CN104638292A - Lithium secondary battery - Google Patents
Lithium secondary battery Download PDFInfo
- Publication number
- CN104638292A CN104638292A CN201410641844.4A CN201410641844A CN104638292A CN 104638292 A CN104638292 A CN 104638292A CN 201410641844 A CN201410641844 A CN 201410641844A CN 104638292 A CN104638292 A CN 104638292A
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- CN
- China
- Prior art keywords
- secondary battery
- lithium secondary
- nonaqueous electrolyte
- quality
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 72
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 75
- -1 lithium tetrafluoroborate Chemical class 0.000 claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
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- 150000003839 salts Chemical class 0.000 claims abstract description 3
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Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
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- H—ELECTRICITY
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Abstract
The present invention provides a lithium secondary battery, is high capacity and high temperature cycle characteristics Storage characteristics are excellent, the reliability of the non-aqueous secondary battery, the lithium secondary battery is the use of a positive electrode, a negative electrode, separator and a non-aqueous electrolyte lithium secondary battery. Characterized in that the non-aqueous electrolyte containing a molecule in which the nitrile groups of the compound, lithium tetrafluoroborate and electrolyte salt, the molecules of the nitrile groups of the compound having the non-aqueous electrolyte in an amount from 0.05 to 5.0 mass%, the lithium tetrafluoroborate in the non-aqueous electrolyte in an amount from 0.05 to about 70 mass%, thereby solving the above-described problems.
Description
Technical field
The present invention relates to the lithium secondary battery of charge/discharge cycle characteristics and storing property excellence.
Background technology
In recent years, along with the prosperity of the portable electronic appliances such as mobile phone, notebook computer, the practical of electric automobile etc., the small-sized light-duty and lithium secondary battery of high power capacity necessitates.
Further, in lithium secondary battery, be suitable for the popularization of machine along with it, require to improve various battery behavior.
As the means realizing the battery behavior improving lithium secondary battery, comprise the improvement of nonaqueous electrolyte.Such as, describe in patent documentation 1 and use dinitrile compound by organic solvent, and use the nonaqueous electrolytic solution of particular types lithium salts, the reduction of the discharge and recharge that the repeated charge due to battery can be suppressed to cause.
In addition, Patent Document 2 discloses a kind of secondary cell, it by containing nitrile compound and the compound containing S=O base, the cycle characteristics of battery and the excellence such as capacitance, preservation characteristics in nonaqueous electrolytic solution.
Patent documentation 1: Japanese Unexamined Patent Publication 2011-222473 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2004-179146 publication
Summary of the invention
Invent problem to be solved
Even if require that lithium secondary battery has such as repeated charge and also can maintain the so good cycle characteristics of capacity, but, although add the nitrile compounds such as dinitrile compound can improve storing property, heat characteristic, high temperature circulation in nonaqueous electrolyte, but on the other hand, especially reduce the cycle characteristics under normal temperature.
In addition, the lithium secondary battery after being used by mobile phone etc. is placed on for a long time under discharge condition under waiting high temperature place in car, this phenomenon of cell expansion can occur.
Further, the known method increasing the discharge capacity of battery by improving the charging upper limit voltage of battery, but, under high voltages, compared with prior art, for battery be placed on exacting terms under, also can have problems thus.
So, the storing property under raising cycle characteristics, discharge condition is required.
The present invention completes in view of the foregoing, its object is to provide a kind of high power capacity and the non-aqueous secondary batteries of storing property excellence under cycle characteristics, discharge condition.
Solve the means of problem
The lithium secondary battery of the present invention of described object can be reached, be the use of the lithium secondary battery of positive pole, negative pole, barrier film and nonaqueous electrolyte, it is characterized in that, described nonaqueous electrolyte contains the compound in LiBF4, molecule represented by following general formula (1) with itrile group respectively with scheduled volume.
NC-R-CN (1)
In general formula (1), R represents the hydrocarbon chain of the straight or branched of carbon number 1 ~ 10.
Invention effect
The present invention can provide a kind of high power capacity and high-temperature cycle, storing property, non-aqueous secondary batteries excellent in reliability.
Accompanying drawing explanation
Fig. 1 is the part longitudinal section schematic diagram of lithium secondary battery one example of the present invention.
Fig. 2 is the stereogram of Fig. 1.
Reference numeral
1: positive pole, 2: negative pole, 3: barrier film.
Embodiment
Lithium secondary battery of the present invention uses nonaqueous electrolyte, this nonaqueous electrolyte is the solution (nonaqueous electrolytic solution) such as lithium salts being dissolved in organic solvent and obtaining, containing the compound in the molecule represented by LiBF4, described general formula (1) with itrile group.
As mentioned above, the compound in molecule with itrile group is used for non-water electrolytic solution additive, although the reliability improving lithium secondary battery can be contributed to thus, reduces the cycle characteristics under normal temperature.
In the present invention, use with the addition of in molecule has the compound of itrile group and the nonaqueous electrolyte of LiBF4.
By adding LiBF4 in nonaqueous electrolytic solution, form the overlay film coming from LiBF4 in negative terminal surface.Because the overlay film coming from LiBF4 formed in negative terminal surface is firm, and there is lithium-ion-conducting, the decomposition reaction of the nonaqueous electrolyte composition in negative terminal surface can be suppressed well, on the other hand, can not obstruction be produced to cell reaction.
Because such overlay film coming from LiBF4 is firm, even if repeated charge, also can suppress the decomposition reaction of the nonaqueous electrolyte composition on negative pole chronically, excellent charge/discharge cycle characteristics can be guaranteed thus.
In addition, non-aqueous secondary batteries is at high temperature preserved for a long time with discharge condition, easily become over-discharge state.Battery under such state causes expansion because producing gas, but when use with the addition of in molecule the nonaqueous electrolyte of compound and the LiBF4 with itrile group, can suppress the generation of relative expansion.
And, in this application, the content of the described LiBF4 in nonaqueous electrolyte is defined as 0.05 ~ 0.70 quality %.If LiBF4 volume add, can produce the expansion of long high-temperature storage (charged state), for a long time carry out keep certain voltage charging time positive active material in metal dissolving.Therefore, by limiting the amount of LiBF4, can cycle characteristics be improved, prevent the variation of the storing property of charged state, prevent metal dissolving.
