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CN106953118A - A kind of nonaqueous electrolytic solution and lithium ion battery for lithium ion battery - Google Patents

A kind of nonaqueous electrolytic solution and lithium ion battery for lithium ion battery Download PDF

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Publication number
CN106953118A
CN106953118A CN201611054855.8A CN201611054855A CN106953118A CN 106953118 A CN106953118 A CN 106953118A CN 201611054855 A CN201611054855 A CN 201611054855A CN 106953118 A CN106953118 A CN 106953118A
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electrolytic solution
nonaqueous electrolytic
compound
structural formula
alkyl
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CN106953118B (en
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石桥
胡时光
林雄贵
贠娇娇
俱龙龙
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Huizhou Capchem Chemicals Co Ltd
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Huizhou Capchem Chemicals Co Ltd
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Priority to PCT/CN2016/113649 priority patent/WO2018094843A1/en
Priority to EP16922345.0A priority patent/EP3547433A4/en
Priority to US16/316,621 priority patent/US11362370B2/en
Priority to JP2018564811A priority patent/JP6814821B2/en
Publication of CN106953118A publication Critical patent/CN106953118A/en
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Publication of CN106953118B publication Critical patent/CN106953118B/en
Priority to JP2020136214A priority patent/JP6963068B2/en
Priority to JP2021169184A priority patent/JP7208330B2/en
Priority to US17/735,109 priority patent/US11757132B2/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0567Liquid materials characterised by the additives
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0568Liquid materials characterised by the solutes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/0025Organic electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/0025Organic electrolyte
    • H01M2300/0028Organic electrolyte characterised by the solvent
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • 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

This application discloses a kind of nonaqueous electrolytic solution and lithium ion battery for lithium ion battery.The nonaqueous electrolytic solution of the application, including structural formula one the first compound at least one and structural formula two second compound at least one;In structural formula one, R1、R2It is independently selected from alkyl or fluoro alkyl that carbon number is 15, R1And R2In at least one be fluoro alkyl, at least two hydrogen are replaced by fluorine in fluoro alkyl, R in structural formula two3、R4、R5It is independently selected from saturated hydrocarbyl, unsaturated alkyl or halohydrocarbyl that carbon number is 15, R3、R4、R5In at least one be unsaturated alkyl.The nonaqueous electrolytic solution of the application, is acted synergistically by the first compound and second compound, had both improved high-voltage lithium ion batteries high temperature cyclic performance, be turn avoid negative terminal surface and is decomposed aerogenesis.And the first compound subparticipation cathode film formation reaction, improve cathode interface situation, ensure battery low temperature performance and high rate performance.

Description

A kind of nonaqueous electrolytic solution and lithium ion battery for lithium ion battery
Technical field
The application is related to lithium-ion battery electrolytes field, more particularly to a kind of non-aqueous solution electrolysis for lithium ion battery Liquid and lithium ion battery.
Background technology
Lithium ion battery because its have light weight, small volume, operating voltage height, energy density height, output power, without note The advantages of recalling effect and have extended cycle life, is not only widely used in the digital product such as mobile phone, notebook computer field, And it is also considered as one of electric motor car, the optimal selection of large-scale energy storage device.The electron numbers such as current smart mobile phone, panel computer Code product requires more and more higher to the energy density of battery so that commercial li-ion battery, which is difficult to meet, to be required.Improve lithium ion The charging voltage of battery is to improve one of most effective approach of battery energy density.
