CN103825048B - Lithium rechargeable battery and electrolyte thereof - Google Patents
Lithium rechargeable battery and electrolyte thereof Download PDFInfo
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- CN103825048B CN103825048B CN201410068856.2A CN201410068856A CN103825048B CN 103825048 B CN103825048 B CN 103825048B CN 201410068856 A CN201410068856 A CN 201410068856A CN 103825048 B CN103825048 B CN 103825048B
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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
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a kind of lithium rechargeable battery and electrolyte thereof. The electrolyte of described lithium rechargeable battery, comprising: non-aqueous organic solvent; Lithium salts, is dissolved in non-aqueous organic solvent; And additive, be dissolved in non-aqueous organic solvent. Described additive comprises the maleic ester type compound with formula I, formula II or formula III structure, and described maleic ester type compound quality is 0.5%～3% of described non-aqueous organic solvent gross mass, wherein, and R1And R2Independently selected from the one in haloalkyl, haloalkene alkyl, halogenophenyl, halogenated biphenyl base, described halogen is F, Cl or Br respectively, and described halo is monosubstituted, partly replacement or replacement entirely. Lithium rechargeable battery of the present invention comprises the electrolyte of above-mentioned lithium rechargeable battery. Lithium rechargeable battery of the present invention can effectively improve its discharge capacity first and memory property under high temperature high voltage.
Description
Technical field
The present invention relates to field of batteries, relate in particular to a kind of lithium rechargeable battery and electrolyte thereof.
Background technology
Along with the electronics mobile devices such as notebook computer, mobile phone, handheld device, panel computer can be realizedIncreasing function, people also get over the requirement of the lithium rechargeable battery as its main drive energyCome higher. Lithium rechargeable battery also becomes increasingly in the application technology of the aspect such as electric automobile, intelligent gridRipe. Extend the service life of lithium rechargeable battery and improve its security performance and become current industry hot topicOne of research topic.
When we improve the energy density of lithium rechargeable battery, particularly improve lithium rechargeable batteryWhen voltage, be equivalent to the activity of the electrochemical reaction that improves electrolyte, at this moment electrolyte will on both positive and negative polarityThere is violent redox reaction, follow the generation of a large amount of side reactions, lithium rechargeable battery simultaneouslyPerformance will be subject to very negative impact. In actual use, electronic product also faces as continued and usesThe environment for use temperature rising of heating or lithium rechargeable battery etc. all may make lithium rechargeable battery placeIn the condition of high temperature, and at high temperature, electrolyte will be subject to stricter test, when serious due to lithium ionThe dilatancy of secondary cell causes lithium rechargeable battery inside to be short-circuited or lithium ion secondary electricityPond packaging is burst and is caused flammable electrolyte to be revealed, thereby causes the security incidents such as fire. Therefore needEffectively technology solves the decomposition of electrolyte, the problem of lithium rechargeable battery flatulence.
Summary of the invention
The object of the present invention is to provide a kind of lithium rechargeable battery and electrolyte thereof, it can effectively changeFirst discharge capacity and the memory property of kind lithium rechargeable battery under high temperature high voltage.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of lithium ion twoThe electrolyte of primary cell, comprising: non-aqueous organic solvent; Lithium salts, is dissolved in non-aqueous organic solvent; WithAnd additive, be dissolved in non-aqueous organic solvent. Described additive comprises having formula I, formula II or formula IIIThe maleic ester type compound of structure, described maleic ester type compound quality is described non-aqueous organic solvent0.5%～3% of gross mass, wherein, R1And R2Respectively independently selected from haloalkyl, haloalkene alkyl,One in halogenophenyl, halogenated biphenyl base, described halogen is F, Cl or Br, described halo is for singly gettingGeneration, part replace or entirely replace,
In a second aspect of the present invention, the invention provides a kind of lithium rechargeable battery, comprising: positive poleSheet; Negative plate; Barrier film, is interval between adjacent positive sheet and negative plate; And electrolyte. Wherein,Described electrolyte is according to the electrolyte of the lithium rechargeable battery of first aspect present invention.
