect is the most inconspicuous.As additive level is too high, then the electrode surface at lithium ion battery is easily formed blocked up SEI film, makes SEI Membrane impedance increases.
Containing electrolyte, organic solvent and additive in electrolyte, wherein:
Electrolyte selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, tetrafluoro oxalic acid lithium phosphate, LiN(SO2Rf)2、LiN(SO2F)(SO2Rf), double trifluoromethanesulfonimide lithium, double (fluorine sulphonyl) imine lithium, double oxalic acid boric acid At least one in lithium, difluorine oxalic acid boracic acid lithium, wherein, Rf=CnF2n+1, n is the integer of 1～10, preferably lithium hexafluoro phosphate or LiN(SO2Rf)2。
Organic solvent is selected from carbonic ester, sulfuric ester, sulfone class, nitrile compounds etc., and carbonic ester is selected from cyclic carbonate, chain Carbonic ester；Sulfuric ester is selected from cyclic sulfates, chain sulfuric ester etc..
Specifically it is selected from following organic solvent and is not limited to this: ethylene carbonate, propylene carbonate, dimethyl carbonate, carbon Diethyl phthalate, dipropyl carbonate, Ethyl methyl carbonate, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, methyl butyrate, At least one in ethyl acetate, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, methyl sulfide.
Preferably, described lithium ion battery is coiled lithium ion battery or stack type lithium ion battery.
Embodiment 1～7
The structural formula of the additive of embodiment 1～7 is as by shown in Formulas I, and it passes through the phosphotriester shown in Formula II and iodate Lithium reaction prepares.In phosphotriester shown in Formula II, substituent group specifically chosen as shown in table 1, the interpolation prepared Substituent group in agent is as shown in table 2:
Table 1
Phosphotriester shown in Formula II R1 R2 R3
II1 Ethyl Ethyl Ethyl
II2 N-pro-pyl N-pro-pyl N-pro-pyl
II3 Isopropyl Isopropyl Isopropyl
II4 Normal-butyl Normal-butyl Normal-butyl
II5 Ethyl N-pro-pyl Ethyl
II6 N-hexyl N-hexyl N-hexyl
II7 Phenyl Phenyl Phenyl
Table 2
Specifically, Formulas I1The preparation method of shown additive is:
Step 1): in the glove box of argon atmosphere, in reaction vessel, add 134g lithium iodide, and add 1L acetone. Then, 134g triethyl phosphate is added dropwise in reaction system.
Step 2): reaction system stirs 24 hours at normal temperatures.After reaction terminates, reacting coarse product is filtered, obtain thick Product solid.
Step 3): the solid after filtering is transferred in reaction vessel, adds acetone, stirs 1 hour, to dissolve and to remove Impurity.Again filter crude product, to be further purified.
Step 4): repeat step 3 twice, use vacuum drying oven desciccate, obtain pure lithium ion battery additive Compound 138g, productivity 86%.
The chemical formula of products therefrom and quality composition are as follows:
C4H10O4PLi (160.05g/mol): C=30.02%；H=6.30%；O=39.99%；P=19.35%；Li =4.34%.
The nuclear-magnetism spectrum of described compound is as follows:
1H NMR(500MHz,CDCl3):δ4.11(4H),1.35(6H).
31P NMR(500MHz,D2O):δ2.97.
Additive in the application other embodiments, also by said method, selects different raw materials to be prepared.
By the additive application for preparing in lithium ion battery, battery it is prepared as follows:
By quality proportioning cobalt nickel lithium manganate ternary material: binding agent PVDF: conductive agent Super P=90:5:5 prepare lithium from Sub-cell cathode pole piece.By quality proportioning graphite material: binding agent PVDF: conductive agent Super P=92:5:3 prepares lithium ion Galvanic anode pole piece.By quality proportioning ethylene carbonate: dimethyl carbonate=4:6 prepares electrolyte, wherein lithium hexafluoro phosphate 1.0mol/L, adds this electrolysis by lithium ion battery additive prepared by embodiment 1～7 by the mass percent of 0.1～0.5% In liquid.Electrolyte is assembled into lithium ion battery respectively together with cathode sheet, anode pole piece, polyethylene diagrams.