In addition, not only limit the amount of LiBF4, if used together with there is in molecule the compound of itrile group, the effect preventing metal dissolving can be improved synergistically.
So, non-aqueous secondary batteries of the present invention, by the composite action of special additive of adding in nonaqueous electrolyte, can not only improve charge/discharge cycle characteristics, and storing property in the discharged condition can also be made excellent.
Lithium secondary battery of the present invention uses nonaqueous electrolyte, this nonaqueous electrolyte is the solution (nonaqueous electrolytic solution) such as lithium salts being dissolved in organic solvent and obtaining, and contains the compound in LiBF4, molecule represented by described general formula (1) with itrile group as additive.
There is the compound of itrile group in molecule, in lithium secondary battery, be adsorbed in positive pole and form overlay film, can suppress thus under high voltages transition metal to the stripping of nonaqueous electrolyte.Thus, lithium secondary battery of the present invention, by adding in molecule the compound with itrile group in nonaqueous electrolyte, can stably use under high voltages.
There is in molecule represented by described general formula (1) compound of itrile group, consider and viscosity can be made to increase and select carbon number to be 1 ~ 10, such as, list malononitrile, succinonitrile, glutaronitrile, adiponitrile, 1, 4-dicyano heptane, 1, 5-dicyano pentane, 1, 6-dicyano hexane, 1, 7-dicyano heptane, 2, 6-dicyano heptane, 1, 8-dicyano octane, 2, 7-dicyano octane, 1, 9-dicyano nonane, 2, 8-dicyano nonane, 1, 10-dicyano decane, 1, 6-dicyano decane, 2, 4-dimethyl-penten dintrile etc., wherein only can use one, also can two or more also use.
In above-mentioned illustrative nitrile compound, more preferably dinitrile compound, wherein preferably improves the respond well adiponitrile of cycle characteristics further.
In the nonaqueous electrolyte being used in battery, having the content of the compound of itrile group in molecule, from more effectively playing this viewpoint of effect using these compounds to obtain, must be more than 0.05 quality %, be preferably more than 0.1 quality %, be more preferably more than 0.2 quality %.But, when the addition of the compound in molecule with itrile group is too much, although obtain storing property under can improving the charged state of such as battery further, the charge/discharge cycle characteristics existed at room temperature reduces, in the discharged condition stored with the risk helping expand.Thus, in the nonaqueous electrolyte being used in battery, the content in molecule with the compound of itrile group is below 5 quality %, is more preferably below 2 quality %.
In addition, the content of LiBF4, from obtaining this viewpoint of above-mentioned effect, is preferably more than 0.05 quality %, more preferably more than 0.1 quality %.In addition, be below 0.70 quality %, more preferably below 0.6 quality %.
As the electrolytic salt in nonaqueous electrolyte, as long as can carry out in a solvent dissociating and forming Li
+ion, the voltage range used at described battery are difficult to the material that the side reactions such as decomposition occur, and do not have special restriction.Such as, LiClO can be used
4, LiPF
6, LiAsF
6, LiSbF
6deng inorganic lithium salt, LiN (FSO
2)
2, LiC
4bO
8, LiCF
3sO
3, LiCF
3cO
2, Li
2c
2f
4(SO
3)
2, LiN (CF
3sO
2)
2, LiC (CF
3sO
2)
3, LiC
nf
2n+1sO
3(n≤2), LiN (RfOSO
2)
2organic lithium salts etc. such as (herein, Rf are fluoroalkyl).
The concentration of this lithium salts in nonaqueous electrolyte, is preferably 0.5 ~ 1.5mol/l, is more preferably 0.9 ~ 1.25mol/l.
As for the organic solvent in nonaqueous electrolyte, as long as described lithium salts can be dissolved, material that the voltage range that uses at described battery is difficult to occur the side reactions such as decomposition, there is no special restriction.Such as, the cyclic carbonates such as ethylene carbonate, propene carbonate, butylene can be enumerated, the linear carbonate such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, the chain esters such as methyl propionate, the cyclic esters such as gamma-butyrolacton, the chain ethers such as dimethoxy-ethane, ether, DOX, diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, Isosorbide-5-Nitrae-two
the cyclic ethers such as alkane, oxolane, 2-methyltetrahydrofuran, the sulfurous esters such as sulfurous acid glycol ester, can above-mentioned two or more material used in combination.It should be noted that, in order to obtain the battery of more superperformance, iting is desirable to use the mixed solvent etc. of ethylene carbonate and linear carbonate can obtain the combination of high conductivity.
In addition, in the nonaqueous electrolyte being used in lithium secondary battery, by containing 1,3-bis-
alkane, forms overlay film in negative terminal surface together with LiBF4, can suppress the charge/discharge cycle characteristics deterioration of lithium secondary battery.
Further, containing 1,3-bis-
alkane and the described nonaqueous electrolyte in molecule with the compound of itrile group, also work to positive electrode surface.As mentioned above, the compound in molecule with itrile group forms overlay film on positive pole, but, before the compound in this molecule with itrile group forms overlay film on positive pole, 1,3-bis-
alkane forms overlay film on positive pole.Thereby, it is possible to suppress the stripping of transition metal.In addition, the reaction between positive pole and nonaqueous electrolyte can be suppressed, prevent electrolytical decomposition and suppress the generation of resistance components.
But under the inferior adverse circumstances of high temperature high voltage, the positive pole especially under charged state, because oxidability is comparatively strong, exists and comes from 1,3-bis-
the problem that overlay film on the positive pole of alkane is destroyed.In this case, by electrolyte the compound with itrile group that remains, again on positive pole, form overlay film, therefore, it is possible to suppress the further stripping of transition metal, the decomposition of electrolyte on positive pole.
