CN1836347A - Lithium secondary cell and its nonaqueous electrolyte - Google Patents
Lithium secondary cell and its nonaqueous electrolyte Download PDFInfo
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- CN1836347A CN1836347A CNA2004800229138A CN200480022913A CN1836347A CN 1836347 A CN1836347 A CN 1836347A CN A2004800229138 A CNA2004800229138 A CN A2004800229138A CN 200480022913 A CN200480022913 A CN 200480022913A CN 1836347 A CN1836347 A CN 1836347A
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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
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A lithium secondary cell exhibiting excellent long term cell characteristics such as cycle characteristics, electric capacity and storage characteristics, and a nonaqueous electrolyte usable in such a lithium secondary cell. The lithium secondary cell comprising a positive electrode, a negative electrode, and a nonaqueous electrolyte produced by dissolving an electrolytic salt into a nonaqueous solvent is characterized in that the positive electrode is a material containing a lithium composite oxide, the negative electrode is a material containing graphite, and the nonaqueous electrolyte contains a dialkyl oxalate, and a vinylene carbonate and/or 1,3-propane sultone.
Description
Technical field
The present invention relates to the lithium secondary battery of the long-term cycle characteristics of battery and battery behavior excellences such as capacitance, preservation characteristics and can be used in nonaqueous electrolytic solution in this lithium secondary battery.
Background technology
Lithium secondary battery is being widely used with power supply as the driving of miniaturized electronics etc. in recent years.Lithium secondary battery mainly is made of positive pole, nonaqueous electrolytic solution and negative pole, particularly with LiCoO
2Deng lithium composite xoide for anodal, be that the lithium secondary battery of negative pole is using with being well suited for material with carbon element or lithium metal.As the nonaqueous electrolytic solution of this secondary lithium batteries, very compatibly using ethylene carbonate (EC), propylene carbonate carbonates such as (PC).
, about battery behaviors such as the cycle characteristics of battery and capacitances, require to have the secondary cell of the characteristic of further excellence.
For example used LiCoO as positive pole
2, LiMn
2O
4, LiNiO
2Deng lithium secondary battery, the solvent in when charging nonaqueous electrolytic solution partial oxidation partly decomposes, this analyte hinders the desirable electrochemical reaction of battery thus, and therefore the reduction of battery performance takes place.Think that this results from the electrochemical oxidation of the solvent on the interface of positive electrode and nonaqueous electrolytic solution.
In addition, for example used the lithium secondary battery of the material with carbon element of native graphite and the contour crystallization of Delanium as negative pole, solvent in the nonaqueous electrolytic solution when charging in the negative terminal surface reduction decomposition, even during repeated charge, also cause the partial reduction decomposition at the EC that generally is widely used as the nonaqueous electrolytic solution solvent, cause the reduction of battery performance.
In order to improve the battery behavior of this lithium secondary battery, open in the flat 8-96849 communique the spy and to put down in writing: the aliphatic acid saturated dicarboxylic acid ester that uses dipropyl adipate etc., more than the preferred 5vol% of its content in solvent, in embodiment 1, putting down in writing the battery of the dimethyl adipate that adds 10vol%., cycle characteristics is about 65% at 15 circulation times, is not the result that can be satisfied with.
Thereby the content that all organic compounds such as the ketone that contains 1-20 volume % in primary cell, alcohols, aldehydes, ester class, organic acid, organo-silicon compound improve preservation characteristics is disclosed in the Te Kaiping 8-321311 communique, proposed to add the dialkyl oxalate of dimethyl oxalate and diethy-aceto oxalate and so on, the scheme of the trial of the preservation characteristics of the primary cell of raising self-discharge rate etc. as above-mentioned organic compound., do not carry out the investigation of lithium secondary battery, it also is different that electrode material constitutes with the nonaqueous electrolytic solution that uses.
Disclose in the Te Kaiping 9-199172 communique: use at least 1 capacity %, the more preferably content of the dialkyl oxalate of the alkyl of 20-80 capacity % with carbon number 1-3., though the cycle characteristics under high voltage and heavy load discharging condition improves, the discharge capacity of the 100th circulation only is 82-92% with respect to the sustainment rate of the discharge capacity of the 10th circulation.
Disclose in the Te Kaiping 8-45545 communique: comprise by the ORGANIC SOLVENT MIXTURES of the 2nd solvent of the cathode of carbon material that contains degree of crystallinity＞0.8, the 1st solvent that contains propylene carbonate etc., dimethyl carbonate, diethyl carbonate etc. and carbonic acid ethenylidene ester (VC) and electrolyte that lithium salts is formed, suppressed the lithium storage battery that material with carbon element is peeled off., cycle characteristics can not be satisfied with.
Open the spy and to disclose a kind of electrolyte in the 2002-367674 communique, it is characterized in that, this electrolyte is that the dissolving lithium salts forms in based on the solvent of at least a kind of non-water solvent being selected from carbonic ester, ether and lactone, in this electrolyte, above-mentioned solvent contains aromatic compounds such as dicarboxylic diester and dibenzofurans., do not carry out the investigation of the essence of cycle characteristics etc.
Open the spy and to disclose a kind of lithium secondary battery in the 2000-3724 communique, it is characterized in that, positive pole is the material that contains lithium composite xoide, negative pole is the material that contains graphite, nonaqueous solvents is a principal component with cyclic carbonate and linear carbonate, and in nonaqueous solvents, contain 1 below the 4 weight % more than the 0.1 weight %, 3-third sultone and/or 1,4-fourth sultone., the discharge capacity sustainment rate under the room temperature, after 50 circulations is 82-95%, and is seeking the raising of long-term cycle characteristics.
Summary of the invention
The objective of the invention is to solve problem, also excellent lithium secondary battery such as the battery behavior of the long-term cycle characteristics excellence of battery and capacitance and the preservation characteristics under charged state etc. is provided and can be used in nonaqueous electrolytic solution in this lithium secondary battery about above-mentioned secondary lithium batteries nonaqueous electrolytic solution.
The inventor studies for addressing the above problem, found that by contain dialkyl oxalate and carbonic acid ethenylidene ester and/or 1 simultaneously in nonaqueous electrolytic solution, 3-third sultone is as additive, in lithium secondary battery, particularly long-term cycle characteristics improves.
That is, the invention provides a kind of lithium secondary battery, the nonaqueous electrolytic solution that it comprises positive pole, negative pole and obtains by be dissolved with electrolytic salt in nonaqueous solvents is characterized in that positive pole is the material that contains lithium composite xoide; Negative pole is the material that contains graphite; In nonaqueous electrolytic solution, contain dialkyl oxalate, and contain carbonic acid ethenylidene ester and/or 1,3-third sultone.
Embodiment
In the present invention, in nonaqueous electrolytic solution with carbonic acid ethenylidene ester (VC) and/or 1,3-third sultone (PS) together and with and the content of the dialkyl oxalate that contains has served as for a long time that battery performance can reduce, can not get desired sufficient battery performance and served as after a little while.Therefore, its content considers from the effect aspect that improves cycle characteristics, with respect to the weight of nonaqueous electrolytic solution, and normally 0.01-10 weight %, preferably 0.1-4 weight %, the special preferably scope of 0.5-3 weight %.
In the present invention, as the alkyl of the dialkyl oxalate that contains in nonaqueous electrolytic solution, the carbon number that can exemplify out methyl, ethyl, propyl group, isopropyl, butyl, hexyl, octyl group, decyl, dodecyl etc. is the alkyl of 1-12.As the concrete example of dialkyl oxalate, can enumerate dimethyl oxalate, diethy-aceto oxalate, dipropyl oxalate, oxalic acid diisopropyl ester, dibutyl oxalate, oxalic acid dihexyl, oxalic acid dioctyl ester, oxalic acid didecyl ester, oxalic acid two (dodecyl) ester.