Beneficial effect of the present invention is as follows:
Lithium rechargeable battery of the present invention and electrolyte thereof have first good under high temperature high voltageDischarge capacity and memory property.
Detailed description of the invention
Describe in detail below according to lithium rechargeable battery of the present invention and electrolyte thereof and comparative example, realityExecute example.
First illustrate according to the electrolyte of the lithium rechargeable battery of first aspect present invention.
According to the electrolyte of the lithium rechargeable battery of first aspect present invention, comprising: non-aqueous organic solvent;Lithium salts, is dissolved in non-aqueous organic solvent; And additive, be dissolved in non-aqueous organic solvent. DescribedAdditive comprises the maleic ester type compound with formula I, formula II or formula III structure, described maleic esterCompounds quality is 0.5%～3% of described non-aqueous organic solvent gross mass, wherein, and R1And R2RespectivelyIndependently selected from the one in haloalkyl, haloalkene alkyl, halogenophenyl, halogenated biphenyl base, described inHalogen is F, Cl or Br, and described halo is monosubstituted, partly replacement or replacement entirely.
Because the molecular weight of described maleic ester type compound is larger, larger to the viscosity influence of electrolyte,In the time that the quality percentage composition of maleic ester type compound is less than 0.5%, cannot on negative pole, form stableSEI film, the impact of the high-temperature storage performance on lithium rechargeable battery and first discharge capacity is also not clearAobvious; In the time that the quality percentage composition of maleic ester type compound is greater than 3%, electrolyte viscosity strengthens, shadowThe electrical conductivity of ringing lithium ion, makes the deintercalation speed of lithium ion be subject to negative impact, worsens lithium ion twoThe discharge capacity first of primary cell.
The compound that contains double bond structure is easily reduced in negative terminal surface conventionally, anodal surperficial by oxygenChange, thereby electrochemical polymerization effect occurs, generate polymer inactivation film, as vinylene carbonate (VC)There is good negative pole passivation, but when under the effect of high pressure, due to its lower oxidizing potential,Can decompose at anodal surface oxidation, make the high-temperature storage performance of lithium rechargeable battery worsen very brightAobvious. And maleic ester type compound is introduced electron withdraw group by the two ends at maleic, improve changeThe oxidizing potential of compound and its oxidative resistance anodal under high voltage. The carbonic ester at maleic molecule two endsMay participate at negative pole half sulphur of catenulate alkyl half lithium carbonate of shape or chain with the structure of sulphonic acid esterWhen acid lithium material, participate in the formation of SEI film. And intramolecular pair of key of maleic ensured its withVC has similar film forming efficiency. In addition, this intramolecular maleic structure can be improved lithium ion twoThe discharge capacity first of primary cell, reaches the film-formation result similar to VC. Carbonic ester and sulphonic acid ester chemical combinationThing itself has higher compatibility with electrolyte system, simultaneously because R1And R2Substituting group is electrophilicGroup, can make the non-oxidizability of this compounds greatly improve, and halogenic substituent, particularlyThe functional group of fluoro also may generate LiF and participate in the formation of SEI film at negative pole, further increases film formingStability.
According in the electrolyte of the lithium rechargeable battery of first aspect present invention, described maleic ester classCompound quality can be 1%～2% of described non-aqueous organic solvent gross mass.
According in the electrolyte of the lithium rechargeable battery of first aspect present invention, described maleic ester classCompound can be selected from one or more in C-1 to C-9 structure.
According in the electrolyte of the lithium rechargeable battery of first aspect present invention, described non-water is organic moltenAgent can be ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate, diethyl carbonate(DEC), dipropyl carbonate, methyl ethyl carbonate (MEC), methyl propyl carbonate, methyl formate, secondAcetoacetic ester, methyl butyrate, methyl acrylate, dimethyl sulfite, diethyl sulfite, acid anhydrides,1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N-methylacetamide, acetonitrile, DMF,Sulfolane, methyl-sulfoxide, methyl sulfide, gamma-butyrolacton, oxolane, fluorine-containing ring-type organic ester, sulfur-bearingRing-type organic ester, containing one or more in unsaturated bond ring-type organic ester.