Current lithium-ion battery electrolytes use carbonic ester as solvent, when the charging voltage of lithium ion battery is more than 4.2V, carbonate solvent can be oxidized on positive electrode surface and decompose, and produce gas and other catabolites.On the one hand, produce Gas can cause battery bulging, bring potential safety hazard to battery, on the other hand, its catabolite can substantially increase the resistance of battery It is anti-, so as to reduce each performance of battery.Therefore, for high-voltage lithium ion batteries, it is necessary to which exploitation aoxidizes electricity than carbonic ester The higher solvent in position.The electricity of a kind of fluorine-containing substituted carboxylate and phosphate is disclosed in Chinese patent application CN104704657A Liquid is solved, the high temperature cyclic performance of high-voltage lithium ion batteries can be improved.But applicants have discovered that, alpha-fluorocarboxylate ester and Carbon anode The compatible performance of material is bad, in battery charging process, and decomposition can be reduced in negative terminal surface and produces substantial amounts of gas, this Battery brings great potential safety hazard, while substantially deteriorating the performance of battery.Although phosphate can suppress fluorine to a certain degree For the decomposition of carboxylate, but high temperature circulation and high-temperature storage performance need further raising.
The content of the invention
The purpose of the application is to provide a kind of new non-aqueous electrolyte for lithium ion cell and the lithium ion using the electrolyte Battery.
To achieve these goals, the application employs following technical scheme:
The one side of the application discloses a kind of nonaqueous electrolytic solution for lithium ion battery, including selected from the institute of structural formula one At least one and in the second compound shown in structural formula two at least one in the first compound shown;
The R of structural formula one1COOR2,
In structural formula one, R1、R2It is independently selected from alkyl or fluoro alkyl that carbon number is 1-5, and R1And R2In At least one is fluoro alkyl;At least two hydrogen are replaced by fluorine in fluoro alkyl;
Structural formula two
In structural formula two, R3、R4、R5Be independently selected from carbon number be 1-5 saturated hydrocarbyl, unsaturated alkyl or Halohydrocarbyl, and R3、R4、R5In at least one be unsaturated alkyl.
It should be noted that the nonaqueous electrolytic solution of the application, it is it is critical that with the first compound shown in structural formula one Used cooperatively with the second compound shown in structural formula two, both act synergistically.Wherein, the first compound is due to oxidizing potential Height, can reduce decomposition reaction of the electrolyte on high-voltage anode material surface, but the first compound can be decomposed in negative terminal surface, So as to produce substantial amounts of gas, potential safety hazard is brought;Second compound in molecular structure due to containing unsaturated bond, in lithium ion During battery initial charge, polymerisation formation passivating film, but the passivation membrane impedance can occur on positive and negative pole material surface It is larger, reduce the low temperature performance and high rate performance of battery.The application makes the first compound and second compound simultaneously Used time, because preferentially in negative terminal surface polymerisation formation passivating film can occur for second compound, it is suppressed that the first compound In the decomposition reaction of negative terminal surface, so as to inhibit lithium ion battery in charging process because structural formula one is decomposed in negative terminal surface And aerogenesis phenomenon.In addition, the first compound also can subparticipation cathode film formation reaction, improve cathode interface situation.The application First compound is used together with second compound, both coordinative roles, generate both be used alone do not have it is special Effect.
In the application, the first compound and second compound are used simultaneously;Wherein, the first compound amount can be in usual amounts Addition, for example, it is preferable in the case of, the first compound amount accounts for the 10%-80% of nonaqueous electrolytic solution gross weight.Second compound, Its consumption for example accounts for the 0.8-1.2% of nonaqueous electrolytic solution gross weight according to the conventional amount used of additive in nonaqueous electrolytic solution Left and right, typically constitutes from the 0.01%-5% of nonaqueous electrolytic solution gross weight.First compound, can be separately as nonaqueous electrolytic solution Non-aqueous organic solvent use, can also be used in mixed way, be used in mixed way with other organic solvents with other machine solvents that common are It will be discussed in detail in follow-up scheme.
It should also be noted that, the key of the application is to have used the first compound and second to change in nonaqueous electrolytic solution Compound, as other conventional constituents, such as lithium salts may be referred to existing nonaqueous electrolytic solution, or even in nonaqueous electrolytic solution also Other conventional reagents can be added, to increase corresponding function, are not specifically limited herein.But, in the preferred of the application In scheme, in order to reach more preferable effect, spy has been carried out to the other organic solvents, lithium salts and other reagents of non-aqueous organic solvent Do not limit, this will be discussed in detail in follow-up scheme.
