CN101124695A - Electrolyte solution and battery - Google Patents
Electrolyte solution and battery Download PDFInfo
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- CN101124695A CN101124695A CNA2006800054467A CN200680005446A CN101124695A CN 101124695 A CN101124695 A CN 101124695A CN A2006800054467 A CNA2006800054467 A CN A2006800054467A CN 200680005446 A CN200680005446 A CN 200680005446A CN 101124695 A CN101124695 A CN 101124695A
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Abstract
Disclosed is an electrolyte solution which enables to improve battery characteristics such as battery swelling and charge/discharge efficiency. Also disclosed is a battery using such an electrolyte solution. Specifically disclosed is a battery wherein a positive electrode (21) and a negative electrode (22) are arranged in layers via an electrolyte layer (24). The electrolyte layer (24) is a gel containing an electrolyte solution and a polymer compound, and the electrolyte solution contains a compound having a proton-collecting function such as hexamethylenetetramine or hexaethylenetetramine. Consequently, a free acid such as hydrofluoric acid can be captured, thereby suppressing decomposition reaction of the electrolyte.
Description
Technical field
The present invention relates to the battery of electrolyte and this electrolyte of use.
Background technology
In recent years, be that the miniaturization of portable electric appts and the lightness of representative obtained promoting energetically with mobile phone, PDA (personal digital assistant) and notebook personal computer.As an one link, strong request is as the particularly improvement of the energy density of secondary cell of battery of its driving power.As the secondary cell that high-energy-density can be provided, for example, use can embed and deviate from the material of lithium (Li) such as lithium rechargeable battery that material with carbon element is used for negative pole is known.
In addition, in recent years, as the secondary cell that high-energy-density can be provided, developed a kind of secondary cell, the material that wherein can embed and deviate from lithium is used for negative pole, the lithium metal is separated out on this surface, and capacity of negative plates comprises because the embedding of lithium and the voxel of deviating from (capacitycomponent) and because the voxel of separating out and dissolving (for example, referring to patent document 1) of lithium thus.
In these secondary cells, for example, reality has been used a kind of secondary cell, and the composite oxides that wherein comprise lithium, cobalt (Co), manganese (Mn) etc. are used for positive pole, and solvent such as ethylene carbonate and electrolytic salt such as lithium hexafluoro phosphate are used for electrolyte.
Patent document 1: international open No.01/22519
Patent document 2: the open No.7-312227 of Japanese Unexamined Patent Application
Patent document 3: the open No.10-177814 of Japanese Unexamined Patent Application
Summary of the invention
But such problem is arranged: when lithium hexafluoro phosphate etc. decomposes when producing free acid such as hydrofluoric acid (HF), cobalt or manganese are washed out from positive pole, and electrolyte decomposition, so battery behavior is as charging and discharging efficiency reduction.
In this secondary cell, considered that in order to improve cycle characteristics for example, the cyclic carbonate that use some of them hydrogen is replaced by fluorine etc. are as solvent (for example, referring to patent document 2 and 3).But, when comprising moisture in the battery, for example,, under the situation of 3-dioxolanes-2-ketone, promote the decomposition reaction of electrolyte by the hydrofluoric acid of hydrolysis generation at the 4-fluoro-1 that uses as one of this cyclic carbonate.In addition, think that the non-oxidizability of the product that produces by hydrolysis is low.Therefore, such problem is arranged: for example, when laminated film when the package member, be kept at cell expansion under the hot environment with charged state.
Consider above problem, the purpose of this invention is to provide and to suppress cell expansion and improve battery behavior as charging and the electrolyte of discharging efficiency and the battery that uses this electrolyte.
First electrolyte according to the present invention comprises 4-fluoro-1,3-dioxolanes-2-ketone and the compound with proton seizure (scavenging) ability.
Second electrolyte according to the present invention comprises six ethylidene tetramines.
First battery according to the present invention comprises positive pole, negative pole and electrolyte, and wherein this electrolyte comprises 4-fluoro-1,3-dioxolanes-2-ketone and the compound with proton capturing ability.
Second battery of the present invention comprises positive pole, negative pole and electrolyte, and wherein this electrolyte comprises six ethylidene tetramines.
First electrolyte of the present invention comprises 4-fluoro-1,3-dioxolanes-2-ketone and the compound with proton capturing ability.Therefore, free acid can be caught by this compound with proton capturing ability effectively.As a result, first battery of the present invention according to using this electrolyte can prevent the decomposition reaction of electrolyte etc.For example, can suppress the expansion of battery.
In addition, when comprising nitrogen compound when having the compound of proton capturing ability, can obtain higher effect with unshared electron pair.
In addition, when the nitrogen compound concentration in electrolyte satisfies mathematical expression 1, can obtain further effect.
[mathematical expression 1]
4-fluoro-1, the concentration (mol/kg) of the 3-dioxolanes-2-ketone/concentration of the quantity of unshared electron pair * 0.4≤nitrogen compound (mol/kg)≤4-fluoro-1 in nitrogen compound, the concentration (mol/kg) of the 3-dioxolanes-2-ketone/quantity of unshared electron pair * 10 in nitrogen compound
In addition, second electrolyte of the present invention comprises six ethylidene tetramines.Therefore, when effectively catching free acid, can reduce its reactivity.As a result, the battery of the present invention for using this electrolyte can prevent the decomposition reaction of electrolyte etc., and can improve battery behavior as charging and discharging efficiency.
Especially, when the content of six ethylidene tetramines in electrolyte is in 0.001 weight %-5 weight % scope, can obtain higher effect.
Description of drawings
Fig. 1 is the decomposition diagram of demonstration according to the structure of the secondary cell of embodiment of the present invention;
Fig. 2 is the cross section of demonstration along the structure of the line II-II of spiral winding electrode shown in Figure 1;
Fig. 3 shows the performance plot of the example of the cycle characteristics of the secondary cell of manufacturing in an embodiment;
Fig. 4 shows in an embodiment the performance plot that concerns between high-temperature storage time of the secondary cell of making and the cell thickness; With
Fig. 5 shows another performance plot of the example of the cycle characteristics of the secondary cell of manufacturing in an embodiment.
Embodiment
Describe embodiments of the present invention below with reference to accompanying drawings in detail.
(first execution mode)
Fig. 1 has shown the example according to the decomposition texture of the secondary cell of first embodiment of the invention.This secondary cell is so-called lithium rechargeable battery, and wherein capacity of negative plates is by owing to represent as the embedding of the lithium of electrode reaction thing and the capacity component of deviating from.This secondary cell has such structure: the spiral winding electrode 20 that is connected with positive wire 11 and negative wire 12 on it is included in membranaceous package member 31 inside.