According in the electrolyte of the lithium rechargeable battery of first aspect present invention, described additive also canComprise vinylene carbonate (VC), fluorinated ethylene carbonate, ethene sulfite, propylene sulfite,One or more in PS (PS).
According in the electrolyte of the lithium rechargeable battery of first aspect present invention, described lithium salts can beLiPF6、LiBF4、LiBOB、LiClO4、LiAsF6、LiCF3SO3、Li(CF3SO2)2In N oneKind or several.
Secondly explanation is according to the lithium rechargeable battery of second aspect present invention.
According to the lithium rechargeable battery of second aspect present invention, comprising: positive plate; Negative plate; IsolationFilm, is interval between adjacent positive sheet and negative plate; And electrolyte. Described electrolyte is according to thisThe electrolyte of the lithium rechargeable battery described in bright first aspect.
According in the lithium rechargeable battery of second aspect present invention, described positive plate can comprise and can take offThe positive electrode active materials of embedding, embedding lithium ion. Described positive electrode active materials can be lithium transition-metal composite oxygenCompound. Described lithium transition-metal oxide can be selected from lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide,One or more in Li, Ni, Mn oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide.
According in the lithium rechargeable battery of second aspect present invention, described negative plate can comprise can embeddingEnter, the negative active core-shell material of removal lithium embedded ion. Described negative active core-shell material can be selected from soft carbon, hard carbon, peopleMake graphite, native graphite, silicon, silicon oxide compound, silicon-carbon compound, lithium titanate or can form and close with lithiumOne or more in the metal of gold.
Next illustrate according to lithium rechargeable battery of the present invention and electrolyte thereof and embodiment, contrastExample.
Comparative example 1
(1) preparation of the positive plate of lithium rechargeable battery
Active material cobalt acid lithium, conductive agent acetylene black, binding agent polyvinylidene fluoride (PVDF) are pressedThe mass ratio of 96:2:2 is coated on collection after fully stirring in solvent 1-METHYLPYRROLIDONE and mixingOn fluid Al paper tinsel, dry, cold pressing, obtain the positive plate of lithium rechargeable battery.
(2) preparation of the negative plate of lithium rechargeable battery
By active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickener carboxylicThe mass ratio that sodium carboxymethylcellulose pyce (CMC) is pressed 95:2:2:1 fully stirs and mixes in solvent deionized waterAfter closing evenly, be coated on collector Cu paper tinsel and dry, cold pressing, obtain the negative pole of lithium rechargeable batterySheet.
(3) preparation of the electrolyte of lithium rechargeable battery
Ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC) are pressed to 30:5:65Mass ratio mix (as non-aqueous organic solvent), and dissolve 1MLiPF6Lithium salts, obtains lithium ion twoThe electrolyte of primary cell.
(4) preparation of lithium rechargeable battery
Positive plate, barrier film PE porous polymer film, negative plate are folded in order, made PE porous poly-Close film and in the middle of positive plate and negative plate, play the effect of isolation, and reel and obtain naked battery core, by nakedBattery core is placed in external packing, injects the electrolyte the encapsulation that prepare, obtains lithium rechargeable battery.
Comparative example 2
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the vinylene carbonate (VC) of non-aqueous organic solvent gross mass 2%.
Comparative example 3
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the carbonic acid maleic lactone (C-10) of non-aqueous organic solvent gross mass 2%.
Comparative example 4
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the propylene carbonate methyl esters (C-11) of non-aqueous organic solvent gross mass 2%.
Comparative example 5
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the maleic-Isosorbide-5-Nitrae-diacetate esters (C-12) of non-aqueous organic solvent gross mass 2%.
Comparative example 6
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is maleic two methanesulfonates (C-13) of non-aqueous organic solvent gross mass 2%.
Comparative example 7
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-2 of non-aqueous organic solvent gross mass 0.1%.
Comparative example 8
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-2 of non-aqueous organic solvent gross mass 4%.