In these materials, dimethyl oxalate has inhibition propylene carbonate (PC) and decomposes this special effect, therefore uses the occasion of PC as the nonaqueous solvents of secondary lithium batteries, considers preferred dimethyl oxalate from the viewpoint that suppresses the PC decomposition.In addition, consider that from the viewpoint of the wetability that improves barrier film the carbon number of the alkyl of preferred oxalic acid dihexyl, oxalic acid dioctyl ester, oxalic acid didecyl ester, oxalic acid two (dodecyl) ester etc. is the dialkyl oxalate of 6-12.
Good considered the different asymmetrical dialkyl oxalate of preferred 2 alkyl by the viewpoint of overlay film from forming at negative pole.For example oxalic acid ethyl-methyl ester, oxalic acid propyl group methyl ester, oxalic acid butyl methyl ester and so on have methyl and carbon number be 2-4 alkyl, asymmetrical dialkyl oxalate and oxalic acid ethyl propyl ester, oxalic acid ethyl-butyl ester and so on have ethyl and carbon number is alkyl, the asymmetrical dialkyl oxalate of 3-4, owing to have the effect that improves cycle characteristics and form good by the effect of overlay film, so be preferred.Among these materials, oxalic acid ethyl-methyl ester most preferably.
In addition, for example oxalic acid hexyl methyl ester, oxalic acid heptyl methyl ester, oxalic acid octyl group methyl ester, oxalic acid nonyl methyl ester, oxalic acid decyl methyl ester, oxalic acid undecyl methyl ester, oxalic acid dodecyl methyl ester, oxalic acid hexyl ethyl ester, oxalic acid octyl group ethyl ester, oxalic acid decyl ethyl ester, oxalic acid dodecyl ethyl ester and so on, to have carbon number be that 1 or 2 alkyl and carbon number are the dialkyl oxalate of the alkyl of 6-12 because have the effect of the wetability that improves barrier film simultaneously and form good by the effect of overlay film so preferred especially.Among these materials, most preferably has the dialkyl oxalate that methyl and carbon number are the alkyl of 6-8.
In the present invention, the content of the carbonic acid ethenylidene ester that contains in nonaqueous electrolytic solution has served as for a long time that battery performance can reduce, and can not get desired sufficient battery performance and served as after a little while.Therefore, described content considers from the effect aspect that improves cycle characteristics, with respect to the weight of nonaqueous electrolytic solution, and normally 0.01-20 weight %, preferably 0.05-10 weight %, the special preferably scope of 0.1-5 weight %.
In the present invention, in nonaqueous electrolytic solution, contain 1, the content of 3-third sultone has served as for a long time that battery performance can reduce, and can not get desired sufficient battery performance and served as after a little while.Therefore, described content considers from the effect aspect that improves cycle characteristics, with respect to the weight of nonaqueous electrolytic solution, and normally 0.01-20 weight %, preferably 0.05-10 weight %, the special preferably scope of 0.1-4 weight %.
As the nonaqueous solvents that uses in the present invention, for example can enumerate the compound etc. that (a) cyclic carbonates, (b) linear carbonate class, (c) lactone, (d) ethers, (e) ester class, (f) nitrile, (g) amide-type, (h) contain S=O.
As (a) cyclic carbonates, for example preferably from ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), carbonic acid dimethyl ethenylidene ester (DMVC), ethylene thiazolinyl ethylidene ester (VEC), select at least a kind or multiple.Among these materials, more preferably comprise ethylene carbonate (EC), propylene carbonate (PC).
As (b) linear carbonate class, preferably from dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), carbonic acid methyl propargyl ester (MPC), carbonic acid ethyl propargyl ester (EPC), carbonic acid dipropargyl ester (DPC), dipropyl carbonate, methylbutyl carbonate, dibutyl carbonate, select at least a kind or multiple.Among these materials, more preferably comprise dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), carbonic acid methyl propargyl ester (MPC), most preferably comprise methyl ethyl carbonate.
As (c) lactone, can exemplify out gamma-butyrolacton (GBL), gamma-valerolactone, alpha-angelica lactone etc.
As (d) ethers, can exemplify out oxolane, 2-methyltetrahydrofuran, 1,4-diox, 1,2-diethoxyethane, 1,2-dibutoxy ethane etc.
As (e) ester class, can exemplify out methyl propionate, methyl trimethylacetate, trimethylace tonitric butyl ester, trimethylace tonitric monooctyl ester etc.
As (f) nitrile, can exemplify out acetonitrile etc., as (g) amide-type, can exemplify out dimethyl formamide etc., the compound that contains S=O as (h), can exemplify out methanesulfonic acid propargyl ester, sulfurous acid diol ester, sulfurous acid propylidene ester, sulfuric acid diol ester, sulfuric acid propylidene ester, sulfurous acid dipropargyl ester, sulfurous acid methyl propargyl ester, divinylsulfone, 1,4-butanediol two methanesulfonates etc.
For the combination of these nonaqueous solventss, for example can enumerate the combination, (a) cyclic carbonates of the combination, (a) cyclic carbonates of the combination, (a) cyclic carbonates of the combination, (a) cyclic carbonates of (a) cyclic carbonates and (b) linear carbonate class and (c) lactone and (b) linear carbonate class and (c) lactone and (b) linear carbonate class and (d) ethers and (b) linear carbonate class and (e) all combinations such as combination of ester class.
Among these combinations, preferably comprise (a) cyclic carbonates and (b) combination of linear carbonate class.For the Capacity Ratio [(a)/{ (a)+(b) }] under the situation of (a) cyclic carbonates and (b) combination of linear carbonate class, consider from the viewpoint that improves cycle characteristics, normally the scope of 0.1-1, preferred 0.2-0.4, preferred especially 0.25-0.35.
Among these solvent systems, the nonaqueous solvents that comprises the combination of PC and DMC, EC and MEC, EC and DEC, occasion in the scope that is in above-mentioned [(a)/{ (a)+(b) }] (Capacity Ratio) shows high cycle characteristics, therefore especially preferably as the secondary lithium batteries nonaqueous electrolytic solution.
In addition, also preferably comprise (a) cyclic carbonates and (c) combination of lactone.For the Capacity Ratio [(a)/{ (a)+(c) }] under the situation of (a) cyclic carbonates and (c) combination of lactone, consider from the viewpoint that improves cycle characteristics and wetability, normally the scope of 0.05-0.8, preferred 0.1-0.6, preferred especially 0.2-0.4.
Among these solvent systems, the nonaqueous solvents that comprises the combination of EC and GBL, VC and GBL, occasion in the scope that is in above-mentioned [(a)/{ (a)+(c) }] (Capacity Ratio), show high cycle characteristics, wetability to barrier film improves simultaneously, therefore especially preferably as the secondary lithium batteries nonaqueous electrolytic solution.
Among the above-mentioned nonaqueous solvents, preferably use carbonic acid dimethyl ethenylidene ester (DMVC), ethylene thiazolinyl ethylidene ester (VEC), alpha-angelica lactone, divinylsulfone etc. to contain a kind of the compound of two keys or multiple.
In addition, further preferably carbonic acid methyl propargyl ester (MPC), carbonic acid ethyl propargyl ester (EPC), carbonic acid dipropargyl ester (DPC), oxalic acid dipropargyl ester, oxalic acid methyl propargyl ester, oxalic acid ethyl propargyl ester, methanesulfonic acid propargyl ester, sulfurous acid dipropargyl ester, sulfurous acid methyl propargyl ester etc. are contained a kind of the compound of triple bond or multiplely use with the above-mentioned compound that contains two keys.