Be used in 1,3-in the nonaqueous electrolyte of lithium secondary battery bis-
the content of alkane, from guaranteeing more well to use by it this viewpoint of described each effect reached, is preferably more than 0.1 quality %, is more preferably more than 0.5 quality %.On the other hand, when 1,3-in nonaqueous electrolyte bis-
when the amount of alkane is too much, exists and reduce the part throttle characteristics of battery and the risk of charge/discharge cycle characteristics.Therefore, 1,3-in the nonaqueous electrolyte of lithium secondary battery bis-is used in
the content of alkane, is preferably below 5 quality %, is more preferably below 2 quality %.
In addition; by containing the phosphine acyl acetic acid ester type compound represented by following general formula (2) in nonaqueous electrolyte; form epithelium in the negative terminal surface of lithium secondary battery together with LiBF4, the deterioration of negative electrode active material, the deterioration of nonaqueous electrolyte can be suppressed.
Further, when containing LiBF4, phosphine acyl acetic acid ester type compound, 1,3-bis-in nonaqueous electrolyte
during alkane, cycle characteristics is further improved.
[changing 1]
In general formula (2), R
1, R
2and R
3separately represent alkyl, the alkenyl or alkynyl that can be carried out the carbon number 1 ~ 12 replaced by halogen atom, n represents the integer of 0 ~ 6.
As the concrete example of the phosphine acyl acetic acid ester type compound represented by described general formula (2), such as, following substances can be enumerated.
The compound of n=0 in described general formula (2):
Trimethyl phosphono formic acid esters (ホ ス ホ ノ Off ォ Le メ ー ト), methyl diethyl phosphonium mesitoyl formic acid ester, methyl dipropyl phosphonium mesitoyl formic acid ester, methyl dibutyl phosphonium mesitoyl formic acid ester, triethyl group phosphono formic acid esters, ethyldimethyl phosphine acyl formic acid esters, ethyl dipropyl phosphonium mesitoyl formic acid ester, ethyl dibutyl phosphonium mesitoyl formic acid ester, tripropyl phosphonium mesitoyl formic acid ester, propyl-dimethyl phosphonium mesitoyl formic acid ester, propyl group diethyl phosphonium mesitoyl formic acid ester, propyl group dibutyl phosphonium mesitoyl formic acid ester, tributyl phosphono formic acid esters, Butyldimethyl phosphonium mesitoyl formic acid ester, butyl diethyl phosphonium mesitoyl formic acid ester, butyl dipropyl phosphonium mesitoyl formic acid ester, methyl two (2, 2, 2-trifluoroethyl) phosphonium mesitoyl formic acid ester, ethyl two (2, 2, 2-trifluoroethyl) phosphonium mesitoyl formic acid ester, propyl group two (2, 2, 2-trifluoroethyl) phosphonium mesitoyl formic acid ester, butyl two (2, 2, 2-trifluoroethyl) phosphonium mesitoyl formic acid ester etc.
The compound of n=1 in described general formula (2):
Trimethyl-phosphine ethyl sodio acetoacetic ester, methyl diethyl phosphinylidyne acetic acid ester, methyl dipropyl phosphinylidyne acetic acid ester, methyl dibutyl phosphinylidyne acetic acid ester, triethyl phosphonium mesitoyl acetate, ethyldimethyl phosphine ethyl sodio acetoacetic ester, ethyl dipropyl phosphinylidyne acetic acid ester, ethyl dibutyl phosphinylidyne acetic acid ester, tripropyl phosphinylidyne acetic acid ester, propyl-dimethyl phosphinylidyne acetic acid ester, propyl group diethyl phosphinylidyne acetic acid ester, propyl group dibutyl phosphinylidyne acetic acid ester, tributylphosphine ethyl sodio acetoacetic ester, Butyldimethyl phosphinylidyne acetic acid ester, butyl diethyl phosphinylidyne acetic acid ester, butyl dipropyl phosphinylidyne acetic acid ester, methyl two (2, 2, 2-trifluoroethyl) phosphinylidyne acetic acid ester, ethyl two (2, 2, 2-trifluoroethyl) phosphinylidyne acetic acid ester, propyl group two (2, 2, 2-trifluoroethyl) phosphinylidyne acetic acid ester, butyl two (2, 2, 2-trifluoroethyl) phosphinylidyne acetic acid ester, allyl dimethyl base phosphinylidyne acetic acid ester, pi-allyl diethyl phosphinylidyne acetic acid ester, 2-propynyl dimethyl phosphine ethyl sodio acetoacetic ester, 2-propynyl diethyl phosphinylidyne acetic acid ester etc.
The compound of n=2 in described general formula (2):
Trimethyl 3-phosphono propionic ester, methyl 3-(diethyl phosphono) propionic ester, methyl 3-(dipropyl phosphono) propionic ester, methyl 3-(dibutyl phosphono) propionic ester, triethyl group 3-phosphono propionic ester, ethyl 3-(dimethyl phosphono) propionic ester, ethyl 3-(dipropyl phosphono) propionic ester, ethyl 3-(dibutyl phosphono) propionic ester, tripropyl 3-phosphono propionic ester, propyl group 3-(dimethyl phosphono) propionic ester, propyl group 3-(diethyl phosphono) propionic ester, propyl group 3-(dibutyl phosphono) propionic ester, tributyl 3-phosphono propionic ester, butyl 3-(dimethyl phosphono) propionic ester, butyl 3-(diethyl phosphono) propionic ester, butyl 3-(dipropyl phosphono) propionic ester, methyl 3-(two (2,2,2-trifluoroethyl) phosphono) propionic ester, ethyl 3-(two (2,2,2-trifluoroethyl) phosphono) propionic ester, propyl group 3-(two (2,2,2-trifluoroethyl) phosphono) propionic ester, butyl 3-(two (2,2,2-trifluoroethyl) phosphono) propionic ester etc.