It is preferred that, in structural formula one, carbon number includes but are not limited to methyl, ethyl, propyl group, second for 1-5 alkyl Alkenyl, pi-allyl, 3- cyclobutenyls, isobutenyl, 4- pentenyls, acetenyl, propargyl, 3- butynyls, the propinyl of 1- methyl -2; Fluoro alkyl includes but are not limited to difluoromethyl, trifluoromethyl, the fluoro ethyls of 2,2- bis-, 2,2,2- trifluoroethyls, 3,3- difluoros Propyl group, 3,3,3- trifluoro propyls, hexafluoro isopropyl;In structural formula two, carbon number includes but not only limited for 1-5 saturated hydrocarbyl In methyl, ethyl, propyl group;Carbon number includes but are not limited to vinyl, pi-allyl, 3- butylene for 1-5 unsaturated alkyl Base, isobutenyl, 4- pentenyls, acetenyl, propargyl, 3- butynyls, the propinyl of 1- methyl -2;Carbon number is 1-5 halogen Difluoromethyl, trifluoromethyl, the fluoro ethyls of 2,2- bis-, 2,2,2- trifluoroethyls, 3,3- difluoros third are included but are not limited to for alkyl Base, 3,3,3- trifluoro propyls, hexafluoro isopropyl.
It is preferred that, the first compound is selected from H3CCOOCH2CF2H (being abbreviated as DFEA), H3CH2CCOOCH2CF2H (is abbreviated as DFEP)、HF2CH2CCOOCH3(being abbreviated as MDFP), HF2CH2CCOOCH2CH3(being abbreviated as EDFP), HF2CH2CH2CCOOCH2CH3 (being abbreviated as EDFB), H3CCOOCH2CH2CF2H (being abbreviated as DFPA), H3CH2CCOOCH2CH2CF2H (being abbreviated as DFPP), CH3COOCH2CF3(being abbreviated as TFEA), HCOOCH2CHF2(being abbreviated as DFEF), HCOOCH2CF3、CH3COOCH2CF2CF2H (abbreviations For TFPA).
It is preferred that, second compound is selected from tricresyl phosphate alkynes propyl ester, dipropargyl methyl phosphorodithioate, dipropargyl ethyl phosphonic acid Ester, dipropargyl propyl phosphate, dipropargyl trifluoromethyl phosphate, dipropargyl 2,2,2- trifluoroethyls phosphate, two Propargyl 3,3,3- trifluoro propyls phosphate, dipropargyl hexafluoro isopropyl phosphate, TAP, diallyl methyl Phosphate, diallyl ethyl phosphonic acid ester, diallyl propyl phosphate, diallyl trifluoromethyl phosphate, diallyl In 2,2,2- trifluoroethyls phosphate, diallyl 3,3,3- trifluoro propyls phosphate or diallyl hexafluoro isopropyl phosphate At least one.
It is preferred that, unsaturated cyclic carbonic ester, unsaturated acid anhydride, cyclic sulfates, ring-type are also included in nonaqueous electrolytic solution One or more in sultones, sulfone class.
Unsaturated cyclic carbonic ester is included in vinylene carbonate (abbreviation VC), vinylethylene carbonate (abbreviation VEC) It is at least one;
It is preferred that, ring-type sultones includes PS (abbreviation 1,3-PS), (abbreviation of Isosorbide-5-Nitrae-butane sultone BS), at least one in 1,3- propene sultones (abbreviation PST) and methane-disulfonic acid methylene ester (abbreviation MMDS).
It is preferred that, unsaturated acid anhydride includes succinic anhydride (abbreviation SA), maleic anhydride (abbreviation MA) and 2- citraconic acids At least one in acid anhydride (CA).
It is preferred that, cyclic sulfates include one kind in sulfuric acid vinyl ester (abbreviation DTD) and sulfuric acid propylene (abbreviation TS) Or two kinds.
It is preferred that, sulfone class includes sulfolane (abbreviation SL).