Particularly in high-capacity battery, when increasing the electrode composition density of battery, can see that cycle characteristics reduces, but when being used in combination above-mentioned compound that contains two keys and/or the above-mentioned compound that contains triple bond with dialkyl oxalate compound of the present invention, cycle characteristics improves, so be preferred.
Consider from the aspect of the effect that improves cycle characteristics, and usefulness above-mentioned contain the compound or the above-mentioned content that contains the compound of triple bond of two keys, the volume all with respect to nonaqueous electrolytic solution is that the scope of 0.01-20 capacity %, preferred 0.05-10 capacity %, preferred especially 0.1-5 capacity % is favourable.
As the electrolytic salt that uses in the present invention, for example can enumerate LiPF
6, LiBF
4, LiClO
4Deng.In addition, can exemplify out LiN (SO
2CF
3)
2, LiN (SO
2C
2F
5)
2, LiC (SO
2CF
3)
3, LiPF
4(CF
3)
2, LiPF
3(C
2F
5)
3, LiPF
3(CF
3)
3, LiPF
3(different-C
3F
7)
3, LiPF
5(different-C
3F
7) wait the lithium salts and the (CF that contain chain-like alkyl
2)
2(SO
2)
2NLi, (CF
2)
3(SO
2)
2NLi etc. contain the lithium salts of cyclic alkylidene chain.In these electrolytic salts, consider preferred LiPF from the viewpoint of conductivity
6, LiBF
4, LiN (SO
2CF
3)
2, LiN (SO
2C
2F
5)
2
These electrolytic salts can use a kind, also can make up two or more uses.These electrolytic salts are dissolved in the above-mentioned nonaqueous solvents with the concentration of 0.1-3 mole (M), preferred 0.5-2.5M, further preferred 0.7-2.0M usually and use.
Electrolyte of the present invention for example by mixing above-mentioned nonaqueous solvents, dissolves above-mentioned electrolytic salt therein, dissolves above-mentioned dimethyl oxalate, dissolving carbonic acid ethenylidene ester and/or 1,3-third sultone and obtaining.
In addition, contain for example air or carbon dioxide, can suppress to take place and battery performances such as raising cycle characteristics and preservation characteristics by the gas due to the electrolyte decomposition by making nonaqueous electrolytic solution of the present invention.
Contain the method for (dissolving) carbon dioxide or air as making in the nonaqueous electrolytic solution in the present invention, can be (1) thus making nonaqueous electrolytic solution contact the method, (2) that make it to contain before in being injected into battery with air or the gas that contains carbon dioxide in advance injects wantonly a kind of method that the back made battery contain air or contains the gas of carbon dioxide before or after battery seal, can also make up these methods uses.Air or the gas that contains carbon dioxide is moisture-free as far as possible preferably, and preferably is in dew point-40 ℃ or low temperature more, especially preferably is in dew point-50 ℃ or low temperature more.
Nonaqueous electrolytic solution of the present invention is as the formation raw material use of secondary cell, particularly lithium secondary battery.Do not limit especially about the formation raw material beyond the nonaqueous electrolytic solution that constitutes secondary cell, can use all formation raw material that in the past used.
For example as positive active material, use and contain cobalt, manganese or nickel and composite metal oxide lithium.These positive active materials can only be selected a kind of use, can also make up two or more uses.As such composite metal oxide, for example can enumerate LiCoO
2, LiMn
2O
4, LiNiO
2, LiCo
1-xNi
xO
z(0.01＜x＜1) etc.In addition, also can look like LiCoO
2And LiMn
2O
4, LiCoO
2And LiNiO
2, LiMn
2O
4And LiNiO
2Like that suitably mix and use.
Among above positive active material, the open circuit voltage after preferred charging ends is that benchmark is shown as 4.3V or above lithium complex metal oxide with Li, for example LiCoO most preferably
2, LiMn
2O
4, LiNiO
2And so on the lithium complex metal oxide that contains Co or Ni.The part of these lithium complex metal oxides also can be used other element substitutions.LiCoO for example
2A part of Co can use displacements such as Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, Cu.
As the conductive agent of positive pole, then be not particularly limited if do not cause the electrically conductive material of chemical change.For example can enumerate carbon black classes such as graphite-likes such as native graphite (flaky graphite etc.), Delanium, acetylene black, section's qin carbon black, channel black, furnace black, dim, pyrolytic carbon black etc.In addition, also can suit admixed graphite class and carbon black class and use.The preferred 1-10 weight of the addition of conductive agent in anode mixture %, preferred especially 2-5 weight %.
As positive pole, make after the anode mixture conductive agents such as above-mentioned positive active material and acetylene black, carbon black and binding agent are mixing, with the calendering of this positive electrode on batten as the aluminium foil of collector body or stainless steel, temperature about 50 ℃-250 ℃ is in heat treated under the vacuum about 2 hours, thereby produces.As above-mentioned binding agent, can exemplify out copolymer (NBR), carboxymethyl cellulose (CMC) of copolymer (SBR), acrylonitrile and the butadiene of polytetrafluoroethylene (PTFE), Kynoar (PVDF), styrene and butadiene etc.
As negative pole (negative electrode active material), use can occlusion and is discharged the material of lithium, for example uses lithium metal or lithium alloy, and material with carbon element [thermally decomposed carbon class, coke class, graphite-like (Delanium, native graphite etc.), organic high molecular compound burner body, carbon fiber], tin or tin compound, silicon or silicon compound.In material with carbon element, the interplanar distance (d of preferred especially crystal face (002)
002) be below the 0.340nm, more preferably use the graphite-like of graphite mould crystal structure with interplanar distance 0.335-0.340nm.These negative electrode active materials can only be selected a kind of use, also can make up 2 kinds or more kinds of and use.
The dusty material of material with carbon element and so on, mixing with copolymer (NBR), the carboxymethyl cellulose binding agents such as (CMC) of copolymer (SBR), acrylonitrile and the butadiene of ethylene-propylene-diene terpolymers (EPDM), polytetrafluoroethylene (PTFE), Kynoar (PVDF), styrene and butadiene, make cathode agent and use.The manufacture method of negative pole does not limit especially, can adopt the method manufacturing same with the manufacture method of above-mentioned positive pole.
As dialkyl oxalate, the carbonic acid ethenylidene ester and/or 1 of additive of the present invention, the additive effect of 3-third sultone, the electrode composition density of battery is high more just big more.Considering from this viewpoint, is 3.2-4.0g/cm particularly preferably in the density of the anode mixture layer that forms on the aluminium foil
3, further preferred 3.3-3.9g/cm
3, 3.4-3.8g/cm most preferably
3When anode mixture density becomes the big 4.0g/cm of surpassing
3The time, make the difficulty that becomes in fact.The preferred 1.3-2.0g/cm of the density of the anode mixture layer that on Copper Foil, forms on the other hand,
3, further preferred 1.4-1.9g/cm
3, 1.5-1.8g/cm most preferably
3The density of anode mixture layer becomes the big 2.0g/cm of surpassing
3The time, make the difficulty that becomes in fact.
In addition, the electrode layers thickness of the above-mentioned positive pole among the present invention (the every single face of collector body) is 30-120 μ m preferably, further 50-100 μ m preferably, the electrode layers thickness of above-mentioned negative pole (the every single face of collector body) is 1-100 μ m preferably, further 3-70 μ m preferably.When the thickness of electrode material layer was thinner than above-mentioned scope, the active matter quality in electrode material layer reduced, so battery capacity diminishes.On the other hand, when described thickness was thicker than above-mentioned scope, cycle characteristics and speed characteristic reduced, so be not preferred.