In order to the contact performance between the inside of improving positive wire 11/ negative wire 12 and package member 31 and prevent that the adhesive film 32 that extraneous air enters from inserting between package members 31 and positive wire 11/ negative wire 12.Adhesive film 32 is made by the material that positive wire 11 and negative wire 12 is had contact performance, for example, when positive wire 11 and negative wire 12 were made by above-mentioned metal material, this adhesive film was preferably made by vistanex such as polyethylene, polypropylene, modified poly ethylene or modified polypropene.
Fig. 2 has shown along the cross-sectional structure of the line II-II of spiral winding electrode shown in Figure 1 20.In spiral winding electrode 20, positive pole 21 and negative pole 22 and barrier film therebetween 23 and electrolyte 24 stacked and screw windings.The outermost of spiral winding electrode 20 is protected with boundary belt 25.
Anodal 21 for example have positive electrode collector 21A and are arranged on the two sides of positive electrode collector 21A or the anode active material layer 21B on the one side.In positive electrode collector 21A, for example, has the expose portion that anode active material layer 21B is not set at the one end in the vertical.Positive wire 11 is linked on this expose portion.Positive electrode collector 21A is made by metal material such as aluminium.
Anode active material layer 21B for example comprises one or more can embed and deviate from positive electrode as the lithium of electrode reaction thing as positive electrode active materials.As the positive electrode that can embed and deviate from lithium, for example, the sulfide of lithium-containing compound such as lithium transition-metal oxide, Lithium Phosphor Oxide, lithium and the intercalation compound that comprises lithium are suitable.Can use its two or more by mixing.Especially, in order to improve energy density, preferably by general formula Li
xMIO
2Or Li
yMIIPO
4The lithium composite xoide and the Lithium Phosphor Oxide of expression.In formula, MI and MII comprise one or more transition metal, and preferably include at least a of cobalt, nickel, manganese, iron (Fe), aluminium, vanadium (V), titanium (Ti) and zirconium (Zr).The value of x and y changes according to the charging and the discharge condition of battery, and usually in the scope of 0.05≤x≤1.10 and 0.05≤y≤1.10.As by Li
xMIO
2The instantiation of the lithium composite xoide of expression can be enumerated LiCoO
2, LiNiO
2, LiNi
0.5Co
0.5O
2, LiNi
0.5Co
0.2Mn
0.3O
2, LiMn with spinel crystal structure
2O
4Deng.As by Li
yMIIPO
4The instantiation of the Lithium Phosphor Oxide of expression can be enumerated LiFePO
4, LiFe
0.5Mn
0.5PO
4Deng.
Anode active material layer 21B comprises for example electric conductor, and if necessary can comprise adhesive.As electric conductor, for example, it is black to enumerate material with carbon element such as graphite, carbon black and Ketjen.Can use it a kind of separately, maybe can use its two or more by mixing.Except material with carbon element, also can use metal material, conducting polymer materials etc., as long as this material has conductivity.As adhesive, for example, can enumerate synthetic rubber such as butadiene-styrene rubber, Viton and ethylene propylene diene rubber; Or polymeric material such as polyvinylidene fluoride.Can use it a kind of separately, maybe can use its two or more by mixing.
Be similar to positive pole 21, negative pole 22 has negative electrode collector 22A and is arranged on the two sides of negative electrode collector 22A or the anode active material layer 22B on the one side.In negative electrode collector 22A, for example, has the expose portion that anode active material layer 22B is not set at the one end in the vertical.Negative wire 12 is linked on this expose portion.Negative electrode collector 22A is made by for example metal material such as copper (Cu).
Anode active material layer 22B for example comprises one or more can embed and deviate from negative material as the lithium of electrode reaction thing as negative active core-shell material.If necessary, anode active material layer 22B can comprise the similar adhesive with anode active material layer 21B.
As the negative material that can embed and deviate from lithium, for example, but can enumerate material with carbon element such as graphite, ungraphitised carbon and graphitized carbon.The preferred material with carbon element that uses is because owing to the changes in crystal structure of charging and discharge causes is very little, can obtain high charging and discharge capacity, and can obtain favourable charging and discharge cycles characteristic.Especially, preferred graphite is because capacity is high and can obtain high-energy-density thus.
As the negative material that can embed and deviate from lithium, also can enumerate to embed and to deviate from lithium and comprise metallic element and at least a material of metalloid element, because can obtain high-energy-density thus as the formation element.This negative material can be simple substance, alloy or the compound of metallic element; The simple substance of metalloid element, alloy or compound; Or the material that has its one or more phases to small part.In the present invention, except the alloy that comprises two or more metallic elements, alloy also comprises the alloy that comprises one or more metallic elements and one or more metalloid elements.In addition, alloy can comprise nonmetalloid.Its structure can be solid solution, eutectic (eutectic mixture (eutectic)), intermetallic compound or the structure of its two or more coexistences wherein.
As the metallic element or the metalloid element that constitute negative material, for example, can enumerate magnesium (Mg), boron (B), aluminium, gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn), plumbous (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium, yttrium (Y), palladium (Pd) or the platinum (Pt) that can form alloy with lithium.This element can be crystallization or unbodied.
Specifically, preferably be contained in the metallic element of 4B family in the short period periodic table of elements or metalloid element as the negative material that constitutes element.Comprising at least a of silicon and tin is particularly preferred as the negative material that constitutes element.The ability that silicon and tin have high embedding and deviates from lithium, and high-energy-density can be provided.
As ashbury metal, for example, can enumerate detin and comprise at least a alloy that is selected from silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony (Sb) and chromium (Cr) outward as the second formation element.As silicon alloy, for example, can enumerate silica removal and comprise at least a alloy that is selected from tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium outward as the second formation element.
As the compound of tin or the compound of silicon, for example, can enumerate the compound that comprises oxygen (O) or carbon (C).Outside detin or the silicon, this compound can comprise that above-mentioned second constitutes element.
As the negative material that can embed and deviate from lithium, can further enumerate other metallic compounds or polymeric material.As other metallic compounds, can enumerate oxide such as iron oxide, ruthenium-oxide and molybdenum oxide, Li
3N etc.As polymeric material, can enumerate polyacetylene etc.
In this secondary cell, the capacity of negative material that can embed and deviate from lithium is greater than anodal 21 capacity.Therefore, in charging process, the lithium metal is not separated out on negative pole 22.