Comparative example 9
(1) preparation of the positive plate of lithium rechargeable battery
By active material LiNi0.5Co0.2Mn0.3O2, conductive agent acetylene black, binding agent polyvinylidene fluoride(PVDF) fully stir in solvent 1-METHYLPYRROLIDONE by the mass ratio of 96:2:2 and mixAfter, be coated on collector Al paper tinsel and dry, cold pressing, obtain the positive plate of lithium rechargeable battery.
(2) preparation of the negative plate of lithium rechargeable battery
By active material graphite, conductive agent acetylene black, binding agent butadiene-styrene rubber (SBR), thickener carboxylicThe mass ratio that sodium carboxymethylcellulose pyce (CMC) is pressed 95:2:2:1 fully stirs and mixes in solvent deionized waterAfter closing evenly, be coated on collector Cu paper tinsel and dry, cold pressing, obtain the negative pole of lithium rechargeable batterySheet.
(3) preparation of the electrolyte of lithium rechargeable battery
Ethylene carbonate (EC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC) are pressedThe mass ratio of 30:35:35 mixes (as non-aqueous organic solvent), and dissolves 0.95MLiPF6And 0.05MLiBF4Lithium salts, obtains the electrolyte of lithium rechargeable battery.
(4) preparation of lithium rechargeable battery
Positive plate, barrier film PE porous polymer film, negative plate are folded in order, made PE porous poly-Close film and play the effect of isolation in the centre of positive plate and negative plate, and reel and obtain naked battery core, willNaked battery core is placed in external packing, injects the electrolyte the encapsulation that prepare, obtains lithium rechargeable battery.
Embodiment 1
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-2 of non-aqueous organic solvent gross mass 0.5%.
Embodiment 2
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-2 of non-aqueous organic solvent gross mass 1%.
Embodiment 3
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-2 of non-aqueous organic solvent gross mass 2%.
Embodiment 4
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-2 of non-aqueous organic solvent gross mass 3%.
Embodiment 5
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-1 of non-aqueous organic solvent gross mass 2%.
Embodiment 6
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-3 of non-aqueous organic solvent gross mass 2%.
Embodiment 7
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-1 of non-aqueous organic solvent gross mass 0.5%.
Embodiment 8
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-1 of non-aqueous organic solvent gross mass 1.0%.
Embodiment 9
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-1 of non-aqueous organic solvent gross mass 3.0%.
Embodiment 10
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-3 of non-aqueous organic solvent gross mass 1.0%.
Embodiment 11
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-4 of non-aqueous organic solvent gross mass 2%.
Embodiment 12
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-5 of non-aqueous organic solvent gross mass 2%.
Embodiment 13
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-5 of non-aqueous organic solvent gross mass 1%.
Embodiment 14
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-5 of non-aqueous organic solvent gross mass 0.5%.
Embodiment 15
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-6 of non-aqueous organic solvent gross mass 2%.
Embodiment 16
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-6 of non-aqueous organic solvent gross mass 1%.
Embodiment 17
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-7 of non-aqueous organic solvent gross mass 1%.
Embodiment 18
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-8 of non-aqueous organic solvent gross mass 2%.
Embodiment 19
Method according to comparative example 1 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is the C-9 of non-aqueous organic solvent gross mass 1%.
Embodiment 20
Method according to comparative example 9 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is 0.5% C-3.
Embodiment 21
Method according to comparative example 9 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, lithium salts is 0.95MLiPF6And 0.05MLi (CF3SO2)2N(LiTFSI), also added additive in electrolyte, additive is that quality percentage composition is that non-water is organicThe C-3 of solvent gross mass 0.5%.
Embodiment 22
Method according to comparative example 9 is prepared lithium rechargeable battery, is the electricity at lithium rechargeable batterySeparate in the preparation (being step (3)) of liquid, also added additive in electrolyte, additive is qualityPercentage composition is that C-3 and the quality percentage composition of non-aqueous organic solvent gross mass 0.5% is that non-water is organic moltenThe PS (PS) of agent gross mass 0.5%.
Test process and the test result of lithium rechargeable battery of the present invention are finally described.