The structure of lithium secondary battery does not limit especially, have positive pole, negative pole and single or multiple lift barrier film Coin-shaped battery and have the cylinder battery of positive pole, negative pole and drum barrier film or square battery etc. is listed as an example.Use known polyolefinic microporosity film, fabric, nonwoven fabrics etc. as barrier film.
In addition, battery separator can be arbitrary formation of individual layer perforated membrane and laminated porous film.The battery separator of Shi Yonging in the present invention, also according to creating conditions difference and difference, but the preferred 50-1000 second/100cc of air permeability, more preferably 100-800 second/100cc, most preferably 300-500 second/100cc.When air permeability was too high, lithium-ion-conducting reduced, and did not therefore give full play to as the function of battery separator, crossed when low when air permeability, and mechanical strength reduces, so be preferably above-mentioned scope.
In addition, the preferred 30-60% of the porosity of battery separator, more preferably 35-55%, most preferably 40-50%.Particularly when making porosity in this scope, the capacity characteristic of battery improves, so preferred.
And in order to increase energy density, preferred battery is thin as far as possible with the thickness of barrier film, but considers from two aspects such as mechanical strength, performances, preferred 5-50 μ m, more preferably 10-40 μ m, most preferably 15-25 μ m.
Lithium secondary battery among the present invention, the cycle characteristics in that end of charge voltage also has excellence chronically greater than the occasion of 4.2V particularly also has excellent cycle characteristics in the occasion as end of charge voltage is 4.3V.Final discharging voltage can be decided to be more than the 2.5V, and then can be decided to be more than the 2.8V.Do not limit especially about current value, but under the constant current discharge of 0.1-3C, use usually.In addition, the lithium secondary battery among the present invention can discharge and recharge at-40 ℃ to 100 ℃ these wide regions, but preferably discharges and recharges at 0-80 ℃.
As pressing the countermeasure that rises in the lithium secondary battery among the present invention, can valve safe in utilization on hush panel.In addition, the method for driving grooving on members such as battery can and sealing gasket also can be utilized.And, preferably possess in the past known various safety elements, for example as the fuse (being fuse) of anti-overcurrent element, bimetallic, PTC element at least a kind or multiple.
Lithium secondary battery among the present invention with a plurality of series connection and/or assembling in parallel, is contained in the battery pack as required.In battery pack, except safety elements such as PTC element, temperature fuse, fuse and/or electric current separating element, safety circuit can also be set, for example have all voltage of each battery of monitoring and/or Battery pack, temperature, electric current etc., cut off the circuit of the function of electric current.
Embodiment
Enumerate embodiment below and comparative example is described more specifically the present invention, but the present invention is not limited to following embodiment, also comprising can be from the various combination released of class easily of the purport of invention.Particularly be not limited to the combination of solvent cited among the embodiment.
Embodiment 1
[modulation of nonaqueous electrolytic solution]
Modulation propylene carbonate (PC): the nonaqueous solvents of dimethyl carbonate (DMC) (Capacity Ratio)=1: 2, dissolve the LiPF as electrolytic salt therein
6, and the feasible concentration that reaches 1M, thereby be modulated into nonaqueous electrolytic solution, afterwards again with respect to nonaqueous electrolytic solution, add dimethyl oxalate and also make it to reach 0.5 weight %, add carbonic acid ethenylidene ester (VC) and also make it to reach 2 weight %.
[making of lithium secondary battery and the mensuration of battery behavior]
With LiCoO
2(positive active material), acetylene black (conductive agent) and Kynoar (binding agent) are to be respectively the mixed of 90 weight %, 5 weight % and 5 weight %, add 1-Methyl-2-Pyrrolidone solvent and mixing therein, resulting mixture is coated on the aluminium foil, dry, extrusion forming, heat treated, thus positive pole made.Interplanar distance (the d that will have crystal face (002)
002) for the Delanium (negative electrode active material) of the graphite mould crystal structure of 0.335nm and Kynoar (binding agent) to be respectively the mixed of 95 weight % and 5 weight %, add 1-Methyl-2-Pyrrolidone solvent and mixing therein, resulting mixture is coated on the Copper Foil, dry, extrusion forming, heat treated, thus negative pole made.Use the barrier film of polypropylene microporosity film, inject after the above-mentioned nonaqueous electrolytic solution, battery is contained be in the air of dew point-60 ℃, made the cylinder battery (diameter 18mm, high 65mm) of 18650 sizes.In battery, be provided with pressure opening port and internal current partition apparatus (PTC element).At this moment, Zheng Ji electrode density is 3.6g/cm
3, the electrode density of negative pole is 1.7g/cm
3Anodal electrode layers thickness (the every single face of collector body) is 60 μ m, and the electrode layers thickness of negative pole (the every single face of collector body) is 60 μ m.
Use this 18650 battery, under normal temperature (20 ℃) with the constant current charge of 2.2A (1C) behind 4.2V, charging under constant voltage as final voltage 4.2V adds up to 3 hours.Then, under the constant current of 2.2A (1C), discharge into final voltage 2.8V, repeat this and discharge and recharge.The 1M LiPF of dimethyl oxalate is not added in initial discharge capacity and use
6-EC/DEC (capacity nonaqueous electrolytic solution 3/7) has measured the battery behavior after the circulation 200 times as the occasion (comparative example 2) of nonaqueous electrolytic solution roughly equal (1.00), and it is 84.2% that the result is designated as 100% o'clock discharge capacity sustainment rate with initial discharge capacity.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 2
As additive, with respect to nonaqueous electrolytic solution, the dimethyl oxalate of 1 weight %, the carbonic acid ethenylidene ester of 2 weight % have been used, modulate nonaqueous electrolytic solution in addition similarly to Example 1, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 85.7% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 3
As additive, with respect to nonaqueous electrolytic solution, the dimethyl oxalate of 2 weight %, the carbonic acid ethenylidene ester of 2 weight % have been used, modulate nonaqueous electrolytic solution in addition similarly to Example 1, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 86.1% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 4
As additive, with respect to nonaqueous electrolytic solution, the dimethyl oxalate of 4 weight %, the carbonic acid ethenylidene ester of 2 weight % have been used, modulate nonaqueous electrolytic solution in addition similarly to Example 1, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 84.3% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 5
As additive, with respect to nonaqueous electrolytic solution, the dimethyl oxalate of 2 weight %, the carbonic acid ethenylidene ester of 0.1 weight % have been used, modulate nonaqueous electrolytic solution in addition similarly to Example 1, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 83.3% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 6
As additive, with respect to nonaqueous electrolytic solution, the dimethyl oxalate of 2 weight %, the carbonic acid ethenylidene ester of 5 weight % have been used, modulate nonaqueous electrolytic solution in addition similarly to Example 1, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 83.4% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 7
As additive, with respect to nonaqueous electrolytic solution, used 2 weight % dimethyl oxalate, 0.1 weight % 1,3-third sultone (PS), modulate nonaqueous electrolytic solution in addition similarly to Example 1, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 82.8% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 8
As additive, with respect to nonaqueous electrolytic solution, used 2 weight % dimethyl oxalate, 2 weight % 1,3-third sultone, modulate nonaqueous electrolytic solution in addition similarly to Example 1, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 84.2% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 9
As additive, with respect to nonaqueous electrolytic solution, used 2 weight % dimethyl oxalate, 4 weight % 1,3-third sultone, modulate nonaqueous electrolytic solution in addition similarly to Example 1, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 82.7% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 10
As additive, with respect to nonaqueous electrolytic solution, used dimethyl oxalate, the 2 weight % of 2 weight % carbonic acid ethenylidene ester, 2 weight % 1,3-third sultone, modulate nonaqueous electrolytic solution in addition similarly to Example 1, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 87.0% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 11
As nonaqueous solvents, use ethylene carbonate (EC)/methyl ethyl carbonate (MEC) (Capacity Ratio 3/7); As additive, with respect to nonaqueous electrolytic solution, the dimethyl oxalate of 2 weight %, the carbonic acid ethenylidene ester of 1 weight % have been used, modulate nonaqueous electrolytic solution in addition similarly to Example 1, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 89.1% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 12
As nonaqueous solvents, use ethylene carbonate (EC)/methyl ethyl carbonate (MEC) (Capacity Ratio 3/7); As additive, with respect to nonaqueous electrolytic solution, used 2 weight % dimethyl oxalate, 1 weight % 1,3-third sultone, modulate nonaqueous electrolytic solution in addition similarly to Example 1, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 88.5% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 13
As nonaqueous solvents, use ethylene carbonate (EC)/carbonic acid diethyl ester (DEC) (Capacity Ratio 1/2); As additive, with respect to nonaqueous electrolytic solution, used dimethyl oxalate, the 1 weight % of 2 weight % carbonic acid ethenylidene ester, 1 weight % 1,3-third sultone, modulate nonaqueous electrolytic solution in addition similarly to Example 1, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 89.0% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 14
As positive active material, replace LiCoO
2Use LiMn
2O
4As additive, with respect to nonaqueous electrolytic solution, used dimethyl oxalate, the 1 weight % of 2 weight % carbonic acid ethenylidene ester, 1 weight % 1,3-third sultone is modulated nonaqueous electrolytic solution in addition similarly to Example 1, makes 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 74.8% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Comparative example 1
Modulation propylene carbonate (PC): the nonaqueous solvents of dimethyl carbonate (DMC) (Capacity Ratio)=1: 2, dissolved LiPF therein
6, and the feasible concentration that reaches 1M.Do not add dialkyl oxalate, carbonic acid ethenylidene esters, 1 such as dimethyl oxalate, 3-third sultone this moment fully.Use this nonaqueous electrolytic solution to make 18650 batteries similarly to Example 1, measured battery behavior, but can not discharge and recharge fully.