The compound of n=3 in described general formula (2):
Trimethyl 4-phosphono butyrate, methyl 4-(diethyl phosphono) butyrate, methyl 4-(dipropyl phosphono) butyrate, methyl 4-(dibutyl phosphono) butyrate, triethyl group 4-phosphono butyrate, ethyl 4-(dimethyl phosphono) butyrate, ethyl 4-(dipropyl phosphono) butyrate, ethyl 4-(dibutyl phosphono) butyrate, tripropyl 4-phosphono butyrate, propyl group 4-(dimethyl phosphono) butyrate, propyl group 4-(diethyl phosphono) butyrate, propyl group (dibutyl phosphono) butyrate, tributyl 4-phosphono butyrate, butyl 4-(dimethyl phosphono) butyrate, butyl 4-(diethyl phosphono) butyrate, butyl 4-(dipropyl phosphono) butyrate etc.
In phosphine acyl acetic acid ester type compound, preferably use 2-propynyl diethyl phosphinylidyne acetic acid ester (PDEA), ethyl diethyl phosphinylidyne acetic acid ester (EDPA).
Be used in the content of the described phosphine acyl acetic acid ester type compound in the nonaqueous electrolyte of lithium secondary battery; from guaranteeing more well to use by it this viewpoint of described each effect reached; be preferably more than 0.1 quality %; preferably more than 0.5 quality %, is more preferably more than 1 quality %.But, when the content of the described phosphine acyl acetic acid ester type compound in nonaqueous electrolyte is too much, the risk that the charge/discharge cycle characteristics that there is battery reduces.Thus, be used in the content of the described phosphine acyl acetic acid ester type compound in the nonaqueous electrolyte of lithium secondary battery, be preferably below 5.0 quality %.
In addition, being used in the electrolyte in lithium secondary battery, by adding vinylene carbonate, 4-fluoro-1,3-dioxolan-2-one, cycle characteristics deterioration can being suppressed.
In addition, in the nonaqueous electrolyte being used in lithium secondary battery, for the further improvement of charge/discharge cycle characteristics, high-temperature storage and the object of raising preventing the fail safes such as overcharge, can suitably add the additives (comprising the derivative of these materials) such as acid anhydrides, sulphonic acid ester, PS, diphenyl disulfide, cyclohexylbenzene, biphenyl, fluorobenzene, tert-butyl benzene.
Further, in the nonaqueous electrolyte of lithium secondary battery, described nonaqueous electrolyte (nonaqueous electrolytic solution) can use and add the known gelating agent such as polymer and by the material of gelation (gel-like electrolyte).
Lithium secondary battery of the present invention has positive pole, negative pole, nonaqueous electrolyte and barrier film, as long as nonaqueous electrolyte wherein uses described nonaqueous electrolyte, other formation and structure are not particularly limited, the various formation and structure that adopt in always known lithium secondary battery can be suitable for.
Positive pole in lithium secondary battery, the single or double that such as can be used in collector body has the material of the structure of the positive electrode material mixture layer containing positive active material, adhesive and conductive auxiliary agent.
Positive active material, what can use in following lithium-contained composite oxide is one kind or two or more: by Li
1+xmO
2the lithium-containing transition metal oxide of the layer structure represented by (-0.1 < x < 0.1, M:Co, Ni, Mn, Al, Mg etc.); LiMn
2o
4, Li
4/3ti
5/3o
4deng spinel structure lithium-contained composite oxide; LiMPO
4olivine compounds represented by (M:Co, Ni, Mn, Fe etc.); Carried out the oxide etc. of replacing by various element for basic composition with above-mentioned oxide.As the concrete example of the lithium-containing transition metal oxide of layered structure, except LiCoO
2deng outside, can also list at least containing the oxide (LiMn of Co, Ni and Mn
1/3ni
1/3co
1/3o
2, LiNi
0.5co
0.3mn
0.2o
2, LiNi
0.85co
0.10al
0.05o
2deng) etc.
Adhesive in positive electrode material mixture layer, suitably can use such as Kynoar (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubbers (SBR), sanlose (CMC) etc.In addition, as the conductive auxiliary agent in positive electrode material mixture layer, such as, the graphite (graphite carbon materials) such as native graphite (flaky graphite etc.), Delanium can be enumerated, the carbon black such as acetylene black, section's qin (KETJEN BLACK), channel carbon black (channel black), furnace black (furnace black), dim (lamp black), thermal black (thermal black), the carbon materialses such as carbon fiber.
Positive pole, such as prepared by following process: positive active material, adhesive and conductive auxiliary agent etc. are scattered in METHYLPYRROLIDONE (NMP) equal solvent with modulate paste-like or pulp-like containing anode mixture composition (but, adhesive can be dissolved in solvent), be coated on the single or double of collector body, after the drying, carry out calendering process to prepare as required.But positive pole is not limited by above-mentioned manufacture method and obtains, also can be obtained by additive method.
In addition, in positive pole, can form by conventional method the lead body being used for carrying out with miscellaneous part in lithium secondary battery being electrically connected as required.
The thickness of positive electrode material mixture layer such as, is preferably 10 ~ 100 μm at the one side of collector body.In addition, as the composition of positive electrode material mixture layer, the amount of such as positive active material is preferably 60 ~ 98 quality %, and the amount of adhesive is preferably 1 ~ 15 quality %, and the amount of conductive auxiliary agent is preferably 1 ~ 20 quality %.
The collector body of positive pole can use and the always known material identical for the material of cathode plate for lithium secondary battery, and such as, preferred thickness is the aluminium foil of 10 ~ 30 μm.
The negative pole of lithium secondary battery, such as can use the material with following structure: have anode mixture layer at the single or double of collector body, this anode mixture layer formed by containing negative electrode active material and adhesive and then the cathode agent as required and containing conductive auxiliary agent.
As negative electrode active material, such as can enumerate graphite, thermal decomposition carbon element class, coke class, glassy carbon element class, the sintered body of organic high molecular compound, carbonaceous mesophase spherules, carbon fibre, activated carbon, can form metal (Si, Sn etc.) or its alloy, the oxide etc. of alloy with lithium, what can use in above-mentioned substance is one kind or two or more.
As Si alloy, such as, SiSn, SiCu, SiCr, SiTi etc. can be enumerated.In addition, as the oxide of Si, can be represented by SiOx.