(1) discharge capacity test relatively first
Under 45 DEG C of conditions, first with the constant current of 0.7C, lithium rechargeable battery is charged to 4.4V,Further under 4.4V constant voltage, charge to electric current and be less than 0.05C, then with the constant current of 0.5CLithium rechargeable battery is discharged to 3.0V. Record the head that current discharge capacity is lithium rechargeable batteryInferior discharge capacity (T), and with (the T of discharge capacity first of comparative example 10) be reference, draw enforcementThe relative r=T/T of discharge capacity first of example 1-19 and comparative example 1-90; Electric discharge first with comparative example 9 is heldAmount (T0) for reference, draw the relative r=T/T of discharge capacity first of embodiment 20-22 and comparative example 90。
(2) high temperature storage test
Each lithium rechargeable battery at normal temperatures with 0.5C constant current charge to voltage higher than 4.4V, enterOne step charges to electric current lower than 0.05C under 4.4V constant voltage, makes it in 4.4V fully charged state.The thickness of the lithium rechargeable battery completely filling before test storage is also designated as D0, then by the lithium ion of fully charged stateSecondary cell is placed in 60 DEG C of baking ovens, after 14 days, lithium rechargeable battery is taken out and tests immediately itThickness after storage is also designated as D1. Thickness swelling before and after lithium rechargeable battery storageε=(D1-D0)/D0×100%
Table 1 provides relevant parameter and the survey of the lithium rechargeable battery of comparative example 1-9 and embodiment 1-22Test result.
(1) discharge capacity test result analysis relatively first
From the contrast of comparative example 1 and embodiment 1-22, can find out the carbonic ester of maleic and sulphonic acid esterCompounds is improved effect to the discharge capacity relatively first of lithium rechargeable battery, this may be due toIn this quasi-molecule, two keys of maleic structure and the collocation of carbonic ester and/or sulfonate functionality can be at negative polesSurface forms good SEI film, and in this process, consumes less lithium ion, has therefore improved lithiumThe discharge capacity relatively first of ion secondary battery.
From the contrast of comparative example 2-5, can find out, add carbonic ester and the sulphonic acid ester chemical combination of non-maleicThing, the discharge capacity relatively first of lithium rechargeable battery is all poor. This is due to VC in comparative example 2Oxidizing potential lower, the discharge capacity relatively first of lithium rechargeable battery is improved to DeGrain;In comparative example 3, film forming efficiency is not high first for carbonic acid maleic lactone (C-10), larger to lithium ion consumption,This may to have larger circulus relevant with it; In comparative example 4 in propylene carbonate methyl esters (C-11)The double bond structure of " exposed " can not form good SEI film, and it becomes membrane impedance greatly and oxidizing potentialLower, can worsen the discharge capacity relatively first of lithium rechargeable battery; Maleic-Isosorbide-5-Nitrae in comparative example 5-Diacetate esters (C-12) is easier at anodal surface oxidation, and neither at the film-formation result of negative terminal surfaceGood especially, easily worsen the performance of lithium rechargeable battery.
Maleic two methanesulfonates (C-13) in comparative example 6 although be the sulfonate compound of maleic,But its substituting group is alkyl, the discharge capacity relatively first of lithium rechargeable battery does not obtain obviouslyImprove. And in embodiment 1-22 the carbonic ester of maleic and sulfonates compounds to lithium rechargeable batteryDischarge capacity relatively be first improved obviously. This may be due in first charge-discharge process, toolThere is halogen-containing R in the maleic ester type compound of formula I, formula II or formula III structure1And R2Functional group canParticipate in film forming procedure, particularly fluorine-containing R1And R2Functional group can generate LiF and form stable SEIFilm, thus improved stability and the efficiency of film forming, and then improve lithium rechargeable battery relatively firstDischarge capacity.
From the contrast of comparative example 7-8 and embodiment 1-4, can find out, when the quality percentage composition of C-2While being less than 0.5%, the discharge capacity relatively first of lithium rechargeable battery does not change; Along with the matter of C-2Amount percentage composition continues to increase, and the discharge capacity relatively first of lithium rechargeable battery also increases; Work as C-2Quality percentage composition while exceeding 3%, the discharge capacity relatively first of lithium rechargeable battery starts to decline.This is that impedance owing to can make it at cathode film formation in the time that the quality percentage composition of C-2 is too high time increases,And then affect the discharge capacity relatively first of lithium rechargeable battery; And when the quality percentage composition mistake of C-2The impact of the discharge capacity relatively first hour on lithium rechargeable battery is also not obvious. Equally, from implementingIn the contrast of example 5 and embodiment 7-9, also can see identical trend.