Comparative example 2
Modulation ethylene carbonate (EC): the nonaqueous solvents of diethyl carbonate (DEC) (Capacity Ratio)=3: 7, dissolved LiPF therein
6, and the feasible concentration that reaches 1M.Do not add dimethyl oxalate, carbonic acid ethenylidene ester, 1,3-third sultone this moment fully.Except having used this nonaqueous electrolytic solution, make 18650 batteries similarly to Example 1, measured battery behavior.With respect to initial discharge capacity, the discharge capacity sustainment rate after 200 circulations is 81.3%.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Comparative example 3
Modulation propylene carbonate (PC): the nonaqueous solvents of dimethyl carbonate (DMC) (Capacity Ratio)=1: 2, dissolved LiPF therein
6, and the feasible concentration that reaches 1M.Add the dimethyl oxalate of 2 weight %, do not add carbonic acid ethenylidene ester, 1 fully, 3-third sultone.Use this nonaqueous electrolytic solution to make 18650 batteries similarly to Example 1, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 71.2% as a result.Table 21 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Comparative example 4
Modulation propylene carbonate (PC): the nonaqueous solvents of dimethyl carbonate (DMC) (Capacity Ratio)=1: 2, dissolved LiPF therein
6, and the feasible concentration that reaches 1M.As additive, added the carbonic acid ethenylidene ester of 2 weight %, make 18650 batteries in addition similarly to Example 1, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 68.9% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Comparative example 5
Modulation propylene carbonate (PC): the nonaqueous solvents of dimethyl carbonate (DMC) (Capacity Ratio)=1: 2, dissolved LiPF therein
6, and the feasible concentration that reaches 1M.As additive, added 1 of 2 weight %, 3-third sultone is made 18650 batteries in addition similarly to Example 1, has measured the battery behavior after the circulation 200 times, and the discharge capacity sustainment rate is 66.9% as a result.
Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Comparative example 6
Modulation propylene carbonate (PC): the nonaqueous solvents of dimethyl carbonate (DMC) (Capacity Ratio)=1: 2, dissolved LiPF therein
6, and the feasible concentration that reaches 1M.At this moment,, add the dimethyl oxalate of 5 weight %, do not add carbonic acid ethenylidene ester, 1 fully, 3-third sultone as additive.Use this nonaqueous electrolytic solution to make 18650 batteries similarly to Example 1, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 81.7% as a result.Table 1 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Table 1
| Anodal | Dialkyl oxalate | VC | PS | Electrolyte is formed (Capacity Ratio) | Initial discharge capacity (relative value) | 200 cyclic discharge capacity sustainment rates (%) | ||
| The kind of alkyl | Addition (wt%) | Addition (wt%) | Addition (wt%) | |||||
| Embodiment 1 | LiCoO 2 | Dimethyl | 0.5 | 2 | 0 | 1M LiPF6PC/DMC＝1/2 | 1.00 | 84.2 |
| Embodiment 2 | LiCoO 2 | Dimethyl | 1 | 2 | 0 | 1M LiPF6PC/DMC＝1/2 | 1.01 | 85.7 |
| Embodiment 3 | LiCoO 2 | Dimethyl | 2 | 2 | 0 | 1M LiPF6PC/DMC＝1/2 | 1.01 | 86.1 |
| Embodiment 4 | LiCoO 2 | Dimethyl | 4 | 2 | 0 | 1M LiPF6PC/DMC＝1/2 | 1.01 | 84.3 |
| Embodiment 5 | LiCoO 2 | Dimethyl | 2 | 0.1 | 0 | 1M LiPF6PC/DMC＝1/2 | 1.00 | 83.3 |
| Embodiment 6 | LiCoO 2 | Dimethyl | 2 | 5 | 0 | 1M LiPF6PC/DMC＝1/2 | 1.01 | 83.4 |
| Embodiment 7 | LiCoO 2 | Dimethyl | 2 | 0 | 0.1 | 1M LiPF6PC/DMC＝1/2 | 1.00 | 82.8 |
| Embodiment 8 | LiCoO 2 | Dimethyl | 2 | 0 | 2 | 1M LiPF6PC/DMC＝1/2 | 1.01 | 84.2 |
| Embodiment 9 | LiCoO 2 | Dimethyl | 2 | 0 | 4 | 1M LiPF6PC/DMC＝1/2 | 1.01 | 82.7 |
| Embodiment 10 | LiCoO 2 | Dimethyl | 2 | 2 | 2 | 1M LiPF6PC/DMC＝1/2 | 1.02 | 87.0 |
| Embodiment 11 | LiCoO 2 | Dimethyl | 2 | 1 | 0 | 1M LiPF6EC/MEC＝3/7 | 1.02 | 89.1 |
| Embodiment 12 | LiCoO 2 | Dimethyl | 2 | 0 | 1 | 1M LiPF6EC/MEC＝3/7 | 1.01 | 88.5 |
| Embodiment 13 | LiCoO 2 | Dimethyl | 2 | 1 | 1 | 1M LiPF6EC/DEC＝1/2 | 1.01 | 89.0 |
| Embodiment 14 | LiMn 2O 4 | Dimethyl | 2 | 1 | 1 | 1M LiPF6PC/DMC＝1/2 | 0.87 | 74.8 |
| Comparative example 1 | LiCoO 2 | Do not have | 0 | 0 | 0 | 1M LiPF6PC/DMC＝1/2 | -- | Can not discharge and recharge |
| Comparative example 2 | LiCoO 2 | Do not have | 0 | 0 | 0 | 1M LiPF6EC/DEC＝3/7 | 1 | 81.3 |
| Comparative example 3 | LiCoO 2 | Dimethyl | 2 | 0 | 0 | 1M LiPF6PC/DMC＝1/2 | 0.99 | 71.2 |
| Comparative example 4 | LiCoO 2 | Do not have | 0 | 2 | 0 | 1M LiPF6PC/DMC＝1/2 | 0.99 | 68.9 |
| Comparative example 5 | LiCoO 2 | Do not have | 0 | 0 | 2 | 1M LiPF6PC/DMC＝1/2 | 0.99 | 66.9 |
| Comparative example 6 | LiCoO 2 | Dimethyl | 5 | 0 | 0 | 1M LiPF6PC/DMC＝1/2 | 1.00 | 81.7 |
Embodiment 15
[modulation of nonaqueous electrolytic solution]
As nonaqueous solvents, use ethylene carbonate (EC)/gamma-butyrolacton (GBL) (Capacity Ratio 2/8), dissolve LiPF therein
6And LiBF
4, and make the concentration reach 0.9M, 0.1M respectively, thereby modulate nonaqueous electrolytic solution, and, as additive, with respect to nonaqueous electrolytic solution, add 5 weight % dimethyl oxalate, 2 weight % 1,3-third sultone.