SiOx can containing the micro-crystallization of Si or amorphous phase, and in the case, the atomic ratio of Si and O is the ratio of the Si of the micro-crystallization or amorphous phase that include Si.That is, in SiOx, be included in amorphous SiO2 matrix the material of the structure being dispersed with Si (such as, micro-crystallization Si), this amorphous SiO2 combines with wherein disperseed Si, as long as described atomic ratio x meets 0.5≤x≤1.5.Such as, be dispersed with in the structure of Si in amorphous SiO2 matrix, when the mol ratio of SiO2 and Si is the material of 1:1, due to x=1, represent with SiO as structural formula.When the material of this structure, in X-ray diffraction analysis, existence can not observe the situation of the peak value caused because of the existence of Si (micro-crystallization Si), when being observed by transmission electron microscope, can confirm the existence of tiny Si.
SiOx can use the complex carrying out Composite with carbon materials, such as, preferably at the surface-coated material having carbon materials of SiOx.Due to the poorly conductive of SiOx, during used as negative electrode active material, from the view point of guaranteeing good battery behavior, be necessary to use conductive material (conductive auxiliary agent), SiOx in negative pole and conductive material are carried out good to mix, dispersion, to form excellent conductive network.When SiOx is the complex with carbon materials Composite, such as, when only the conductive materials such as SiOx and carbon materials being carried out the material mixing gained compared to use, good conductive network can be formed at negative pole.
When negative pole uses the complex of SiOx and carbon materials, the ratio of SiOx and carbon materials, this viewpoint of good performance is obtained from making the effect brought with the Composite of carbon materials, relative to SiOx:100 mass parts, carbon materials is preferably more than 5 mass parts, is more preferably more than 10 mass parts.In addition, in described complex, the too much words of the ratio of the carbon materials of Composite are carried out with SiOx, by the reduction that the SiOx caused in anode mixture layer measures, the risk that the effect that there is high capacity reduces, therefore, relative to SiOx:100 mass parts, carbon materials is preferably below 50 mass parts, is more preferably below 40 mass parts.
In negative electrode active material, the while of with Si, Si alloy or SiOx, preferably use graphite.Graphite as nonaqueous electrolytic solution secondary battery negative electrode active material and be used widely, capacity is comparatively large comparatively speaking for it, and on the other hand, the discharge and recharge volume change with battery is less than described high-capacity cathode material.Therefore, by in negative electrode active material and with described high-capacity cathode material and graphite, along with the reduction of the use amount of high-capacity cathode material, the increase effect of battery capacity reduces, but the volume change of the anode mixture layer that the discharge and recharge along with battery can be suppressed as much as possible to produce.
The graphite used as negative electrode active material, such as can enumerate: the native graphites such as flaky graphite, easy to thermal decomposition carbon element class, carbonaceous mesophase spherules (MCMB), carbon fibre etc. graphitization carbon element be carried out more than 2800 DEG C the Delanium etc. of graphitization processing.
The content of Si, Si alloy in overall negative electrode active material and SiOx (only use wherein a kind, it is its amount, use wherein in situation of more than two kinds, its total amount), from the view point of the effect guaranteeing high capacity well, be preferably more than 0.01 quality %, be more preferably more than 1 quality %, be more preferably more than 3 quality %.In addition, from the view point of the problem that the change in volume can evading Si, Si alloy or the SiOx produced along with discharge and recharge better produces, Si, Si alloy in overall negative electrode active material and SiOx content, be preferably below 20 quality %, be more preferably below 15 quality %.
In negative electrode active material, except SiOx, Si, Si alloy and graphite, also can use other active materials with these active materials simultaneously.As other active materials this, such as, thermal decomposition carbon element class, coke class, glassy carbon element class, the sintered body of organic high molecular compound, MCMB, carbon fibre, activated carbon can be enumerated, metal (Sn etc.) and alloy, the oxide etc. of alloy can be formed with lithium.But the use amount of these other active materials, in overall negative electrode active material, is preferably below 10 quality %.
In addition, the adhesive of negative pole and conductive auxiliary agent, can use and can be used in the material of positive pole and the material that illustrative material is identical before.
Negative pole is prepared through following process: prepare the paste-like that negative electrode active material and adhesive, conductive auxiliary agent used as required is further dispersed in and formed in NMP or water equal solvent or pulp-like composition containing cathode agent (but, adhesive can dissolve in a solvent), be coated on the single or double of collector body, after the drying, calendering process is carried out as required.But negative pole is not limited to be manufactured by described manufacture method obtain, and additive method manufacture also can be used to obtain.
In addition, in negative pole, as required, can also form by conventional method the lead body being used for carrying out with the miscellaneous part in lithium secondary battery being electrically connected.
The thickness of anode mixture layer, such as, the every one side thickness of preferred collector body is 10 ~ 100 μm.In addition, as the composition of anode mixture layer, such as preferred negative electrode active material is 80.0 ~ 99.8 quality %, adhesive is 0.1 ~ 10 quality %.Further, in anode mixture layer containing conductive auxiliary agent, the amount of the conductive auxiliary agent in anode mixture layer is preferably 0.1 ~ 10 quality %.
As the collector body of negative pole, the paper tinsel of copper or nickel, punch metal, net, expanded metal etc. can be used, usually use Copper Foil.This negative electrode collector, when in order to obtain the battery of high-energy-density and make the reduced thickness of negative pole entirety, the preferred thickness upper limit is 30 μm, wishes that lower limit is 5 μm in order to ensure machinery.
Barrier film in lithium secondary battery, preferably more than 80 DEG C during (more preferably more than 100 DEG C) less than 170 DEG C (more preferably below 150 DEG C), its hole has inaccessible character (i.e. closing function), the barrier film that common lithium secondary battery etc. uses can be used, such as, the polyolefin microporous film such as polyethylene (PE) or polypropylene (PP).Form the micro-porous film of barrier film, such as, can be the film that only only used PE, or only only used the film of PP, in addition, can also be the duplexer of the micro-porous film of PE and the micro-porous film of PP.Further, can also use the resin porous layer (I) that has for guaranteeing closing property with for improving the barrier film of the heat-resisting porous layer (II) of the thermal endurance of barrier film.Such as, resin porous layer (I) uses the polyolefin such as polyethylene or polypropylene micro-porous film, heat-resisting porous layer (II) use heat resisting temperature be more than 150 DEG C inorganic fine particles as filler, and by binding agent carry out bonding come with resin porous layer (I) stacked.