From the contrast of embodiment 6, embodiment 11 and embodiment 12, can find out substituent chain lengthIncrease, the discharge capacity relatively first of lithium rechargeable battery declines, and this may be the increase due to chain lengthCause electrolyte viscosity increase and can cause the SEI membrane structure of formation stable not, thereby affect lithium fromThe discharge capacity relatively first of sub-secondary cell.
From the contrast of embodiment 2, embodiment 8 and embodiment 10, can find out to there is formula II structureMaleic ester type compound is put first than the relative of maleic ester type compound with formula I and formula III structureCapacitance is all poor, and the maleic ester type compound at least with a carbonic ester is all sulphonic acid ester than two endsThe discharge capacity relatively first of maleic ester type compound (formula II) to get well, this may tie with maleicThe arrange in pairs or groups impedance of the SEI film that forms of structure and carbonic ester is lower relevant, and the compound of sulphonic acid ester structure is generalCan on negative pole, reduce film forming prior to the compound of carbonic ester structure, and become film activity higher, therefore film formingImpedance may be larger, thereby the discharge capacity relatively first of lithium rechargeable battery is brought to negative shadowRing. Comparative example 3, embodiment 5 and embodiment 6, comparative example 1 and embodiment 7, contrast are in factExecute example 4 and embodiment 9, also find identical trend, at least there is the maleic ester of a carbonic esterCompounds is all that the electric discharge relatively first of the maleic ester type compound (formula II) of sulphonic acid ester is held than two endsAmount will be got well.
From the contrast of comparative example 9 and embodiment 20-22, can find out, when containing two lithium salts in electrolyteAnd when the maleic ester type compound of carbonic ester and sulphonic acid ester, than the two lithium salts (comparative example 9) of independent useThe discharge capacity relatively first of lithium rechargeable battery want high, this is due to a kind of lithium salts LiBF wherein4Or LiTFSI can produce synergy, thereby lithium ion two with maleic ester type compound as additiveIt is high that the discharge capacity relatively first of primary cell is wanted.
(2) high temperature storage test result analysis
From the contrast of comparative example 1 and embodiment 1-22, can find out the carbonic ester of maleic and sulphonic acid esterCompounds improves significantly to the high temperature thickness swelling of lithium rechargeable battery, this may be due toIn this quasi-molecule, two keys of maleic structure and the collocation of carbonic ester and/or sulfonate functionality can be at negative polesSurface forms stable SEI film, and halogen-containing R1And R2Functional group can participate in film forming procedure, consolidatesGu the stability of SEI film, the further reaction of isolated electrolyte; In addition this two sideband electron-withdrawing groups,The non-oxidizability of the maleic ester type compound of group is further enhanced, thereby improves lithium ion secondary electricityThe high-temperature storage performance in pond.
From the contrast of comparative example 2-5, can find out, add carbonic ester and the sulfonic acid esterification of non-maleic esterCompound, the high temperature thickness swelling of lithium rechargeable battery is all higher, and high-temperature storage performance is all poor. ThisBe because the oxidizing potential of VC in comparative example 2 is low, under HTHP, can worsen lithium rechargeable batteryMemory property; Carbonic acid maleic lactone (C-10) in comparative example 3, has lower oxidation electricity equallyPosition, and can not form good SEI film in negative terminal surface, to the high temperature storage of lithium rechargeable batteryThe deterioration of energy is also obvious. Two keys of " exposed " in propylene carbonate methyl esters (C-11) in comparative example 4Structure can not form good SEI film, and it becomes, and membrane impedance is large and oxidizing potential is lower, to lithium ionThe high-temperature storage performance of secondary cell is not improved effect; Maleic-Isosorbide-5-Nitrae-diacetate esters in comparative example 5(C-12) be easier at anodal surface oxidation, and neither be good especially at the filming performance of negative terminal surface,Easily worsen the high-temperature storage performance of lithium rechargeable battery.