Comparative example 1～3:
Comparative example 1: ethylene carbonate in mass ratio: dimethyl carbonate=4:6 prepares electrolyte, wherein hexafluoro phosphorus Acid lithium 1.0mol/L, does not use additive, and the preparation process of other battery is same as in Example 1.
Comparative example 2: ethylene carbonate in mass ratio: dimethyl carbonate=4:6 prepares electrolyte, wherein hexafluoro phosphorus Acid lithium 1.0mol/L, adds the triphenyl phosphite of 0.2% in this electrolyte.The preparation process of other battery and embodiment 1 is identical.
Comparative example 3: ethylene carbonate in mass ratio: dimethyl carbonate=4:6 prepares electrolyte, wherein hexafluoro phosphorus Acid lithium 1.0mol/L, adds phosphate ester shown in the formula III of 0.2% in this electrolyte.The preparation process of other battery and enforcement Example 1 is identical.
In the electrolyte of embodiment and comparative example, the concrete ratio of each composition is as shown in table 3.
Table 3
Electrolyte Organic solvent Additive
Battery 1 Electrolyte 1 1M LiPF6 EC:DMC=4:6 0.2%I1
Battery 2 Electrolyte 1 1M LiPF6 EC:DMC=4:6 0.1%I1
Battery 3 Electrolyte 1 1M LiPF6 EC:DMC=4:6 0.3%I1
Battery 4 Electrolyte 4 1M LiPF6 EC:DMC=4:6 0.5%I1
Battery 5 Electrolyte 5 1M LiPF6 EC:DMC=4:6 0.2%I2
Battery 6 Electrolyte 6 1M LiPF6 EC:DMC=4:6 0.2%I3
Battery 7 Electrolyte 7 1M LiPF6 EC:DMC=4:6 0.2%I4
Battery D1 Electrolyte D1 1M LiPF6 EC:DMC=4:6 —
Battery D2 Electrolyte D2 1M LiPF6 EC:DMC=4:6 0.2% triphenyl phosphite
Battery D3 Electrolyte D3 1M LiPF6 EC:DMC=4:6 0.2% phosphate ester
Wherein, "-" represents and is not added with any material.
Testing example and comparative example prepare the high rate performance of battery, cycle life and safety of acupuncture, and detection method is such as Under:
Battery high rate performance is tested, carry out in accordance with the following steps:
A) battery with 3C multiplying power electric current constant-current charge to 4.2V time, turn constant-voltage charge, be down to 0.05C multiplying power to charging current Charging is stopped during electric current；
B) battery discharges to stopping during 2.8V with 3C multiplying power electric current constant-current discharge；
C) percentage ratio of discharge capacity of the cell and charging capacity is calculated.
Battery cycle life is tested, carry out in accordance with the following steps:
A) battery with 1C multiplying power electric current constant-current charge to 4.2V time, turn constant-voltage charge, be down to 0.05C multiplying power to charging current Charging is stopped during electric current；
B) battery discharges to stopping during 2.8V with 1C multiplying power electric current constant-current discharge；
C) repeat charge and discharge cycles to battery capacity be down to initial capacity 80% time stop test.
Battery impact testing, with reference to GB/T 31485-2015, carry out in accordance with the following steps:
A) battery with 1C multiplying power electric current constant-current charge to 4.2V time, turn constant-voltage charge, be down to 0.05C multiplying power to charging current Charging is stopped during electric current.
B) with the high temperature resistant draw point of diameter 5～8mm, with the speed of (25 ± 5) mm/s, from the side being perpendicular to accumulator plate To running through, running through position preferably near the geometric center in thorn face, draw point rests in accumulator；
C) observe 1 hour.
The data detected are as shown in table 4.