It should be noted that vinylene carbonate (abbreviation VC), vinylethylene carbonate (abbreviation VEC), fluoro ethylene Alkene ester (abbreviation FEC), or PS (abbreviation 1,3PS), Isosorbide-5-Nitrae-butane sultone (abbreviation BS), 1,3- propylene sulphurs Lactone (abbreviation PST), methane-disulfonic acid methylene ester (abbreviation MMDS), succinic anhydride (abbreviation SA), maleic anhydride (abbreviation MA), 2- Methyl maleic anhydride (abbreviation CA), sulfuric acid vinyl ester (abbreviation DTD), sulfuric acid propylene (abbreviation TS), sulfolane (abbreviation SL) and GBL (abbreviation GBL), these are all it has been reported that the conventional reagent for nonaqueous electrolytic solution crossed, wherein some examinations Agent, you can using as additive, can also be as solvent, such as FEC, when its amount ratio is larger, it is considered to be non-aqueous organic molten Agent, its amount ratio is considered as additive when smaller.For example, in the present invention, it is preferred in the case of, VC consumptions account for nonaqueous electrolytic solution The 0.1%-4% of gross weight, more preferably 0.5-1.5%.VEC consumptions account for the 0.1%-3% of nonaqueous electrolytic solution gross weight, More preferably 0.2-1.5%.1,3-PS consumption accounts for the 0.1%-10% of nonaqueous electrolytic solution gross weight, more preferably 1- 3%.BS consumptions account for the 0.1%-10% of nonaqueous electrolytic solution gross weight, more preferably 1-3%.PST consumptions account for non-aqueous solution electrolysis The 0.1%-3% of liquid gross weight, more preferably 0.5-2%.MMDS consumptions account for the 0.1%- of nonaqueous electrolytic solution gross weight 4%, more preferably 0.5-2%.SA consumptions account for the 0.1%-4% of nonaqueous electrolytic solution gross weight, more preferably 0.5- 2%.MA consumptions account for the 0.1%-4% of nonaqueous electrolytic solution gross weight, more preferably 0.5-2%.CA consumptions account for non-aqueous solution electrolysis The 0.1%-4% of liquid gross weight, more preferably 0.5-2%.DTD consumptions account for the 0.1%-5% of nonaqueous electrolytic solution gross weight, More preferably 0.5-3%.TS consumptions account for the 0.1%-4% of nonaqueous electrolytic solution gross weight, more preferably 0.5-3%. SL consumptions account for the 0.1%-30% of nonaqueous electrolytic solution gross weight, more preferably 2-15%.It is total that GBL consumptions account for nonaqueous electrolytic solution The 0.1%-30% of weight, more preferably 2-15%.
It is preferred that, nonaqueous electrolytic solution is also included selected from ethylene carbonate, fluorinated ethylene carbonate (abbreviation FEC), carbonic acid third At least one in alkene ester, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate.It contains Amount can change interior in a big way, and under preferable case, its content accounts for the 1%-40% of nonaqueous electrolytic solution gross weight.It is appreciated that , as a variety of in containing above-mentioned substance, above-mentioned content range is the total content proportion of above-mentioned many kinds of substance.
It is furthermore preferred that nonaqueous electrolytic solution is also included in ethylene carbonate, fluorinated ethylene carbonate and propene carbonate extremely Few one kind.
The another side of the application discloses the nonaqueous electrolytic solution of the application answering in lithium ion battery or energy-storage capacitor With.
The another side of the application discloses a kind of lithium ion battery, including positive pole, negative pole, is placed between positive pole and negative pole Barrier film, and electrolyte, wherein, electrolyte is the non-aqueous electrolyte for lithium ion cell of the application.
It is appreciated that the lithium ion battery of the application, its key is the nonaqueous electrolytic solution for employing the application so that Its both positive and negative polarity surface forms passivating film, so as to effectively suppress decomposition reaction of the electrolyte on both positive and negative polarity surface, suppresses positive electrode It is destructurized, analysis lithium phenomenon is reduced, the high temperature performance and high rate performance of battery has been ensured.As in lithium ion battery Other components, such as positive pole, negative pole and barrier film may be referred to conventional lithium ion battery.In the preferred scheme of the application, to positive pole Active material be particularly limited to.