As nonaqueous solvents, for example, can enumerate ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, gamma-butyrolacton, gamma-valerolactone, 1,2-dimethoxy-ethane, oxolane, 2-methyltetrahydrofuran, 1,3-dioxolanes, 4-methyl isophthalic acid, 3-dioxolanes, methyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, sulfolane, dimethyl sulfoxide (DMSO), trimethyl phosphate or wherein above-claimed cpd to small part hydrogen by halogen substituted compounds.Specifically, preferably comprise the 4-fluoro-1 as fluorine compounds of ethylene carbonate, 3-dioxolanes-2-ketone.4-fluoro-1,3-dioxolanes-2-ketone can form stable protective finish on the surface of negative pole 22, and can prevent the decomposition reaction of solvent thus.This solvent can use separately, maybe can use its two or more by mixing.
As electrolytic salt, for example, can enumerate lithium salts, as LiAsF
6, LiPF
6, LiBF
4, LiClO
4, LiB (C
6H
5)
4, LiCH
3SO
3, LiCF
3SO
3, LiC (CF
3SO
2)
3, LiAlCl
4, Li
2SiF
6, LiCl and LiBr.Specifically, preferably has the lithium salts of fluorine atom, because can obtain high conductivity thus.Can use a kind of of this electrolytic salt separately, maybe can use its two or more by mixing.
With respect to solvent, the content of electrolytic salt is preferably in the scope of 0.5mol/kg-3.0mol/kg.When content was outside this scope, ionic conductance reduced greatly, and therefore might can't obtain sufficient battery behavior.
Electrolyte further comprise have the proton capturing ability compound as additive.For example, this compound can effectively be caught free acid as passing through 4-fluoro-1, the hydrofluoric acid that 3-dioxolanes-2-ketone hydrolysis produces etc.Thus, even at high temperature, also can prevent the decomposition reaction of electrolyte etc.As compound, can enumerate nitrogen compound, because the unshared electron pair in the nitrogen of this nitrogen compound can be caught free acid with unshared electron pair with proton capturing ability.Specifically, the cyclic compound shown in the hexa of preferably representing, the cyclic compound shown in the Chemical formula 2 or the chemical formula 3 by structural formula shown in the Chemical formula 1.Thus, can obtain higher effect.
[Chemical formula 1]
[Chemical formula 2]
[chemical formula 3]
In Chemical formula 2 and chemical formula 3, R1, R2, R3 represent hydrogen group or substituting group group.R2 and R3 can be same to each other or different to each other.P and q represent 2 or bigger integer respectively.As substituting group, for example, can enumerate halogen group, alkyl, alkylidene, phenyl, naphthyl or alkoxyl.
As the cyclic compound shown in cyclic compound shown in the Chemical formula 2 and the chemical formula 3,2 shown in 1,3,5 triazines shown in the preferred chemical formula 4, the chemical formula 5,2,4,4,6,6-hexafluoro-1,3,5-three azepines-2,4, shown in 6-three phospha benzene (triphosphorine) or the chemical formula 62,2,4,4,6,6-chlordene-1,3,5-three azepines-2,4,6-three phospha benzene.Thus, can obtain higher effect.
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
As nitrogen compound with unshared electron pair, the lithium salts shown in the also preferred chemical formula 7.As this lithium salts, for example, can enumerate the two pentafluoroethane sulfonic acid imide lis shown in two trifluoromethayl sulfonic acid imide lis shown in the chemical formula 8 or the chemical formula 9.
[chemical formula 7]
(C
mF
2m+1SO
2)(C
nF
2n+1SO
2)NLi
In formula, m and n represent integer.
[chemical formula 8]
LiN(CF
3SO
2)
2
[chemical formula 9]
LiN(C
2F
5SO
2)
2
As nitrogen compound with unshared electron pair; can enumerate 1 shown in the 3-methyl shown in the Chemical formula 1 0-2- oxazolidone, the Chemical formula 11; 5-fluoro-1 shown in N methyl succinimide shown in 3-diacetyl-2-imidazolone, the Chemical formula 12, the Chemical formula 13, the pyrazine shown in the pyridine shown in the triphenylamine shown in 3-dimethyl uracil, the Chemical formula 14, the Chemical formula 15, the Chemical formula 16 etc.
[Chemical formula 1 0]
[Chemical formula 1 1]
[Chemical formula 1 2]
[Chemical formula 1 3]
[Chemical formula 1 4]
[Chemical formula 1 5]
[Chemical formula 1 6]
The concentration of nitrogen compound preferably satisfies mathematical expression 2 in electrolyte.In this scope, can obtain high effect.
[mathematical expression 2]
4-fluoro-1, concentration (the mol/kg)≤4-fluoro-1 of the quantity * 0.4≤nitrogen compound of the unshared electron pair of the concentration (mol/kg) of 3-dioxolanes-2-ketone/in nitrogen compound, the concentration (mol/kg) of the 3-dioxolanes-2-ketone/quantity of unshared electron pair * 10 in nitrogen compound
In addition, as nitrogen compound with unshared electron pair, the six ethylidene tetramines that the structural formula shown in the preferred especially Chemical formula 17 is represented.This compound is three ring big cage shape (macrocage) compounds.In this compound, the unshared electron pair of all bridgehead position nitrogen-atoms is in a minute subcenter coordination, and has the molecule room with high electron density.Thus, six ethylidene tetramines have the high seizure free acid such as the ability of hydrofluoric acid.In addition, sterically hinderedly prevent reactions such as the free acid of catching and solvent.
[Chemical formula 1 7]
The content of six ethylidene tetramines is preferably in 0.001 weight %-5 weight % scope in electrolyte.When this content is low, catch the effect deficiency of free acid.When this content is high, the ionic conductance step-down.
Can use any macromolecular compound, need only this macromolecular compound lyosoption and make its gelation.For example, can enumerate the copolymer of fluoridizing macromolecular compound such as polyvinylidene fluoride and vinylidene fluoride and hexafluoropropylene, ether macromolecular compound such as poly(ethylene oxide) and comprise the crosslinked body of poly(ethylene oxide) comprise that polyacrylonitrile, polyacrylate or polymethacrylates are as the compound of repetitive etc.Especially, according to oxidation-reduction stability, fluoridize macromolecular compound and expect.Can use a kind of of these macromolecular compounds separately, maybe can use its two or more by mixing.
For example, this secondary cell can followingly be made.
At first, for example, positive electrode active materials, adhesive and electric conductor are mixed with the preparation cathode mix.This cathode mix is dispersed in solvent such as the N-N-methyl-2-2-pyrrolidone N-to form the cathode mix slurry.Then, the two sides of positive electrode collector 21A or its are simultaneously applied with this cathode mix slurry, drying, and with the gains compression molding.Thereby, form anode active material layer 21B and form anodal 21.Subsequently, for example, positive wire 11 is linked on the positive electrode collector 21A by for example ultra-sonic welded or spot welding.Afterwards, preparation electrolyte and macromolecular compound, and on anode active material layer 21B, promptly on anodal 21 two sides or its one side, form dielectric substrate 24.