Maleic two methanesulfonates (C-13) in comparative example 6 although be the sulfonate compound of maleic,But its substituting group is alkyl, the thickness swelling of lithium rechargeable battery is compared other and is had electron-withdrawing groupThe thickness swelling of the lithium rechargeable battery of group's substituent structure wants high, and high-temperature storage performance is poor. ThisThat its non-oxidizability is further carried due in the time containing electron withdraw group in maleic ester type compoundHeight, especially in the time that substituting group is fluoro-functional groups, fluoro-functional groups can negative terminal surface form LiF fromAnd form stable SEI film, stop the further reduction of electrolyte, simultaneously its relatively high oxidation electricityPosition, makes to be also improved in the non-oxidizability on anodal surface, thereby improves the height of lithium rechargeable batteryTemperature memory property.
From the contrast of comparative example 7-8 and embodiment 1-4, can find out, when the quality percentage composition of C-2While being 0.1%, the high temperature thickness swelling of lithium rechargeable battery is higher, reaches 50.8%; And work as C-2Quality percentage composition while reaching 0.5%, the high temperature thickness swelling of lithium rechargeable battery obtains significantlyImprove, be reduced to 30.2%; Along with the quality percentage composition of C-2 continues to increase, lithium rechargeable batteryHigh temperature thickness swelling constantly reduce; In the time that the quality percentage composition of C-2 exceedes 3%, lithium ion twoThe high temperature thickness swelling of primary cell starts again to increase. This is because the quality percentage composition as C-2 is too highTime can make its impedance in the time of cathode film formation increase, and the viscosity of electrolyte also can obviously strengthen, althoughHigh-temperature storage performance to lithium rechargeable battery is still improved, but can obviously affect lithium ion secondaryOther performance of battery; In the time that the quality percentage composition of C-2 is too small, the component that participates in film forming is less, noCan obviously improve the stability of film forming, so can not effectively improve the high temperature storage of lithium rechargeable batteryEnergy. Equally, from the contrast of embodiment 5 and embodiment 7-9, also can see identical trend.
From the contrast of embodiment 6, embodiment 11 and embodiment 12, can find out, change substituentChain length is larger on the high temperature thickness swelling impact of lithium rechargeable battery, along with the increasing of substituting group chain lengthAdd, the high temperature thickness swelling of lithium rechargeable battery increases, and therefore high-temperature storage performance variation replacesBase chain length is unsuitable long. This may be that the structure of the diaphragm that forms due to the substituting group of long-chain is steady notFixed, can not effectively protect the generation side reaction of electrolyte on anodal and negative pole and decompose, cause gas productionIncrease, thereby the high-temperature storage performance variation of lithium rechargeable battery.
From the contrast of embodiment 2, embodiment 8 and embodiment 10, can find out to there is formula I and formula IIIThe maleic ester type compound of structure, than the lithium ion two of maleic ester type compound with formula II structureThe high temperature thickness swelling of primary cell will be got well, and at least has the maleic ester type compound of a carbonic esterThe high-temperature storage performance of maleic ester type compound that than two ends is all sulphonic acid ester is good, this may be due toCarbonic ester and maleic structure matching can produce synergy, form stable SEI film and can not bringLarge one-tenth membrane impedance; In addition,, with respect to sulphonic acid ester, carbonic ester is to the acid-base value in chemical systemSensitiveness is lower. Comparative example 3, embodiment 5 and embodiment 6, comparative example 1 and embodiment 7,Comparative example 4 and embodiment 9, also find identical trend, at least has a carbonic esterMaleic ester type compound is all that the height of maleic ester type compound (formula II) of sulphonic acid ester is gentle than two endsStorage performance will be got well.