It is preferred that, the active material of positive pole is LiNixCoyMnzL(1-x-y-z)O2、LiCox’L(1-x’)O2And LiNix”L’y’ Mn(2-x”-y’)O4In at least one, wherein, L be Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0≤x≤1,0≤y≤1,0 ≤ z≤1,0 < x+y+z≤1,0<X '≤1,0.3≤x "≤0.6,0.01≤y '≤0.2, L ' be Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe.
Due to being using the beneficial effect of above technical scheme, the application:
The nonaqueous electrolytic solution of the application, with the second chemical combination shown in the first compound and structural formula two shown in structural formula one Thing is used cooperatively, and both act synergistically, and have both improved the high temperature cyclic performance of high-voltage lithium ion batteries, and turn avoid negative pole table Decompose and aerogenesis phenomenon in face.Also, the first compound also can subparticipation cathode film formation reaction, improve cathode interface situation, enter And ensure the low temperature performance and high rate performance of battery.
Embodiment
The applicant has found the first compound, used as non-aqueous organic solvent in a series of research of electrolyte When, aerogenesis can be decomposed in negative pole, there is potential safety hazard;Although second compound can improve high-temperature behavior, it is positive and negative Polymerisation formation passivating film occurs for pole surface, and the passivation membrane impedance is larger, reduces the low temperature performance and multiplying power of battery Performance.After substantial amounts of research and experiment, the application is proposed, the first compound and second compound is used in mixed way, two Person acts synergistically, and on the basis of the first compound and the respective advantage of second compound and function is retained, both overcomes first Compound decomposes the potential safety hazard of aerogenesis in negative pole, and second compound is alleviated again to battery low temperature performance and high rate performance Influence, substantially increase the properties of battery.
The application is described in further detail below by specific embodiment.Following examples only are entered to advance to the application One step illustrates, should not be construed as the limitation to the application.
Embodiment
This example prepares electrolyte according to the component and proportioning shown in table 1, wherein, devise multiple the application be used for lithium from The nonaqueous electrolytic solution of sub- battery, and multiple comparative examples, refer to table 1.
The preparation method of the electrolyte of this example is:According to the proportions non-aqueous organic solvent shown in table 1, then thereto The lithium hexafluoro phosphate that ultimate density is 1.0mol/L is added, then additive is added by table 1.Percentage in table 1 is weight percent Than it is 12.5% that is, additive, which accounts for lithium salt content in the percentage of electrolyte gross weight, electrolyte, and remaining is added for grade solvent Agent.
Each component and consumption in the electrolyte of table 1
The lithium ion battery of this example, positive active material uses LiNi0.5Co0.2Mn0.3O2, negative pole is using graphite and conduction Carbon black, barrier film uses polypropylene, three layers of barrier film of polyethylene and polypropylene.It is specific as follows:
Anode preparation method is:By 96.8:2.0:1.2 quality is than blended anode active material LiNi0.5Co0.2Mn0.3O2, conductive carbon black and binding agent polyvinylidene fluoride, be dispersed in METHYLPYRROLIDONE, obtain Anode sizing agent, anode sizing agent is uniformly coated on the two sides of aluminium foil, by drying, calendering and vacuum drying, and uses ultrasonic wave Welding machine to be burn-on and obtain positive plate after aluminum lead-out wire, and the thickness of pole plate is between 120-150 μm.
Negative pole preparation method is:By 96:1:1.2:1.8 quality is than admixed graphite, conductive carbon black, binding agent butadiene-styrene rubber And carboxymethyl cellulose, disperse in deionized water, to obtain cathode size, cathode size is coated on the two sides of Copper Foil, pass through Cross drying, calendering and be dried in vacuo, and burn-on with supersonic welder and obtain negative plate after nickel lead-out wire, the thickness of pole plate exists Between 120-150 μm.