The thickness of barrier film, such as, is preferably 10 ~ 30 μm.
Described positive pole and described negative pole and described barrier film, with the multilayer electrode body overlapping across barrier film between positive pole with negative pole or and then can come for lithium battery of the present invention with the form being wound into spiral helicine spiral winding electrode.
As the form of lithium secondary battery of the present invention, the tubular (square tube shape or cylindrical shape etc.) etc. using stainless cylinder of steel or aluminium pot etc. as outer package jar can be enumerated.In addition, the flexible-packed battery metal having the laminate film of metal to be external packing body with evaporation can be formed.
Lithium secondary battery of the present invention, is set in more than 4.3V to use by the upper voltage limit of charging, thus while realizing high capacity, even if use under high voltage like this, also can play higher reliability and storing property.It should be noted that, the charging upper limit voltage in lithium secondary battery of the present invention is preferably below 4.7V.
Lithium secondary battery of the present invention, may be used for always known lithium secondary battery the identical purposes of the various uses that is suitable for.
Embodiment
Below, the present invention is described in detail based on embodiment.But, the invention is not restricted to following embodiment.
Embodiment 1
1. the preparation of positive pole
By LiCoO
2with Li
1.0ni
0.5co
0.2mn
0.3o
2positive active material 100 mass parts be obtained by mixing using the ratio of 8:2 (mass ratio), nmp solution 20 mass parts containing adhesive PVDF 10 quality % concentration, as Delanium 1 mass parts of conductive auxiliary agent and section's qin 1 mass parts, Dual-screw kneader is used to carry out mixing, add NMP further and carry out adjusting viscosity, thus make the paste containing anode mixture.
By the described paste containing anode mixture, being coated on thickness is behind the two sides of aluminium foil (positive electrode collector) of 15 μm, carries out the vacuumize of 12 hours at 120 DEG C, forms positive electrode material mixture layer on the two sides of aluminium foil.After this, carry out pressurized treatments, to regulate thickness and the density of positive electrode material mixture layer, in the exposed division welding nickel lead body of aluminium foil, the banded positive pole of obtained length 375mm, width 43mm.The thickness of every one side of the positive electrode material mixture layer in the positive pole of gained is 55 μm.
2. the preparation of negative pole
To be that the SiO surface of 8 μm to be coated to the graphite that the complex (in complex, the amount of carbon materials is 10 quality %) that obtains and averaged particles footpath D50% are 16 μm and to have the amount of the complex of carbon materials to be mixture 97.5 mass parts, adhesive SBR 1.5 mass parts, tackifier CMC 1 mass parts that 3.75 quality % carry out being mixed to get so that SiO is surface-coated by carbon materials as the average grain diameter D50% of negative electrode active material, add water and mix, preparation is containing the paste of cathode agent.
By the described paste containing cathode agent, being coated on thickness is behind the two sides of aluminium foil (negative electrode collector) of 15 μm, carries out the vacuumize of 12 hours at 120 DEG C, forms anode mixture layer on the two sides of aluminium foil.After this, carry out pressurized treatments, to regulate thickness and the density of anode mixture layer, in the exposed division welding nickel lead body of aluminium foil, the banded negative pole of obtained length 380mm, width 44mm.Anode mixture layer in the negative pole of gained, the thickness of every one side is 65 μm.
3. the preparation of nonaqueous electrolytic solution
In the mixed solvent of the volume ratio 3:7 of ethylene carbonate and diethyl carbonate, dissolve LiPF with the concentration of 1.1mol/l
6, add adiponitrile 0.5 quality %, LiBF4 0.3 quality %, VC 2.75 quality % and FEC 1.75 quality % respectively, prepare nonaqueous electrolyte.
4. the assembling of battery
By above-mentioned banded positive pole, between be the microporous polyethylene barrier film (porosity: 41%) be superimposed on above-mentioned banded negative pole of 16 μm across thickness, after being wound into helical form, pressurize to become flat thus obtain having the spiral winding electrode of flat winding-structure, the insulating tape of this electrode coiling body polypropylene is fixed.Then, described spiral winding electrode being inserted overall dimension is in the cubic battery of thickness 4.0mm, width 34mm, the highly aluminum alloy of 50mm, while lead body being carried out welding, the bridge welding of aluminum alloy is connected on the open end of battery case.After this, inject described nonaqueous electrolyte from the inlet be arranged at cover plate, inlet encapsulated leaving standstill after 1 hour, obtain structure as shown in Figure 1, outward appearance lithium secondary battery as shown in Figure 2.
Herein, battery shown in Fig. 1 and Fig. 2 is described, Fig. 1 is its partial cross sectional view, positive pole 1 with negative pole 2 after barrier film 3 is wound into helical form, pressurize to become flat thus obtain the spiral winding electrode 6 of flat, being contained in together with nonaqueous electrolyte in the battery case 4 of square (square tube shape).But, in Fig. 1, in order to avoid complicated, the metal forming and nonaqueous electrolyte etc. that use as collector body when preparing positive pole 1 and negative pole 2 are not illustrated.
Battery case 4 is standby to form the exterior body of battery by aluminum alloy, and this battery case 4 also doubles as positive terminal simultaneously.And, the insulator 5 formed by PE sheet material is configured with in the bottom of battery case 4, from the flat spiral winding electrode 6 formed by positive pole 1, negative pole 2 and barrier film 3, draw the positive wire body 7 and negative wire body 8 that are connected with one end of positive pole 1 and negative pole 2 respectively.In addition, the aluminum alloy sealing cover plate 9 for sealing the peristome of battery case 4 being provided with across polypropylene insulation spacer 10 terminal 11 of stainless steel, this terminal 11 being provided with the lead plate 13 of stainless steel across insulator 12.