[making of lithium secondary battery and the mensuration of battery behavior]
With LiCoO
2(positive active material), acetylene black (conductive agent) and Kynoar (binding agent) are to be respectively the mixed of 90 weight %, 5 weight % and 5 weight %, add 1-Methyl-2-Pyrrolidone solvent and mixing therein, resulting mixture is coated on the aluminium foil, dry, extrusion forming, heat treated has prepared positive pole.Interplanar distance (the d that will have crystal face (002)
002) for the Delanium (negative electrode active material) of the graphite mould crystal structure of 0.336nm, Kynoar (binding agent) to be respectively the mixed of 95 weight % and 5 weight %, add 1-Methyl-2-Pyrrolidone solvent and mixing therein, resulting mixture is coated on the Copper Foil, dry, extrusion forming, heat treated has prepared negative pole.Use the barrier film of polypropylene microporosity film, inject after the above-mentioned nonaqueous electrolytic solution, battery is contained be in the carbon dioxide of dew point-60 ℃, made the cylinder battery (diameter 18mm, high 65mm) of 18650 sizes.In battery, be provided with pressure opening port and internal current partition apparatus (PTC element).At this moment, Zheng Ji electrode density is 3.4g/cm
3, the electrode density of negative pole is 1.4g/cm
3Anodal electrode layers thickness (the every single face of collector body) is 70 μ m, and the electrode layers thickness of negative pole (the every single face of collector body) is 75 μ m.
Use this 18650 battery, under normal temperature (20 ℃) with the constant current charge of 0.6A (0.3C) behind 4.2V, charging under constant voltage as final voltage 4.2V adds up to 5 hours.Then, under the constant current of 0.6A (0.3C), discharge into final voltage 2.8V, repeat this and discharge and recharge.Measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 81.3% as a result.Table 2 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 16
As additive, with respect to nonaqueous electrolytic solution, used dibutyl oxalate, the 2 weight % of 4 weight % carbonic acid ethenylidene ester, 2 weight % 1,3-third sultone, modulate nonaqueous electrolytic solution in addition similarly to Example 15, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 81.0% as a result.Table 2 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 17
As additive, with respect to nonaqueous electrolytic solution, the oxalic acid dihexyl of 3 weight %, the carbonic acid ethenylidene ester of 3 weight % have been used, do not use 1,3-third sultone is modulated nonaqueous electrolytic solution in addition similarly to Example 15, makes 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 81.1% as a result.Table 2 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 18
As additive, with respect to nonaqueous electrolytic solution, used oxalic acid dioctyl ester, the 2 weight % of 2 weight % carbonic acid ethenylidene ester, 2 weight % 1,3-third sultone, modulate nonaqueous electrolytic solution in addition similarly to Example 15, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 82.7% as a result.Table 2 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 19
As additive, with respect to nonaqueous electrolytic solution, oxalic acid two (dodecyl) ester of 1 weight %, the carbonic acid ethenylidene ester of 3 weight % have been used, do not use 1,3-third sultone is modulated nonaqueous electrolytic solution in addition similarly to Example 15, makes 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 80.5% as a result.Table 2 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Comparative example 7
As additive, with respect to nonaqueous electrolytic solution, used the carbonic acid ethenylidene ester of 3 weight %, do not use dialkyl oxalate and 1,3-third sultone is modulated nonaqueous electrolytic solution in addition similarly to Example 15, makes 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 65.4% as a result.Table 2 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Table 2
| Anodal | Dialkyl oxalate | VC | PS | Electrolyte is formed (Capacity Ratio) | Initial discharge capacity (relative value) | 200 cyclic discharge capacity sustainment rates (%) | ||
| The kind of alkyl | Addition (wt%) | Addition (wt%) | Addition (wt%) | |||||
| Embodiment 15 | LiCoO 2 | Dimethyl | 5 | 2 | 2 | 1M(LiPF6/LiBF4＝9/1) EC/GBL＝2/8 | 1.00 | 81.3 |
| Embodiment 16 | LiCoO 2 | Dibutyl | 4 | 2 | 2 | 1M(LiPF6/LiBF4＝9/1) EC/GBL＝2/8 | 100 | 81.0 |
| Embodiment 17 | LiCoO 2 | Dihexyl | 3 | 3 | 0 | 1M(LiPF6/LiBF4＝9/1) EC/GBL＝2/8 | 1.00 | 81.1 |
| Embodiment 18 | LiCoO 2 | Dioctyl | 2 | 2 | 2 | 1M(LiPF6/LiBF4＝9/1) EC/GBL＝2/8 | 1.00 | 82.7 |
| Embodiment 19 | LiCoO 2 | Two (dodecyls) | 1 | 3 | 0 | 1M(LiPF6/LiBF4＝9/1) EC/GBL＝2/8 | 1.00 | 80.5 |
| Comparative example 7 | LiCoO 2 | Do not have | 0 | 3 | 0 | 1M(LiPF6/LiBF4＝9/1) EC/GBL＝2/8 | 0.97 | 65.4 |
Embodiment 20, embodiment 21
[wetability evaluation] adopts following method to carry out the evaluation of wetability.That is, with barrier film (the polypropylene microporosity film of CELGARDInc. system; The dipping of the electrolyte that obtains during CELGARDO 2500# (trade mark)) for the various dialkyl oxalate that adds ormal weight in the solution of 1M LiPF6 carbonic acid ethenylidene ester (VC)/gamma-butyrolacton (GBL)=2.5/97.5 (Capacity Ratio) [VC/GBL=3/97 (weight ratio)] is estimated as wetability.Make it dipping, the dipping of the barrier film of Visual Confirmation after 20 seconds.
Table 3 is expressed its result.In the table 3, * expression is not wetting, △ represents wetting a little, zero state that expression is wetting substantially, ◎ represents complete wetting.
As can be known from the results of Table 3, the carbon number of the alkyl of alcohol residue is the dialkyl oxalate more than 6, is that 2 dimethyl oxalate and carbon number are 4 dibutyl oxalate height to the affinity of barrier film than the carbon number of the alkyl of pure residue, therefore, contact following time when placing, be impregnated into rapidly in the loose structure of barrier film with the microporosity barrier film.This makes the manufacturing time in the manufacturing process of lithium secondary battery shorten.Promptly, in the manufacturing process of lithium secondary battery, in battery case, install by after positive wafer thin, barrier film, the laminar duplexer of negative pole, filling electrolyte, the operation of the lid of battery case then is installed, the installation of this lid, the electrolyte displacement that needs to be filled be present in the air in the microporosity structure of barrier film, and after being filled in this microporosity structure and implement.Therefore, by using the electrolyte in the microporosity structure that is impregnated into barrier film in the short time, realize the shortening of the manufacturing time of lithium secondary battery.