Barrier film preparation method is:Using polypropylene, three layers of barrier film of polyethylene and polypropylene, thickness is 20 μm.
Battery assembly method is:Three layers of barrier film that thickness is 20 μm are placed between positive plate and negative plate, then will The sandwich structure of positive plate, negative plate and barrier film composition is wound, then is put into aluminum foil sack after coiling body is flattened, Vacuum bakeout 48h at 75 DEG C, obtains treating the battery core of fluid injection;The electrolyte of above-mentioned preparation is injected in battery core, it is quiet through Vacuum Package Only 24h.
Battery formation:0.05C constant-current charges 180min, 0.1C constant-current charge to 3.95V, secondary vacuum is sealed, and 45 DEG C are put 48h is put, then further with 0.2C electric current constant-current charge to 4.4V, with 0.2C electric current constant-current discharge to 3.0V.
This example tests each electrolyte lithium ion battery respectively, and 45 DEG C of 1C circulation volume conservation rates decay to 80% and followed Capability retention, capacity restoration rate and thickness swelling after being stored 14 days at ring number of times, and 60 DEG C.Stored at wherein 60 DEG C Refer to behind some days, the electrolyte of comparative example, its lithium ion battery is tested after being stored 7 days at 60 DEG C, and test example is 60 Tested after being stored 14 days at DEG C.Specific method of testing is as follows:
(1) 45 DEG C of 1C circulation volume conservation rate decays to 80% cycle-index, and what is actually embodied is the high temperature of battery Cycle performance, specific method of testing includes:At 45 DEG C, the battery after chemical conversion is charged to 4.4V, Jie Zhi electricity with 1C constant current constant voltages Flow for 0.01C, then with 1C constant-current discharges to 3.0V, so circulation, until capability retention decays to 80%, statistics is now Cycle-index.Capability retention computing formula is as follows:
Capability retention (%)=(n-th cyclic discharge capacity/first time cyclic discharge capacity) × 100%.
The method of testing of capability retention, capacity restoration rate and thickness swelling after being stored 14 days at (2) 60 DEG C includes: Battery after chemical conversion is charged to 4.4V with 1C constant current constant voltages at normal temperatures, is 0.01C by electric current, then 1C constant-current discharges are extremely 3.0V, measures battery initial discharge capacity, then with 1C constant-current constant-voltage chargings to 4.4V, be 0.01C by electric current, measure battery Original depth, then after 60 DEG C store 14 days, measures the thickness of battery, then with 1C constant-current discharges to 3.0V, measurement battery Capacity is kept, then it is 0.01C to be filled with 1C constant current constant voltages by electric current, then measures it to 3.0V with 1C electric current constant-current discharge Recover capacity.Computing formula is as follows:
Battery capacity conservation rate (%)=holding capacity/initial capacity × 100%
Capacity resuming rate (%)=recovery capacity/initial capacity × 100%
Cell thickness expansion rate (%)=(thickness-original depth after 14 days)/original depth × 100%.
(3) low temperature performance is tested
At 25 DEG C, the battery after chemical conversion is charged to 4.4V with 1C constant current constant voltages, then constant-voltage charge to electric current drops to 0.01C, then with 1C constant-current discharges to 3.0V, records normal temperature discharge capacity.Then 1C constant currents are charged to 4.4V, then constant-voltage charge is extremely Electric current drops to 0.01C, is shelved in the environment that battery is placed in -20 DEG C after 12h, then 0.2C constant-current discharges are to 3.0V, record -20 DEG C discharge capacity.
- 20 DEG C of low temperature discharging efficiency=0.2C discharge capacities (- 20 DEG C)/1C discharge capacities (25 DEG C) × 100%.
Every test result is as shown in table 2.