From the contrast of comparative example 9 and embodiment 20-22, can find out, when containing two lithium salts in electrolyteAnd when the maleic ester type compound of carbonic ester and sulphonic acid ester, than the two lithium salts (comparative example 9) of independent useThe high temperature thickness swelling of lithium rechargeable battery to get well, this is due to a kind of lithium salts LiBF wherein4OrLiTFSI can produce synergy with maleic ester type compound as additive, thereby can improve lithium ionThe high-temperature storage performance of secondary cell.
Total the above, in electrolyte of lithium-ion secondary battery, adding quality percentage composition is that non-water is organic moltenAgent 0.5%～3%, especially 1%～2% the maleic ester class with formula I, formula II or formula III structureCompound, first discharge capacity and the memory property of lithium rechargeable battery under HTHP is all better.
The relevant parameter of table 1 comparative example 1-9 and embodiment 1-22 and test result
Claims (10)
1. an electrolyte for lithium rechargeable battery, comprising:
Non-aqueous organic solvent;
Lithium salts, is dissolved in non-aqueous organic solvent; And
Additive, is dissolved in non-aqueous organic solvent;
It is characterized in that,
Described additive comprises the maleic ester compounds with formula I, formula II or formula III structure, described suitableButene esters compound quality is 0.5%～3% of described non-aqueous organic solvent gross mass, wherein, and R1And R2Respectively independently selected from the one in haloalkyl, haloalkene alkyl, halogenophenyl, halogenated biphenyl base,Described halogen is F, Cl or Br, and described halo is monosubstituted, partly replacement or replacement entirely,
2. the electrolyte of lithium rechargeable battery according to claim 1, is characterized in that, described inMaleic ester compounds quality is 1%～2% of described non-aqueous organic solvent gross mass.
3. the electrolyte of lithium rechargeable battery according to claim 1, is characterized in that, described inMaleic ester compounds is selected from one or more in C-1 to C-9 structure,
4. the electrolyte of lithium rechargeable battery according to claim 1, is characterized in that, described inNon-aqueous organic solvent is ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, carbonic acidDipropyl, methyl ethyl carbonate, methyl propyl carbonate, methyl formate, ethyl acetate, methyl butyrate, propyleneAcid methyl esters, dimethyl sulfite, diethyl sulfite, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE,N-methylacetamide, acetonitrile, DMF, sulfolane, methyl-sulfoxide, methyl sulfide, γ-One or more in butyrolactone, oxolane.
5. the electrolyte of lithium rechargeable battery according to claim 1, is characterized in that, described inAdditive also comprises vinylene carbonate, fluorinated ethylene carbonate, ethene sulfite, propylene sulfurous acidOne or more in ester, PS.
6. the electrolyte of lithium rechargeable battery according to claim 1, is characterized in that, described inLithium salts is LiPF6、LiBF4、LiBOB、LiClO4、LiAsF6、LiCF3SO3、Li(CF3SO2)2NIn one or more.
7. a lithium rechargeable battery, comprising:
Positive plate;
Negative plate;
Barrier film, is interval between adjacent positive sheet and negative plate; And
Electrolyte;
It is characterized in that,
Described electrolyte is according to the electrolysis of the lithium rechargeable battery described in any one in claim 1-6Liquid.
8. lithium rechargeable battery according to claim 7, is characterized in that, described positive plate bagContaining positive electrode active materials, described positive electrode active materials is lithium-transition metal composite oxide.
9. lithium rechargeable battery according to claim 8, is characterized in that, described lithium transition goldBelong to composite oxides be selected from lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, Li, Ni, Mn oxide,One or more in lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide.
10. lithium rechargeable battery according to claim 7, is characterized in that, described negative plate bagDraw together negative active core-shell material, described negative active core-shell material be selected from soft carbon, hard carbon, Delanium, native graphite,Silicon, silicon oxide compound, silicon-carbon compound, lithium titanate or can with lithium form a kind of in the metal of alloy orSeveral.
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| CN104600364B (en) * | 2015-02-06 | 2017-08-25 | 宁德新能源科技有限公司 | A kind of lithium ion battery of electrolyte and the application electrolyte |
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| CN114267877A (en) * | 2021-11-30 | 2022-04-01 | 合肥国轩高科动力能源有限公司 | Lithium ion battery electrolyte and lithium ion battery |
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