Further, this cover plate 9 inserts in the peristome of battery case 4, and by being welded at both junction surfaces, sealed by the peristome of battery case 4, inside battery is sealed.In addition, in the battery of Fig. 1, cover plate 9 is provided with nonaqueous electrolyte inlet 14, at this nonaqueous electrolyte inlet 14, under the state inserting package parts, such as, carries out welding encapsulation, to guarantee the sealing of battery by laser welding etc.Further, on cover plate 9, as when the temperature of battery rises, the gas of inside is discharged outside mechanism, be provided with air vent hole 15.
The cell arrangement of this embodiment 1 is, outer tinning 5 is made to play function with cover plate 9 as positive terminal by being directly welded on by positive wire body 7 on cover plate 9, by negative wire body 8 is welded on lead plate 13, negative wire body 8 and terminal 11 mutual conduction is made by this lead plate 13, terminal 11 plays function as negative terminal thus, according to differences such as the materials of battery case 4, there is the situation that both positive and negative polarity is contrary.
Fig. 2 is the schematic perspective view of the outward appearance of battery shown in Fig. 1, and this Fig. 2 object is rectangular cell to show described battery, simply battery is shown, illustrate only particular elements in the component parts of battery in this Fig. 1.In addition, in FIG, the inner circumferential side part of electrode body does not carry out cross section.
Embodiment 2
Except adding adiponitrile 0.5 quality %, LiBF4 0.3 quality %, VC 2.75 quality %, FEC1.75 quality %, 1,3-bis-respectively
outside alkane 0.75 quality %, prepare nonaqueous electrolyte in the same manner as example 1, except using this nonaqueous electrolyte, prepare lithium secondary battery in the same manner as example 1.
Embodiment 3
Except adding adiponitrile 0.5 quality %, LiBF4 0.3 quality %, VC2.75 quality %, FEC1.75 quality %, 1,3-bis-respectively
outside alkane 0.75 quality %, PDEA 1.25 quality %, prepare nonaqueous electrolyte in the same manner as example 1, except using this nonaqueous electrolyte, prepare lithium secondary battery in the same manner as example 1.
Embodiment 4 ~ embodiment 13, comparative example 1 ~ comparative example 8
Adjust except nonaqueous electrolyte except as shown in table 1, prepare nonaqueous electrolyte in the same manner as example 1, except using this nonaqueous electrolyte, prepare lithium secondary battery in the same manner as example 1.
For the lithium secondary battery of embodiment and comparative example, carry out following every evaluation.
1. charge/discharge cycle characteristics evaluation
By the lithium secondary battery of embodiment and comparative example, first under the environment of 23 DEG C, constant current charge is carried out to 4.35V with the current value of 0.5C, then constant-potential charge (total charging time of constant current charge and constant-potential charge is 5 hours) is carried out with 4.35V, after this carry out discharging until 2.75V with the constant current of 0.2C, obtain discharge capacity first.Then, by each battery at 23 DEG C with the current value constant current charge of 1C to 4.35V, next carry out charging until current value is for 0.05C with the constant voltage of 4.35V, be after this discharged to 3.0V with the current value of 1C, using this series of operation as a circulation, repeatedly carry out repeatedly.Further, carry out 500 circulations for each battery, condition identical during to measure with described discharge capacity first carries out constant current-constant-potential charge and constant current discharges, and obtains the discharge capacity of the 500th circulation time.In addition, the value of these discharge capacities divided by discharge capacity gained is first represented with percentage, calculate the capacity dimension holdup of the 500th circulation.After this, carry out discharge and recharge until capacity dimension holdup reaches 50% (condition is identical with above-mentioned circulation), obtain cycle-index when capacity dimension holdup reaches 50%.
In addition, for each lithium secondary battery of embodiment and comparative example, except ambient temperature being changed to except 45 DEG C, carry out the same mensuration of discharge capacity first, charge and discharge cycles and discharge capacity to measure as above-mentioned, the value of discharge capacity divided by discharge capacity gained is first represented with percentage, calculates the capacity dimension holdup of the 500th circulation.After this, carry out discharge and recharge until capacity dimension holdup reaches 50% (condition is identical with above-mentioned circulation), obtain cycle-index when capacity dimension holdup reaches 50%.
2. the high-temperature storage evaluating characteristics under discharge condition
By each lithium secondary battery of embodiment and comparative example, carry out discharging until 2.75V with the constant current of 0.1C, after this carry out resistance measurement and thickness measurement.After this, each battery is put into the thermostat remaining on 60 DEG C, preserve 20 days.After this, each battery is taken out from thermostat, after 2 hours, carrying out resistance measurement and thickness measurement.
Further, for resistance, deduct the value before storage by the value after storage, calculate the variable quantity (Ω) of resistance.
In addition, about the thickness of battery, use following formula calculated thickness rate of change.
Thickness-100 before thickness ÷ after variable quantity (%)=100 × storage of thickness preserves
3.1C discharge load evaluating characteristics
For the lithium secondary battery of embodiment and comparative example, carry out constant current charge until 4.35V with the current value of 0.5C, then under 4.35V with constant-potential charge after discharge with 0.2C.After this, carry out constant current charge until 4.35V with the current value of 0.5C, then under 4.35V with constant-potential charge after discharge with 1C.Represent with percentage with the value of discharge capacity during 1C divided by discharge capacity during 0.2C, calculate speed characteristic.
4. floating charge evaluation
For the lithium secondary battery of embodiment and comparative example, under the environment of 60 DEG C, carry out constant current charge until after 4.35V with the current value of 1.0C, carry out constant-potential charge with the voltage of 4.4V, while continuing to carry out constant-potential charge, measure the time that current value occurs to rise.Specifically, in constant-potential charge region current value reach minimum after, be then judged as " rising " increasing the time point of more than 1.5mA.
The content of the additive of the nonaqueous electrolyte in the lithium secondary battery of embodiment and comparative example is shown in table 1, and described each evaluation result is shown in table 2, table 3.