The test result of table 2
Comparative example 1 can be seen that according to the result of table 2 and use only second compound as additive, without using First compound is as solvent, and therefore, high temperature cyclic performance is weaker, and capability retention is left with 80% after being circulated at 290, and And the holding capacity and recovery capacity of 60 DEG C of storages 14 days are also undesirable, especially low temperature performance is poor.Comparative example 2 is adopted With the first compound as solvent, without using second compound as additive, its high-temperature storage performance and high temperature storage Sustainability can be all very poor.Comparative example 3-9, using the first compound as solvent, and using saturation phosphate as additive, together When solvent combination is also optimized adjustment, although the high temperature cyclic performance and high-temperature storage performance of battery have larger change It is kind, but requirement can not be met, need further raising.Embodiment 1-21 employ simultaneously the first compound as solvent and Second compound as additive, while to solvent combination and additive combination be all optimized, its high temperature cyclic performance and High-temperature storage storage performance improves significantly, while taking into account low temperature performance.The high temperature cyclic performance of embodiment 21 is best, Capability retention can be circulated 662 times when decaying to 80%, and high-temperature storage performance is also quite excellent.
Above content is to combine the further description that specific embodiment is made to the application, it is impossible to assert this Shen Specific implementation please is confined to these explanations.For the application person of an ordinary skill in the technical field, do not taking off On the premise of from the application design, some simple deduction or replace can also be made, the protection of the application should be all considered as belonging to Scope.

Claims (10)

1. a kind of nonaqueous electrolytic solution for lithium ion battery, it is characterised in that:Including changing selected from first shown in structural formula one At least one and in the second compound shown in structural formula two at least one in compound;
The R of structural formula one1COOR2,
In structural formula one, R1、R2It is independently selected from alkyl or fluoro alkyl that carbon number is 1-5, and R1And R2In at least One is the fluoro alkyl;At least two hydrogen are replaced by fluorine in the fluoro alkyl;
Structural formula two
In structural formula two, R3、R4、R5It is independently selected from saturated hydrocarbyl, unsaturated alkyl or halo that carbon number is 1-5 Alkyl, and R3、R4、R5In at least one be unsaturated alkyl.
2. nonaqueous electrolytic solution according to claim 1, it is characterised in that:In the structural formula one, carbon number is 1-5's Alkyl includes but are not limited to methyl, ethyl, propyl group, vinyl, pi-allyl, 3- cyclobutenyls, isobutenyl, 4- pentenyls, second Alkynyl, propargyl, 3- butynyls, the propinyl of 1- methyl -2;The fluoro alkyl includes but are not limited to difluoromethyl, fluoroform Base, the fluoro ethyls of 2,2- bis-, 2,2,2- trifluoroethyls, the fluoropropyls of 3,3- bis-, 3,3,3- trifluoro propyls, hexafluoro isopropyl;
In the structural formula two, carbon number includes but are not limited to methyl, ethyl, propyl group for 1-5 saturated hydrocarbyl;Carbon atom Number includes but are not limited to vinyl, pi-allyl, 3- cyclobutenyls, isobutenyl, 4- pentenyls, second for 1-5 unsaturated alkyl Alkynyl, propargyl, 3- butynyls, the propinyl of 1- methyl -2;Carbon number includes but are not limited to difluoro for 1-5 halohydrocarbyl Methyl, trifluoromethyl, the fluoro ethyls of 2,2- bis-, 2,2,2- trifluoroethyls, the fluoropropyls of 3,3- bis-, 3,3,3- trifluoro propyls, hexafluoro are different Propyl group.
3. nonaqueous electrolytic solution according to claim 1, it is characterised in that:First compound is selected from H3CCOOCH2CF2H、H3CH2CCOOCH2CF2H、HF2CH2CCOOCH3、HF2CH2CCOOCH2CH3、HF2CH2CH2CCOOCH2CH3、 H3CCOOCH2CH2CF2H、H3CH2CCOOCH2CH2CF2H、CH3COOCH2CF3、HCOOCH2CHF2、HCOOCH2CF3With CH3COOCH2CF2CF2At least one in H.