In addition, for example, negative active core-shell material and adhesive are mixed with preparation negative pole mixture.This negative pole mixture is dispersed in solvent such as the N-N-methyl-2-2-pyrrolidone N-to form negative pole mixture slurry.Then, the two sides of negative electrode collector 22A or its are simultaneously applied with this negative pole mixture slurry and dry.Then, with the gains compression molding.Thereby, form anode active material layer 22B and form negative pole 22.Subsequently, negative wire 12 is connected on the negative electrode collector 22A by for example ultra-sonic welded or spot welding.With with anodal 21 identical modes, on anode active material layer 22B, promptly on the two sides or its one side of negative pole 22, form dielectric substrate 24.
Afterwards, positive pole 21 and the negative pole 22 and the barrier film 23 stacked and screw windings therebetween of dielectric substrate 24 will be formed with separately.Boundary belt 25 is adhered to outermost to form spiral winding electrode 20.At last, for example, spiral winding electrode 20 is clipped between the package member 31, and with the outer rim of package member 31 by sealings hermetically such as thermofussion weldings, and encapsulation spiral winding electrode 20.Then, adhesive film 32 is inserted between positive wire 11/ negative wire 12 and the package member 31.Thus, finish the secondary cell shown in Fig. 1 and 2.
In addition, above-mentioned secondary cell can followingly be made.At first, formation as implied above anodal 21 and negative pole 22, and with positive wire 11 and negative wire 12 link anodal 21 and negative pole 22 on.Afterwards, with positive pole 21 and negative pole 22 and barrier film 23 stacked and screw windings therebetween.Boundary belt 25 is adhered to its outermost, and form the screw winding body.Then, this screw winding body is clipped between the package member 31, will except that the outermost thermofussion welding the side obtaining a bag shape, and this screw winding body is included in this package member 31 inside.Subsequently, preparation comprises electrolyte, as the monomer of raw material that is used for macromolecular compound and the electrolyte composition of other materials if necessary such as polymerization initiator and polymerization inhibitor, and it is injected in the package member 31.
After the injection electrolyte is with composition, with opening thermofussion welding and sealing hermetically under vacuum atmosphere of package member 31.Then, with gains heating so that monomer polymerization to obtain macromolecular compound.Thus, form gel-like electrolyte layer 24, and the secondary cell shown in assembling Fig. 1 and 2.
In this secondary cell, when when charging, for example, lithium ion is deviate from and is embedded the negative pole 22 by electrolyte from anodal 21.When discharge, for example, lithium ion is deviate from and is embedded anodal 21 by electrolyte from negative pole 22.In electrolyte, comprise 4-fluoro-1,3-dioxolanes-2-ketone and when having the compound of proton capturing ability, free acid is as passing through 4-fluoro-1, the quilts such as hydrofluoric acid that 3-dioxolanes-2-ketone hydrolysis produces have the compound of proton capturing ability catches effectively, and prevents the decomposition reaction of electrolyte thus.
In addition, when comprising six ethylidene tetramines in the electrolyte, free acid is caught effectively, its reactive reduction, and therefore prevent the decomposition reaction etc. of electrolyte.
As above, according to the secondary cell of this execution mode, owing in electrolyte, comprise 4-fluoro-1,3-dioxolanes-2-ketone and compound with proton capturing ability, free acid can be had the compound of proton capturing ability catches effectively, and can prevent decomposition reaction of electrolyte etc. thus.Therefore, can suppress the expansion of battery.
In addition, when comprising nitrogen compound when having the compound of proton capturing ability, can obtain higher effect with unshared electron pair.
In addition, when the concentration of nitrogen compound in the electrolyte satisfies mathematical expression 2, can obtain higher effect.
According to the electrolyte of this execution mode,, when effectively catching free acid, can reduce its reactivity owing to wherein comprise six ethylidene tetramines.Therefore, the secondary cell according to this execution mode that uses this electrolyte can prevent the decomposition reaction of electrolyte etc., and can improve battery behavior as charging and discharging efficiency.
Especially, when the content of six ethylidene tetramines in the electrolyte is in 0.001 weight %-5 weight % scope, can obtain higher effect.
(second execution mode)
Secondary cell according to second embodiment of the invention is such secondary cell, and wherein capacity of negative plates comprises because as the embedding of the lithium of electrode reaction thing and the voxel of deviating from because the voxel of separating out and dissolving of lithium, and by itself and expression.
Except the structure difference of anode active material layer, this secondary cell have with according to similar structure of the secondary cell of first execution mode and effect, and can make similarly.Therefore, provide description with Fig. 2 by using identical symbol with reference to figure 1 here.Detailed description for same components will be omitted.
In anode active material layer 22B, for example, the charging capacity that can embed and deviate from the negative material of lithium by setting is the value less than the charging capacity of positive pole 21, in charging process, when open circuit voltage (that is, cell voltage) when being lower than overcharge voltage, the lithium metal begins to separate out on negative pole 22.Therefore, in this secondary cell, can embed and deviate from the negative material of lithium and the effect that the lithium metal plays negative active core-shell material, and when the lithium metal was separated out, the negative material that can embed and deviate from lithium was a basis material.As the negative material that can embed and deviate from lithium, can enumerate and the first execution mode materials similar.Specifically, preferably can embed and deviate from the material with carbon element of lithium.
Overcharge voltage is meant the open circuit voltage when battery becomes overcharge condition.For example, overcharge voltage is meant than (it is the high voltage of open circuit voltage of the battery of " charging fully " of description in the Japanese The Storage Battery Industry in China association (Japanese battery association) (one of policy of Japan StorageBattery industries association (Battery Association of Japan) appointment) and definition at " Guideline for safety assessment of lithium secondary batteries " (SBA G1101).In other words, overcharge voltage is meant than the high voltage of open circuit voltage after employed charging method, standard charging method or the charging of recommendation charging method in the rated capacity that is obtaining each battery by use.
Thus, in this secondary cell, high-energy-density can be obtained, and the cycle characteristics of the challenge in the existing lithium metal secondary batteries and the improvement of quick charge characteristic can be realized having become.Use the negative material can embed and deviate from lithium be used for negative pole 22 aspect, this secondary cell and existing lithium rechargeable battery are similar.In addition, aspect lithium was separated out on negative pole 22, this secondary cell and existing lithium metal secondary batteries were similar.