Table 1
Table 2
Table 3
As shown in table 1 and table 2, use the lithium secondary battery of embodiment 1 of the nonaqueous electrolyte containing adiponitrile, LiBF4, at capacity when charge/discharge cycle characteristics is evaluated and 45 DEG C 500 circulate after capacity dimension holdup, there is good charge/discharge cycle characteristics.In addition, 1,3-bis-is added
then more good during alkane, then show better cycle characteristics when adding PDEA.In addition, the lithium secondary battery of embodiment 1 ~ 2, in the discharged condition after high-temperature storage, inhibit the change of the increase of resistance and thickness (expanding), the high-temperature storage characteristic under discharge condition is good.Further, LiBF4 until 0.7 quality %, shows good floating charge characteristic in nonaqueous electrolyte.
Relative to this, in the battery of the battery of the comparative example 1 not containing LiBF4, the comparative example 4 of the nonaqueous electrolyte of use containing LiBF4 0.3 quality %, adiponitrile 7.0%, although the cycle characteristics at 45 DEG C is good, but the cycle characteristics under room temperature compare do not add adiponitrile, the result of comparative example 5 of LiBF4 decreases, in the discharged condition after high-temperature storage, the increase of resistance also increases relative to the battery of embodiment.This can think that the protection overlay film due to negative pole is not firm, or to decompose at negative pole due to the more thus adiponitrile of the addition of adiponitrile and become resistance components.
Do not add the battery of the comparative example 2 of adiponitrile, due to the effect of LiBF4, at room temperature, cycle characteristics at 45 DEG C, increase compared to the battery of the comparative example 5 not containing adiponitrile and LiBF4, but the cycle characteristics compared with embodiment at 45 DEG C is poor.
In addition, employ the battery of the comparative example 3 of the nonaqueous electrolyte containing LiBF4 4.0%, although cycle characteristics is good, the speed characteristic under storing property, 1C is poor.
Employ the battery of the comparative example 5 of the nonaqueous electrolyte not containing adiponitrile and LiBF4, charge/discharge cycle characteristics at 45 DEG C is poorer than embodiment, in discharge condition after high-temperature storage, the recruitment of resistance and the rate of change of thickness, be all greater than the battery of embodiment.
Further, the comparative example 6 of the nonaqueous electrolyte containing LiBF4, floating test result is poor.
Claims (10)
1. a lithium secondary battery, be the use of the lithium secondary battery of positive pole, negative pole, barrier film and nonaqueous electrolyte, it is characterized in that, described nonaqueous electrolyte contains the compound in LiBF4, molecule represented by following general formula (1) with itrile group
The content of the described LiBF4 in described nonaqueous electrolyte is 0.05 ~ 0.7 quality %,
The content in the described molecule in described nonaqueous electrolyte with the compound of itrile group is 0.05 ~ 5.0 quality %,
NC-R-CN (1)
In formula, R is the hydrocarbon chain of the straight or branched of carbon number 1 ~ 10.
2. lithium secondary battery as claimed in claim 1, wherein, contains LiPF as electrolytic salt in described nonaqueous electrolyte
6.
3. lithium secondary battery as claimed in claim 1 or 2, wherein, the content employing the compound in described molecule with itrile group is the nonaqueous electrolyte of 0.05 ~ 2.0 quality %.
4. the lithium secondary battery according to any one of claims 1 to 3, wherein, the content employing described LiBF4 is the nonaqueous electrolyte of 0.05 ~ 0.60 quality %.
5. the lithium secondary battery according to any one of Claims 1 to 4, wherein, uses containing 1,3-bis-
the nonaqueous electrolyte of alkane.
6. lithium secondary battery as claimed in claim 5, wherein, described in the nonaqueous electrolyte of use 1,3-bis-
the content of alkane is 0.1 ~ 5.0 quality %.
7. the lithium secondary battery according to any one of claim 1 ~ 6, wherein, described nonaqueous electrolyte contains the phosphine acyl acetic acid ester type compound represented by following general formula (2),
[changing 1]
In general formula (2), R
1, R
2and R
3represent alkyl, the alkenyl or alkynyl that can be carried out the carbon number 1 ~ 12 replaced by halogen atom independently of one another, n represents the integer of 0 ~ 6.
8. lithium secondary battery as claimed in claim 7, wherein, the content employed containing the phosphine acyl acetic acid ester type compound represented by described general formula (2) is the nonaqueous electrolytic solution of 0.1 ~ 5.0 quality %.
9. the lithium secondary battery according to any one of claim 1 ~ 8, wherein, described nonaqueous electrolyte is also containing vinylene carbonate.
10. the lithium secondary battery according to any one of claim 1 ~ 9, wherein, described nonaqueous electrolyte contains 4-fluoro-1,3-dioxolan-2-one.
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| JP2013233191 | 2013-11-11 | ||
| JP2013-233191 | 2013-11-11 | ||
| JP2014201342A JP2015111552A (en) | 2013-11-11 | 2014-09-30 | Lithium secondary battery |
| JP2014-201342 | 2014-09-30 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002334718A (en) * | 2001-05-10 | 2002-11-22 | Yuasa Corp | Nonaqueous electrolyte and nonaqueous electrolyte battery |
| CN1848511A (en) * | 2005-02-28 | 2006-10-18 | 三洋电机株式会社 | Non-aqueous electrolyte secondary cell |
| CN101814630A (en) * | 2009-02-25 | 2010-08-25 | 三洋电机株式会社 | Non-aqueous electrolyte secondary cell |
| CN103038928A (en) * | 2010-07-29 | 2013-04-10 | 日立麦克赛尔能源株式会社 | Lithium secondary battery |
-
2014
- 2014-11-07 CN CN201410641844.4A patent/CN104638292A/en active Pending
- 2014-11-10 KR KR1020140155379A patent/KR20150054683A/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002334718A (en) * | 2001-05-10 | 2002-11-22 | Yuasa Corp | Nonaqueous electrolyte and nonaqueous electrolyte battery |
| CN1848511A (en) * | 2005-02-28 | 2006-10-18 | 三洋电机株式会社 | Non-aqueous electrolyte secondary cell |
| CN101814630A (en) * | 2009-02-25 | 2010-08-25 | 三洋电机株式会社 | Non-aqueous electrolyte secondary cell |
| CN103038928A (en) * | 2010-07-29 | 2013-04-10 | 日立麦克赛尔能源株式会社 | Lithium secondary battery |
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