4. nonaqueous electrolytic solution according to claim 1, it is characterised in that:The second compound is selected from tricresyl phosphate alkynes third Ester, dipropargyl methyl phosphorodithioate, dipropargyl ethyl phosphonic acid ester, dipropargyl propyl phosphate, dipropargyl trifluoromethyl Phosphate, dipropargyl 2,2,2- trifluoroethyls phosphate, dipropargyl 3,3,3- trifluoro propyls phosphate, dipropargyl hexafluoro Isopropyl phosphoric acid ester, TAP, diallyl methyl phosphorodithioate, diallyl ethyl phosphonic acid ester, diallyl propyl group Phosphate, diallyl trifluoromethyl phosphate, diallyl 2,2,2- trifluoroethyls phosphate, diallyl 3,3,3- trifluoros At least one in propyl phosphate and diallyl hexafluoro isopropyl phosphate.
5. the nonaqueous electrolytic solution according to claim any one of 1-4, it is characterised in that:It is described in the nonaqueous electrolytic solution First compound amount accounts for the 10%-80% of nonaqueous electrolytic solution gross weight;It is total that the second compound consumption accounts for nonaqueous electrolytic solution The 0.01%-5% of weight.
6. the nonaqueous electrolytic solution according to claim any one of 1-4, it is characterised in that:Also include in the nonaqueous electrolytic solution One or more in unsaturated cyclic carbonic ester, unsaturated acid anhydride, cyclic sulfates, ring-type sultones, sulfone class.
7. nonaqueous electrolytic solution according to claim 6, it is characterised in that:It is sub- that the unsaturated cyclic carbonic ester is selected from carbonic acid At least one in vinyl acetate, vinylethylene carbonate;The unsaturated acid anhydride is selected from succinic anhydride, maleic anhydride and 2- methyl At least one in maleic anhydride;One or two of the cyclic sulfates in sulfuric acid vinyl ester and sulfuric acid propylene; The ring-type sultones is selected from 1,3- propane sultones, 1,4- butane sultones, 1,3- propene sultones and methane-disulfonic acid At least one in methylene ester;The sulfone class material is sulfolane.
8. the nonaqueous electrolytic solution according to claim any one of 1-4, it is characterised in that:The nonaqueous electrolytic solution also includes choosing From ethylene carbonate, fluorinated ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, carbonic acid At least one in methyl ethyl ester and methyl propyl carbonate, 1,4- butyrolactone;It is preferred that, nonaqueous electrolytic solution also include ethylene carbonate, At least one in fluorinated ethylene carbonate and propene carbonate.
9. a kind of lithium ion battery, including positive pole, negative pole, the barrier film that is placed between positive pole and negative pole, and electrolyte, its feature It is:The electrolyte is the nonaqueous electrolytic solution described in claim any one of 1-8.
10. lithium ion battery according to claim 9, it is characterised in that:The active material of the positive pole is LiNixCoyMnzL(1-x-y-z)O2、LiCox’L(1-x’)O2And LiNix”L’y’Mn(2-x”-y’)O4In at least one, wherein, L be Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, 0≤x≤1,0≤y≤1,0≤z≤1,0 < x+y+z≤1,0<X '≤1,0.3≤x " ≤ 0.6,0.01≤y '≤0.2, L ' are Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe.
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US16/316,621 US11362370B2 (en) 2016-11-25 2016-12-30 Non-aqueous electrolyte for lithium-ion battery and lithium-ion battery
JP2018564811A JP6814821B2 (en) 2016-11-25 2016-12-30 Non-aqueous electrolyte for lithium-ion batteries
PCT/CN2016/113649 WO2018094843A1 (en) 2016-11-25 2016-12-30 Non-aqueous electrolyte for lithium-ion battery and lithium-ion battery
JP2020136214A JP6963068B2 (en) 2016-11-25 2020-08-12 Non-aqueous electrolyte for lithium-ion batteries
JP2021169184A JP7208330B2 (en) 2016-11-25 2021-10-14 Non-aqueous electrolyte for lithium-ion batteries
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