In order more effectively to obtain above-mentioned characteristic, for example, during maximum voltage before open circuit voltage becomes overcharge voltage, the maximum capacity of separating out of the lithium metal of separating out on negative pole 22 is preferably 0.05 times-3.0 times of charging capacity ability of the negative material that can embed and deviate from lithium.Separate out when too many when the lithium metal, cause and existing lithium metal secondary batteries similar problem.Simultaneously, when the lithium metal was separated out very little, charging and discharge capacity can not substantially improve.In addition, for example, the discharge capacity ability that can embed and deviate from the negative material of lithium is preferably 150mAh/g or bigger.Embed and to deviate from the ability of lithium high more, the quantitative change of separating out of lithium metal gets relatively more little.The charging capacity ability of negative material obtains by the electric weight when lithium metal wherein is discharged to 0V as the electrochemical cell of positive electrode active materials with constant current and constant-voltage method as negative pole and the negative material that can embed and deviate from lithium.The discharge capacity ability of negative material for example by when after above-mentioned charging, charged 10 hours with constant flow method or more the electric weight during as many as 2.5V obtain.
In this secondary cell, when when charging, lithium ion is deviate from from anodal 21, and at first embeds by electrolyte and to be included in can embed and deviate from the negative material of lithium in the negative pole 22.When further charging, be lower than at open circuit voltage under the state of overcharge voltage, the lithium metal begins to separate out on the surface of the negative material that can embed and deviate from lithium.Afterwards, the lithium metal continues to separate out up to charging on negative pole 22 and finishes.Then, when discharge, at first, the lithium metal of separating out on negative pole 22 is washed out as ion, and it embeds in anodal 21 by electrolyte.When further discharge, the lithium ion that embeds in the negative material of lithium that can embed and deviate from negative pole 22 is deviate from, and embeds in anodal 21 by electrolyte.When electrolyte comprises 4-fluoro-1,3-dioxolanes-2-ketone and when having the compound of proton capturing ability, free acid is as by 4-fluoro-1, and the quilts such as hydrofluoric acid that 3-dioxolanes-2-ketone hydrolysis produces have the compound of proton capturing ability catches effectively, and prevents the decomposition reaction of electrolyte thus.
In addition, when comprising six ethylidene tetramines in the electrolyte, free acid is caught effectively, its reactive reduction, and therefore prevent the decomposition reaction etc. of electrolyte.
Embodiment
Further, will describe specific embodiments of the invention in detail.
(embodiment 1-1 to 1-13)
Make capacity of negative plates wherein by because the battery that the embedding of lithium and the voxel deviate from are represented, promptly so-called lithium rechargeable battery.
At first, will be as cobalt acid lithium (lithium the cobaltate) (LiCoO of positive electrode active materials
2), as the graphite of electric conductor, mix with the preparation cathode mix as the polyvinylidene fluoride of adhesive.Subsequently, this cathode mix is dispersed in as starching to obtain cathode mix in the N-N-methyl-2-2-pyrrolidone N-of solvent.Afterwards, will be applied equably with this cathode mix slurry by the positive electrode collector 21A that aluminium foil is made, it is dried and also forms anodal 21 thus by the roll squeezer compression molding to form anode active material layer 21B.Afterwards, positive wire 11 is linked on the positive electrode collector 21A.
In addition, will mix with preparation negative pole mixture as the Delanium of negative active core-shell material with as the polyvinylidene fluoride of adhesive.This negative pole mixture is dispersed in as starching to obtain the negative pole mixture in the N-N-methyl-2-2-pyrrolidone N-of solvent.Afterwards, will be applied equably with this negative pole mixture slurry by the negative electrode collector 22A that Copper Foil is made, it is dried and also forms negative pole 22 by the roll squeezer compression molding thus to form anode active material layer 22B.Capacity Ratio between design anodal 21 and the negative pole 22, make negative pole 22 capacity by since the embedding of lithium and the voxel of deviating from represent.Afterwards, negative wire 12 is linked on the negative electrode collector 22A.
Subsequently, following formation electrolyte.Will be as the LiPF of electrolytic salt
6Be dissolved in the solvent, in this solvent as the ethylene carbonate of solvent and propylene carbonate with ethylene carbonate: the weight ratio of propylene carbonate=6: 4 is mixed.In addition, with 4-fluoro-1,3-dioxolanes-2-ketone and additive mix with it with preparation electrolyte.LiPF in the electrolyte
6Concentration be 0.7mol/kg.4-fluoro-1, the concentration of 3-dioxolanes-2-ketone is 0.1mol/kg.The concentration of additive is 0.06mol/kg.In addition, additive is the nitrogen compound with unshared electron pair.Specifically, in embodiment 1-1, use hexa, in embodiment 1-2, use 3-methyl-2- oxazolidone; use 1 in embodiment 1-3,3-diacetyl-2-imidazolone uses N methyl succinimide in embodiment 1-4; use 5-fluoro-1 in embodiment 1-5, the 3-dimethyl uracil uses triphenylamine in embodiment 1-6; in embodiment 1-7, use two trifluoromethayl sulfonic acid imide lis, in embodiment 1-8, use two pentafluoroethane sulfonic acid imide lis, in embodiment 1-9, use pyridine; in embodiment 1-10, use pyrazine, in embodiment 1-11, use 1,3; the 5-triazine uses 2,2 in embodiment 1-12; 4,4,6; 6-hexafluoro-1,3,5-three azepines-2; 4,6-three phospha benzene and in embodiment 1-13, use 2; 2,4,4; 6,6-chlordene-1,3; 5-three azepines-2,4,6-three phospha benzene.
Then, by keeping resulting electrolyte as the hexafluoropropylene of macromolecular compound and the copolymer of vinylidene fluoride.Thus, on positive pole 21 and negative pole 22, form gel-like electrolyte layer 24 respectively.The ratio of hexafluoropropylene is 6.9 weight % in copolymer.
Afterwards, will be formed with the stacked and screw winding of barrier film that the positive pole 21 of dielectric substrate 24 and negative pole 22 and the polyethylene film by thick 20 μ m therebetween make 23 separately to form spiral winding electrode 20.
Gained spiral winding electrode 20 is clipped between the package member of being made by laminated film 31, and under reduced pressure embeds wherein.Thus, make secondary cell illustrated in figures 1 and 2.
As comparative example 1-1, make secondary cell in the mode identical, except not adding additive with embodiment 1-1 to 1-13 with respect to embodiment 1-1 to 1-13.
For the secondary cell of embodiment 1-1 to 1-13 and comparative example 1-1 gained, following detection high-temperature storage characteristics.At first, after the upper limit of 4.2V, under 4.2V, carry out constant voltage charge at the constant current charge that carries out 1C under 23 ℃ the environment.Total charging interval is 3 hours.Subsequently, this secondary cell is stored 1 month under 60 ℃ environment.For high-temperature storage characteristics, with the expansion ratio that [thickness before (thickness before the thickness-storage after the storage)/storage] * 100 (%) are at high temperature stored.The results are shown in the table 1.1C is the current value that theoretical capacity discharged in 1 hour fully.