Table 4
High rate performance and cycle life test show, in embodiment 1～7,3C discharge capacity and the cycle life of battery are the highest In comparative example, illustrate that additive application that the application proposes is in lithium ion battery, it is possible to improve film-forming state and the group of SEI film Become, reduce the polarization of battery, promote high rate performance and the cycle life of battery.
Lancing test shows, in embodiment 1～7, battery blast the most on fire, illustrates the additive application that the application proposes In lithium ion battery, being more easy to vaporization when being heated and decompose, discharge phosphorous free radical, this phosphorous free radical has capture system The ability of middle hydroperoxyl radical, thus terminate proceeding of chain reaction, stops burning or the blast of organic solvent, promote lithium from The safety of sub-battery.
Although the application is open as above with preferred embodiment, but is not for limiting claim.Any this area skill Art personnel, on the premise of conceiving without departing from the application, can make some possible variations and amendment, therefore the application Protection domain should be defined in the range of standard with claim.

Claims (10)

1. an additive, it is characterised in that at least one in compound shown in formula I of described additive:
Wherein, described R1And R2It is each independently selected from substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C26 Aryl, substituted or unsubstituted C5～C22Heterocyclic base, substituent group is halogen.
Additive the most according to claim 1, it is characterised in that described R1And R2It is each independently selected from C1～C8Alkyl.
Additive the most according to claim 2, it is characterised in that described R1And R2It is each independently selected from C1～C3Alkyl.
Additive the most according to claim 1, it is characterised in that the structural formula of described additive such as Formulas I1Shown in:
5. prepare the method for additive as according to any one of claims 1 to 3 for one kind, it is characterised in that described method is at least Compound shown in formula I is prepared with the phosphotriester as shown in Formula II by substitution reaction including lithium iodide,
Wherein, R3Selected from substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C26Aryl, replaces or unsubstituted C5～C22Heterocyclic base, substituent group is halogen.
Method the most according to claim 5, it is characterised in that described reaction is carried out in inert gas atmosphere, reaction temperature Degree is 20 DEG C～30 DEG C, and the response time is 22～26 hours, and lithium iodide is 0.9～1.1:0.9 with the mol ratio of triethyl phosphate ～1.1.
Method the most according to claim 5, it is characterised in that in inert gas atmosphere, adds lithium iodide in solvent React with triethyl phosphate, obtain Formulas I1Shown additive.
Method the most according to claim 7, it is characterised in that described solvent is acetone, lithium iodide and triethyl phosphate Mol ratio is 1:1, and reaction temperature is room temperature, and the time is 24 hours.
9. a lithium ion battery, it is characterised in that described lithium ion battery includes positive plate, negative plate, barrier film and electrolysis Liquid, containing electrolyte, organic solvent and the additive according to any one of claims 1 to 3 in described electrolyte.
Battery the most according to claim 9, it is characterised in that described additive mass content in the electrolytic solution is 0.1 ～0.5%.
CN201610751307.4A 2016-08-29 2016-08-29 Additive, preparation method thereof and lithium ion battery containing additive Pending CN106252724A (en)

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WO2018040763A1 (en) * 2016-08-29 2018-03-08 宁德时代新能源科技股份有限公司 Additive, preparation method therefor and lithium ion battery containing same
CN109962294A (en) * 2019-03-20 2019-07-02 珠海市赛纬电子材料股份有限公司 A kind of nonaqueous lithium ion battery electrolyte and lithium ion battery
CN110048162A (en) * 2019-04-04 2019-07-23 李秀艳 High-voltage electrolyte additive, electrolyte and battery containing the additive
CN110112463A (en) * 2019-04-04 2019-08-09 李秀艳 A kind of electrolysis additive, high-voltage electrolyte and battery containing the additive
WO2021196427A1 (en) * 2020-03-30 2021-10-07 山东海容电源材料股份有限公司 Flame-retardant electrolyte for lithium-ion battery
CN113945853A (en) * 2021-08-04 2022-01-18 惠州锂威新能源科技有限公司 Method for detecting stability of battery SEI film
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