Table 3
| Weight (%) | Dimethyl oxalate | Dibutyl oxalate | The oxalic acid dihexyl | The oxalic acid dioctyl ester | Oxalic acid didecyl ester | Oxalic acid two (dodecyl) ester | |
| Embodiment 20 | 3 | × | △ | ○ | ◎ | ◎ | ◎ |
| Embodiment 21 | 2 | × | × | △ | ○ | ○ | ○ |
Embodiment 22
[modulation of nonaqueous electrolytic solution]
As nonaqueous solvents, use propylene carbonate (PC)/dimethyl carbonate (DMC) (Capacity Ratio 1/2), dissolved LiPF therein
6, and the feasible concentration that reaches 1M, modulate nonaqueous electrolytic solution, and, as additive,, add the oxalic acid ethyl-methyl ester of 1 weight %, the carbonic acid ethenylidene ester of 2 weight % with respect to nonaqueous electrolytic solution.
[making of lithium secondary battery and the mensuration of battery behavior]
With LiCoO
2(positive active material), acetylene black (conductive agent), Kynoar (binding agent) are to be respectively the mixed of 90 weight %, 5 weight % and 5 weight %, add 1-Methyl-2-Pyrrolidone solvent and mixing therein, resulting mixture is coated on the aluminium foil, dry, extrusion forming, heat treated, thus positive pole made.Interplanar distance (the d that will have crystal face (002)
002) for the Delanium (negative electrode active material) of the graphite mould crystal structure of 0.336nm, Kynoar (binding agent) to be respectively the mixed of 95 weight % and 5 weight %, add 1-Methyl-2-Pyrrolidone solvent and mixing therein, resulting mixture is coated on the Copper Foil, dry, extrusion forming, heat treated has prepared negative pole.Use the barrier film of polypropylene microporosity film, inject after the above-mentioned nonaqueous electrolytic solution, battery is contained be in the carbon dioxide of dew point-60 ℃, made the cylinder battery (diameter 18mm, high 65mm) of 18650 sizes.In battery, be provided with pressure opening port and internal current partition apparatus (PTC element).At this moment, Zheng Ji electrode density is 3.4g/cm
3, the electrode density of negative pole is 1.4g/cm
3Anodal electrode layers thickness (the every single face of collector body) is 70 μ m, and the electrode layers thickness of negative pole (the every single face of collector body) is 75 μ m.
Use this 18650 battery, under normal temperature (20 ℃) with the constant current charge of 0.6A (0.3C) behind 4.2V, charging under constant voltage as final voltage 4.2V adds up to 5 hours.Then, under the constant current of 0.6A (0.3C), discharge into final voltage 2.8V, repeat this and discharge and recharge.Initial discharge capacity will add the 1M LiPF of the dimethyl malenate of 2 weight % with replacing dialkyl oxalate
6-EC/DEC (Capacity Ratio 3/7) is 1.01 as occasion (comparative example 9) ratio that nonaqueous electrolytic solution uses, and has measured the battery behavior after the circulation 200 times, and the discharge capacity sustainment rate is 86.3% as a result.Table 4 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 23
As additive, with respect to nonaqueous electrolytic solution, used 2 weight % oxalic acid ethyl-methyl ester, 2 weight % 1,3-third sultone, modulate nonaqueous electrolytic solution in addition similarly to Example 22, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 85.1% as a result.Table 4 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 24
Use ethylene carbonate (EC)/methyl ethyl carbonate (MEC) (Capacity Ratio 3/7) as nonaqueous solvents, as additive, with respect to nonaqueous electrolytic solution, the oxalic acid ethyl-methyl ester of 2 weight %, the carbonic acid ethenylidene ester of 1 weight % have been used, modulate nonaqueous electrolytic solution in addition similarly to Example 22, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 89.4% as a result.Table 4 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 25
Use ethylene carbonate (EC)/methyl ethyl carbonate (MEC) (Capacity Ratio 3/7) as nonaqueous solvents, as additive, with respect to nonaqueous electrolytic solution, used 2 weight % oxalic acid ethyl-methyl ester, 1 weight % 1,3-third sultone is modulated nonaqueous electrolytic solution in addition similarly to Example 22, makes 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 88.9% as a result.Table 4 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 26
Use ethylene carbonate (EC)/carbonic acid diethyl ester (DEC) (Capacity Ratio 1/2) as nonaqueous solvents, as additive, with respect to nonaqueous electrolytic solution, used oxalic acid ethyl-methyl ester, the 1 weight % of 2 weight % carbonic acid ethenylidene ester, 1 weight % 1,3-third sultone is modulated nonaqueous electrolytic solution in addition similarly to Example 22, makes 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 90.2% as a result.Table 4 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Comparative example 8
As additive,, replace the dialkyl oxalate of oxalic acid ethyl-methyl ester and so on respect to nonaqueous electrolytic solution, used the dimethyl malenate of 2 weight %, do not use carbonic acid ethenylidene ester and 1,3-third sultone has been modulated nonaqueous electrolytic solution in addition similarly to Example 22.Use this nonaqueous electrolytic solution to make 18650 batteries similarly to Example 22, measured battery behavior, but can not discharge and recharge fully.
Comparative example 9
Use ethylene carbonate (EC)/carbonic acid diethyl ester (DEC) (Capacity Ratio 3/7) as nonaqueous solvents, as additive, with respect to nonaqueous electrolytic solution, the dialkyl oxalate that replaces oxalic acid ethyl-methyl ester and so on, used the dimethyl malenate of 2 weight %, do not use carbonic acid ethenylidene ester and 1,3-third sultone, modulate nonaqueous electrolytic solution in addition similarly to Example 22, make 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 78.4% as a result.Table 4 shows the manufacturing conditions and the battery behavior of 18650 batteries.
Table 4
| Anodal | Dialkyl oxalate | VC | PS | Electrolyte is formed (Capacity Ratio) | Initial discharge capacity (relative value) | 20 cyclic discharge capacity sustainment rates (%) | ||
| The kind of alkyl | Addition (wt%) | Addition (wt%) | Addition (wt%) | |||||
| Embodiment 22 | LiCoO 2 | Ethyl-methyl | 1 | 2 | 0 | 1M LiPF6PC/DMC＝1/2 | 1.01 | 86.3 |
| Embodiment 23 | LiCoO 2 | Ethyl-methyl | 2 | 0 | 2 | 1M LiPF6PC/DMC＝1/2 | 1.01 | 85.1 |
| Embodiment 24 | LiCoO 2 | Ethyl-methyl | 2 | 1 | 0 | 1M LiPF6EC/MEC＝3/7 | 1.02 | 89.4 |
| Embodiment 25 | LiCoO 2 | Ethyl-methyl | 2 | 0 | 1 | 1M LiPF6EC/MEC＝3/7 | 1.01 | 88.9 |
| Embodiment 26 | LiCoO 2 | Ethyl-methyl | 2 | 1 | 1 | 1M LiPF6EC/DEC＝1/2 | 1.01 | 90.2 |
| Comparative example 8 | LiCoO 2 | Dimethyl malenate | 2 | 0 | 0 | 1M LiPF6PC/DMC＝1/2 | Can not discharge and recharge | |
| Comparative example 9 | LiCoO 2 | Dimethyl malenate | 2 | 0 | 0 | 1M LiPF6EC/DEC＝3/7 | 1 | 78.4 |
Embodiment 27
As nonaqueous solvents, use ethylene carbonate (EC)/methyl ethyl carbonate (MEC) (Capacity Ratio 3/7); As additive, with respect to nonaqueous electrolytic solution, use the oxalic acid ethyl-methyl ester of 1 weight %, the carbonic acid ethenylidene ester of 1 weight %, the carbonic acid methyl propargyl ester (MPC) of 1 weight %, modulated nonaqueous electrolytic solution in addition similarly to Example 22, made 18650 batteries.Initial discharge capacity will add the 1M LiPF of the dimethyl malenate of 2 weight % with replacing dialkyl oxalate
6-EC/DEC (Capacity Ratio 3/7) is 1.02 as occasion (comparative example 9) ratio that nonaqueous electrolytic solution uses, and has measured the battery behavior after the circulation 200 times, and the discharge capacity sustainment rate is 90.1% as a result.