[table 1]
| Additive | Expansion ratio (%) | |
| Embodiment 1-1 | Hexa | 1.8 |
| Embodiment 1-2 | 3-methyl-2- oxazolidone | 7.2 |
| Embodiment 1-3 | 1,3-diacetyl-2-imidazolone | 8.7 |
| Embodiment 1-4 | N methyl succinimide | 8.1 |
| Embodiment 1-5 | 5-fluoro-1, the 3-dimethyl uracil | 3.5 |
| Embodiment 1-6 | Triphenylamine | 7.0 |
| Embodiment 1-7 | Two trifluoromethayl sulfonic acid imide lis | 4.3 |
| Embodiment 1-8 | Two pentafluoroethane sulfonic acid imide lis | 6.6 |
| Embodiment 1-9 | Pyridine | 6.2 |
| Embodiment 1-10 | Pyrazine | 4.2 |
| Embodiment 1-11 | 1,3,5-triazines | 3.1 |
| Embodiment 1-12 | 2,2,4,4,6,6-hexafluoro-1,3,5-triaza-2,4,6-triphosphorines-three phospha benzene | 2.8 |
| Embodiment 1-13 | 2,2,4,4,6,6-chlordene-1,3,5-triaza-2,4,6-triphosphorines-three phospha benzene | 3.0 |
| Comparative example 1-1 | Do not have | 51.2 |
As demonstrated in Table 1, have the embodiment 1-1 to 1-13 of the nitrogen compound of unshared electron pair according to use, the expansion ratio when at high temperature storing reduces.
That is, find when in electrolyte, comprising compound, even also can suppress the expansion of battery when at high temperature storing with proton capturing ability.
(embodiment 2-1 to 2-5 and 3-1 to 3-5)
As embodiment 2-1 to 2-5, make secondary cell in the mode identical with embodiment 1-1, the concentration of additive is as shown in table 2 in electrolyte in the scope of 0.005mol/kg-0.5mol/kg, change.4-fluoro-1 in the electrolyte, the concentration of 3-dioxolanes-2-ketone is 0.1mol/kg.In the quantity as unshared electron pair in the hexa of additive is 4 pairs.In mathematical expression 2, [4-fluoro-1, the quantity of the unshared electron pair of the concentration (mol/kg) of 3-dioxolanes-2-ketone/in nitrogen compound] * 0.4 be 0.01mol/kg, and [4-fluoro-1, the concentration (mol/kg) of the 3-dioxolanes-2-ketone/quantity of unshared electron pair in nitrogen compound] * 10 are 0.25mol/kg.
[table 2]
| Additive | Expansion ratio (%) | ||
| Kind | Concentration (mol/kg) | ||
| Embodiment 2-1 | Hexa | 0.5 | 12.3 |
| Embodiment 2-2 | 0.25 | 2.6 | |
| Embodiment 2-3 | 0.1 | 1.7 | |
| Embodiment 1-1 | 0.06 | 1.8 | |
| Embodiment 2-4 | 0.01 | 3.7 | |
| Embodiment 2-5 | 0.005 | 10.1 | |
| Comparative example 1-1 | Do not have | 0 | 51.2 |
4-fluoro-1,3-dioxolanes-2-ketone: 0.1mol/kg
As embodiment 3-1 to 3-5, make secondary cell in the mode identical with embodiment 1-1, the concentration of additive is as shown in table 3 in electrolyte in the scope of 0.005mol/kg-0.5mol/kg, change.4-fluoro-1 in the electrolyte, the concentration of 3-dioxolanes-2-ketone is 0.2mol/kg.In mathematical expression 2, [4-fluoro-1, the quantity of the unshared electron pair of the concentration (mol/kg) of 3-dioxolanes-2-ketone/in nitrogen compound] * 0.4 be 0.02mol/kg, and [4-fluoro-1, the concentration (mol/kg) of the 3-dioxolanes-2-ketone/quantity of unshared electron pair in nitrogen compound] * 10 are 0.5mol/kg.
[table 3]
| Additive | Expansion ratio (%) | ||
| Kind | Concentration (mol/kg) | ||
| Embodiment 3-1 | Hexa | 0.5 | 3.5 |
| Embodiment 3-2 | 0.25 | 2.9 | |
| Embodiment 3-3 | 0.1 | 2.0 | |
| Embodiment 3-4 | 0.01 | 9.2 | |
| Embodiment 3-5 | 0.005 | 15.1 | |
4-fluoro-1,3-dioxolanes-2-ketone: 0.2mol/kg
Prove as table 2 and table 3, embodiment 1-1 and the 2-2 to 2-4 of concentration in the 0.01mol/kg-0.25mol/kg scope according to hexa in the electrolyte wherein, or according to the embodiment 3-1 to 3-3 of concentration in the 0.02mol/kg-0.5mol/kg scope of hexa in the electrolyte wherein, the expansion ratio when at high temperature storing is lower than the embodiment 2-1 of concentration outside this scope and the expansion ratio of 2-5 or embodiment 3-4 and 3-5 of hexa in the electrolyte wherein.
That is, find that concentration as the hexa of additive is preferably in the scope of mathematical expression 2.
(embodiment 4-1 to 4-5 and 5-1 to 5-5)
As embodiment 4-1 to 4-5, make secondary cell in the mode identical with embodiment 1-7, the concentration of additive is as shown in table 4 in electrolyte in the scope of 0.02mol/kg-2.0mol/kg, change.4-fluoro-1 in the electrolyte, the concentration of 3-dioxolanes-2-ketone is 0.1mol/kg.In the quantity as unshared electron pair in two trifluoromethayl sulfonic acid imide lis of additive is 1 pair.In mathematical expression 2, [4-fluoro-1, the quantity of the unshared electron pair of the concentration (mol/kg) of 3-dioxolanes-2-ketone/in nitrogen compound] * 0.4 be 0.04mol/kg, and [4-fluoro-1, the concentration (mol/kg) of the 3-dioxolanes-2-ketone/quantity of unshared electron pair in nitrogen compound] * 10 are 1.0mol/kg.
[table 4]
| Additive | Expansion ratio (%) | ||
| Kind | Concentration (mol/kg) | ||
| Embodiment 4-1 | Two trifluoromethayl sulfonic acid imide lis | 2.0 | 7.7 |
| Embodiment 4-2 | 1.0 | 3.3 | |
| Embodiment 4-3 | 0.4 | 3.3 | |
| Embodiment 1-7 | 0.06 | 4.3 | |
| Embodiment 4-4 | 0.04 | 5.8 | |
| Embodiment 4-5 | 0.02 | 13.2 | |
| Comparative example 1-1 | N/ |
0 | 51.2 |
4-fluoro-1,3-dioxolanes-2-ketone: 0.1mol/kg
As embodiment 5-1 to 5-5, make secondary cell in the mode identical with embodiment 1-7, the concentration of additive is as shown in table 5 in electrolyte in the scope of 0.02mol/kg-2.0mol/kg, change.4-fluoro-1 in the electrolyte, the concentration of 3-dioxolanes-2-ketone is 0.2mol/kg.In mathematical expression 2, [4-fluoro-1, the quantity of the unshared electron pair of the concentration (mol/kg) of 3-dioxolanes-2-ketone/in nitrogen compound] * 0.4 be 0.08mol/kg, and [4-fluoro-1, the concentration (mol/kg) of the 3-dioxolanes-2-ketone/quantity of unshared electron pair in nitrogen compound] * 10 are 2.0mol/kg.
[table 5]
| Additive | Expansion ratio (%) | ||
| Kind | Concentration (mol/kg) | ||
| Embodiment 5-1 | Two trifluoromethayl sulfonic acid imide lis | 2.0 | 3.8 |
| Embodiment 5-2 | 1.0 | 3.9 | |
| Embodiment 5-3 | 0.4 | 4.0 | |
| Embodiment 5-4 | 0.04 | 10.4 | |
| Embodiment 5-5 | 0.02 | 18.7 | |
4-fluoro-1,3-dioxolanes-2-ketone: 0.2mol/kg
Prove as table 4 and table 5, embodiment 1-7 and the 4-2 to 4-4 of concentration in the 0.04mol/kg-1.0mol/kg scope according to two trifluoromethayl sulfonic acid imide lis in the electrolyte wherein, or according to the embodiment 5-1 to 5-3 of concentration in the 0.08mol/kg-2.0mol/kg scope of two trifluoromethayl sulfonic acid imide lis in the electrolyte wherein, the expansion ratio when at high temperature storing is lower than the embodiment 4-1 of concentration outside this scope and the expansion ratio of 4-5 or embodiment 5-4 and 5-5 of two trifluoromethayl sulfonic acid imide lis in the electrolyte wherein.
That is, find even preferably use other additives, as long as the concentration of this other additives is in the scope of mathematical expression 2.
(embodiment 6-1 and 6-2)
Make secondary cell illustrated in figures 1 and 2.At first, will be as the cobalt acid lithium (LiCoO of positive electrode active materials
2), as the graphite of electric conductor, mix with the preparation cathode mix as the polyvinylidene fluoride of adhesive.Subsequently, this cathode mix is dispersed in as starching to obtain cathode mix in the N-N-methyl-2-2-pyrrolidone N-of solvent.Afterwards, will be applied equably with this cathode mix slurry by the positive electrode collector 21A that aluminium foil is made, it is dried and also forms anodal 21 thus by the roll squeezer compression molding to form anode active material layer 21B.Afterwards, positive wire 11 is linked on the positive electrode collector 21A.
In addition, will mix with preparation negative pole mixture as the carbonaceous mesophase spherules (MCMB) of negative active core-shell material with as the polyvinylidene fluoride of adhesive.This negative pole mixture is dispersed in as starching to obtain the negative pole mixture in the N-N-methyl-2-2-pyrrolidone N-of solvent.Afterwards, will be applied equably with this negative pole mixture slurry by the negative electrode collector 22A that Copper Foil is made, it is dried and also forms negative pole 22 by the roll squeezer compression molding thus to form anode active material layer 22B.Afterwards, negative wire 12 is linked on the negative electrode collector 22A.
Subsequently, following formation electrolyte.Will be as the LiPF of electrolytic salt
6Be dissolved in the solvent, wherein as the ethylene carbonate of solvent and propylene carbonate with ethylene carbonate: the weight ratio of propylene carbonate=1: 1 is mixed.In addition, additive is mixed with it to form electrolyte.LiPF in the electrolyte
6Concentration be 1mol/kg.As additive, in embodiment 6-1, use six ethylidene tetramines and in embodiment 6-2, use hexa.Content of additive is 0.5 weight % in the electrolyte.In the hexa shown in Chemical formula 1, the unshared electron pair of nitrogen-atoms side positioning outside molecule.
Then, by keeping resulting electrolyte as the hexafluoropropylene of macromolecular compound and the copolymer of vinylidene fluoride.Thus, on positive pole 21 and negative pole 22, form gel-like electrolyte layer 24 respectively.The ratio of hexafluoropropylene is 6.9 weight % in copolymer.
Afterwards, will be formed with the stacked and screw winding of barrier film that the positive pole 21 of dielectric substrate 24 and negative pole 22 and the polyethylene film by thick 20 μ m therebetween make 23 separately to form spiral winding electrode 20.
Gained spiral winding electrode 20 is clipped between the package member of being made by laminated film 31, and under reduced pressure embeds wherein.Thus, make secondary cell illustrated in figures 1 and 2.
As comparative example 6-1, make secondary cell in the mode identical with 6-2, except not mixing six ethylidene tetramines or hexa as additive with embodiment 6-1 with respect to embodiment 6-1 and 6-2.
Secondary cell for embodiment 6-1 and 6-2 and comparative example 6-1 manufacturing detects cycle characteristics and high-temperature storage characteristics.
For cycle characteristics, recharge and discharge are wherein carried out the constant current of 1C and constant voltage charge up to the upper limit of 4.2V under 23 ℃, after total charging time is 2.5 hours, carry out the final voltage of the constant-current discharge of 1C up to 3.0V under 23 ℃.With the discharge capacity ratio in each circulation of the discharge capacity that circulates with respect to the first time, promptly (discharge capacity in the discharge capacity in the each circulation/circulation first time) * 100 (%) obtain cycle characteristics.The results are shown among Fig. 3.
For high-temperature storage characteristics, following acquisition cell thickness and discharge capacitance.At first, carry out the constant current of 1C and the constant voltage charge upper limit up to 4.2V under 23 ℃, total charging time is 2.5 hours.Afterwards, under 23 ℃, carry out the final voltage of the constant-current discharge of 1C up to 3.0V, and the discharge capacity before obtaining to store.Subsequently, carry out the constant current of 1C and the constant voltage charge upper limit up to 4.31V under 23 ℃, total charging time is 2.5 hours, to obtain overcharge condition.Afterwards, this battery storage in being set at 60 ℃ constant temperature bath, and is measured cell thickness with respect to the storage time.Then, battery storage being set in 60 ℃ the constant temperature bath after 28 days, under 23 ℃, carry out the final voltage of the constant-current discharge of 1C up to 3.0V.Subsequently, carry out the constant current of 1C and the constant voltage charge upper limit up to 4.2V once more under 23 ℃, total charging time is 2.5 hours.Afterwards, under 23 ℃, carry out the final voltage of the constant-current discharge of 1C up to 3.0V, and the discharge capacity after obtaining to store.With discharge capacity after storing and the ratio that stores preceding discharge capacity, promptly (discharge capacity before the discharge capacity/storage after the storage) * 100 (%) obtain discharge capacitance.The results are shown among Fig. 4 and the table 6.