Embodiment 28
As nonaqueous solvents, use ethylene carbonate (EC)/gamma-butyrolacton (GBL) (Capacity Ratio 2/8), dissolve LiPF therein
6And LiBF
4And the feasible concentration that reaches 0.9M, 0.1M respectively, thereby modulate nonaqueous electrolytic solution, and, as additive, with respect to nonaqueous electrolytic solution, use the oxalic acid hexyl methyl ester of 3 weight %, the carbonic acid ethenylidene ester of 3 weight %, modulated nonaqueous electrolytic solution in addition similarly to Example 22, made 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 81.8% as a result.Table 5 is expressed the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 29
As nonaqueous solvents, use ethylene carbonate (EC)/gamma-butyrolacton (GBL) (Capacity Ratio 2/8), dissolve LiPF therein
6And LiBF
4And the feasible concentration that reaches 0.9M, 0.1M respectively, thereby modulate nonaqueous electrolytic solution, and, as additive, with respect to nonaqueous electrolytic solution, use the oxalic acid octyl group methyl ester of 2 weight %, the carbonic acid ethenylidene ester of 3 weight %, modulated nonaqueous electrolytic solution in addition similarly to Example 22, made 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 82.3% as a result.Table 5 is expressed the manufacturing conditions and the battery behavior of 18650 batteries.
Embodiment 30
As nonaqueous solvents, use ethylene carbonate (EC)/gamma-butyrolacton (GBL) (Capacity Ratio 2/8), dissolve LiPF therein
6And LiBF
4And the feasible concentration that reaches 0.9M, 0.1M respectively, thereby modulate nonaqueous electrolytic solution, and, as additive, with respect to nonaqueous electrolytic solution, use the oxalic acid dodecyl methyl ester of 1 weight %, the carbonic acid ethenylidene ester of 3 weight %, modulated nonaqueous electrolytic solution in addition similarly to Example 22, made 18650 batteries, measured the battery behavior after the circulation 200 times, the discharge capacity sustainment rate is 81.2% as a result.Table 5 is expressed the manufacturing conditions and the battery behavior of 18650 batteries.
Table 5
| Anodal | Dialkyl oxalate | VC | PS | Electrolyte is formed (Capacity Ratio) | Initial discharge capacity (relative value) | 200 cyclic discharge capacity sustainment rates (%) | ||
| The kind of alkyl | Addition (wt%) | Addition (wt%) | Addition (wt%) | |||||
| Embodiment 28 | LiCoO 2 | Hexyl methyl | 3 | 3 | 0 | 1M(LiPF6/LiBF4＝9/1) EC/GBL＝2/8 | 1.00 | 81.8 |
| Embodiment 29 | LiCoO 2 | The octyl group methyl | 2 | 3 | 0 | 1M(LiPF6/LiBF4＝9/1) EC/GBL＝2/8 | 1.00 | 82.3 |
| Embodiment 30 | LiCoO 2 | Dodecyl methyl | 1 | 3 | 0 | 1M(LiPF6/LiBF4＝9/1) EC/GBL＝2/8 | 1.00 | 81.2 |
Embodiment 31, embodiment 32
As dialkyl oxalate, change use amount about oxalic acid hexyl methyl ester, oxalic acid octyl group methyl ester, oxalic acid dodecyl methyl ester, carried out the evaluation of wetability similarly to Example 20.
Table 6 is expressed its result.In the table 6, that △ represents is wetting a little, zero state that expression is roughly wetting, ◎ represents complete wetting.
From the result of table 6, oxalic acid hexyl methyl ester, oxalic acid octyl group methyl ester, oxalic acid dodecyl methyl ester all demonstrate excellent wetability, even particularly oxalic acid octyl group methyl ester, a small amount of interpolation of oxalic acid dodecyl methyl ester, wetability is also excellent.
Table 6
| Weight (%) | Oxalic acid hexyl methyl ester | Oxalic acid octyl group methyl ester | Oxalic acid dodecyl methyl ester | |
| Embodiment 31 | 3 | ○ | ◎ | ◎ |
| Embodiment 32 | 2 | △ | ○ | ○ |
The foregoing description is about 18650 batteries, but the present invention also is applicable to the battery of cylindrical shape, prismatic, stacked-up type.
According to the present invention, can provide battery battery behavior excellence such as long-term cycle characteristics, capacitance, preservation characteristics lithium secondary battery and can be used in nonaqueous electrolytic solution in this lithium secondary battery.
Claims (9)
1. lithium secondary battery, the nonaqueous electrolytic solution that it comprises positive pole, negative pole and obtains by be dissolved with electrolytic salt in nonaqueous solvents is characterized in that positive pole is the material that contains lithium composite xoide; Negative pole is the material that contains graphite; In described nonaqueous electrolytic solution, contain dialkyl oxalate, and contain carbonic acid ethenylidene ester and/or 1,3-third sultone.
2. lithium secondary battery according to claim 1, wherein, the alkyl of described dialkyl oxalate is that carbon number is the alkyl of 1-12.
3. lithium secondary battery according to claim 1 and 2, wherein, weight with respect to described nonaqueous electrolytic solution, the content of described dialkyl oxalate is 0.01-10 weight %, the content of described carbonic acid ethenylidene ester is 0.01-20 weight %, described 1, the content of 3-third sultone is 0.01-20 weight %.
4. lithium secondary battery according to claim 1 and 2, wherein, described nonaqueous solvents is the solvent that comprises the combination of the combination of cyclic carbonates and linear carbonate class or cyclic carbonates and lactone.
5. lithium secondary battery according to claim 1 and 2 wherein, comprises methyl ethyl carbonate as described linear carbonate.
6. lithium secondary battery according to claim 1 and 2, wherein, described nonaqueous solvents is made up of the combination of combination, ethylene carbonate and the diethyl carbonate of combination, ethylene carbonate and the methyl ethyl carbonate of propylene carbonate and dimethyl carbonate or the combination of ethylene carbonate and gamma-butyrolacton.
7. lithium secondary battery according to claim 1 and 2, wherein, the interplanar distance (d of the crystal face of described graphite (002)
002) be 0.340nm or following.
8. lithium secondary battery according to claim 1 and 2, wherein, positive active material is that the open circuit voltage after charging ends is that benchmark is shown as 4.3V or above lithium complex metal oxide with Li.
9. the nonaqueous electrolytic solution of a secondary lithium batteries, the nonaqueous electrolytic solution that this lithium secondary battery comprises positive pole, negative pole and obtains by be dissolved with electrolytic salt in nonaqueous solvents, it is characterized in that, in this nonaqueous electrolytic solution, contain dialkyl oxalate, and contain carbonic acid ethenylidene ester and/or 1,3-third sultone.
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| CN103460495A (en) * | 2011-04-12 | 2013-12-18 | 宇部兴产株式会社 | Non-aqueous electrolyte solution and electricity-storage device using same |
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| CN105814731A (en) * | 2013-12-05 | 2016-07-27 | 大金工业株式会社 | Electrolyte solution, electrochemical device, lithium ion secondary battery, and module |
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| JP4934914B2 (en) * | 2001-06-11 | 2012-05-23 | 三菱化学株式会社 | Electrolyte and secondary battery |
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