[table 6]
| Discharge capacitance (%) | |
| Embodiment 6-1 | 95 |
| Embodiment 6-2 | 80 |
| Comparative example 6-1 | 78 |
Simultaneously, with LiPF
6Be dissolved in each solvent of propylene carbonate, ethylene carbonate, gamma-butyrolacton, dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate, make LiPF
6Concentration become lmol/l.In addition, six ethylidene tetramines or hexa are further mixed with preparation electrolyte with it.The content of six ethylidene tetramines or hexa is 0.5 weight % in the electrolyte.In addition, prepare wherein LiPF
6Be dissolved in and make LiPF in each solvent of propylene carbonate, ethylene carbonate, gamma-butyrolacton, dimethyl carbonate, diethyl carbonate or methyl ethyl carbonate
6Concentration become the electrolyte of 1mol/l.Each electrolyte of 50ml is included in the withstand voltage closed shell of stainless steel hermetically, kept 100 hours down at 80 ℃.Afterwards, measure the concentration of hydrofluoric acid (HF) by alkalim-etry.The results are shown in the table 7.
[table 7]
| Additive | HF concentration (ppm by weight) | |||||
| Propylene carbonate | Ethylene carbonate | Gamma-butyrolacton | Dimethyl carbonate | Diethyl carbonate | Methyl ethyl carbonate | |
| Six ethylidene tetramines | 10 | 31 | 5 | 6 | 10 | 34 |
| Hexa | 13 | 30 | 4 | 8 | 13 | 36 |
| Do not have | 175 | 206 | 149 | 190 | 174 | 320 |
As demonstrated in Table 7, when the electrolyte that mixes with six ethylidene tetramines at high temperature stores, the concentration of hydrofluoric acid can be lower than the concentration of hydrofluoric acid in the electrolyte that does not add six ethylidene tetramines or hexa, and also is like this under the situation of the electrolyte that mixes with hexa.In addition, electrolyte that mixes with six ethylidene tetramines and the electrolyte that mixes with hexa can reduce the concentration of hydrofluoric acid comparably.
Simultaneously, prove as table 6 and Fig. 3 and Fig. 4, when forming battery, comprise in the electrolyte therein among the embodiment 6-1 of six ethylidene tetramines, compare with the comparative example 6-1 that does not comprise six ethylidene tetramines or hexa with the embodiment 6-2 that comprises hexa, cycle characteristics improve and at high temperature expand and the reduction of discharge capacity less.
That is, find when comprising six ethylidene tetramines in the electrolyte, can catch free acid such as hydrofluoric acid, and particularly in battery, even because charging and discharge when oxidizing atmosphere becomes stronger, also can obtain this effect.
(embodiment 7-1 to 7-6)
Make secondary cell in the mode identical with embodiment 6-1, the content of six ethylidene tetramines is 0.001 weight %, 0.01 weight %, 0.1 weight %, 1 weight %, 5 weight % or the 10 weight % in electrolyte.
Secondary cell for embodiment 7-1 to 7-6 makes detects cycle characteristics in the mode identical with 6-2 with embodiment 6-1.The result is shown among Fig. 5 with the result of embodiment 6-1 and comparative example 6-1.In addition, also detect ionic conductance.
Prove that as Fig. 5 along with the content increase of six ethylidene tetramines in the electrolyte, cycle characteristics improves, and the approximately constant that when the content of six ethylidene tetramines in the electrolyte surpasses 5 weight %, becomes.Simultaneously, the content along with six ethylidene tetramines in the electrolyte increases the ionic conductance reduction.
That is, find that the content of six ethylidene tetramines in the electrolyte is preferably in 0.001 weight %-5 weight % scope.
With reference to execution mode and embodiment the present invention has been described.But, the invention is not restricted to above-mentioned execution mode and the foregoing description, and can carry out various improvement.For example, in above-mentioned execution mode and the foregoing description, the instantiation of the secondary cell with screw winding structure has been described.But the present invention can be applied to have the secondary cell of wherein anodal and the structure that negative pole is folding similarly or have secondary cells wherein anodal and other stepped constructions that negative pole is stacked.
In addition, in above-mentioned execution mode and the foregoing description, the situation of lithium as the electrode reaction thing of using described.But the present invention also can be applicable to wherein use other elements such as sodium (Na) and the potassium (K) in 1 family of the long period periodic table of elements; Other elements in 2 families of the long period periodic table of elements such as magnesium and calcium (Ca); Other light metals such as aluminium; Or the situation of the alloy of lithium or above-mentioned element.In this case, also can obtain similar effects.According to the electrode reaction thing, can select to embed and to deviate from positive electrode active materials, solvent of electrode reaction thing etc.
In addition, in above-mentioned execution mode and the foregoing description, described and used electrolyte wherein to remain on the situation of the gel-like electrolyte in the macromolecular compound.But, can use other electrolyte to replace above-mentioned electrolyte.As other electrolyte, for example, can enumerate the mixture of the electrolyte that only comprises electrolyte, solid electrolyte and electrolyte or the mixture of solid electrolyte and gel-like electrolyte with ionic conductivity.
As solid electrolyte, for example, the inorganic solid electrolyte that can use electrolytic salt wherein to be dispersed in the copolymer solid electrolyte in the macromolecular compound with ionic conductivity or to form by ionic conducting glass, ionic crystals etc.As macromolecular compound, for example, can be individually, by mixing or by copolymerization in molecule, use ether macromolecular compound such as poly(ethylene oxide) and comprise crosslinked body or ester macromolecular compound such as the polymethacrylates and the polyacrylate of poly(ethylene oxide).As inorganic solid electrolyte, can use lithium nitride, lithium iodide etc.
In addition, in above-mentioned execution mode and the foregoing description, described and used film to be used for the situation of package member 31.But the present invention can be applicable to use canister to be used for the secondary cell with other shapes such as cylinder type, Coin shape and button type of package member.In this case, can obtain similar effects.In addition, except that secondary cell, the present invention also can be applicable to primary cell.
Claims (17)
1. one kind comprises 4-fluoro-1,3-dioxolanes-2-ketone and the electrolyte with compound of proton capturing ability.
2. the electrolyte of claim 1, wherein this compound with proton capturing ability comprises the nitrogen compound with unshared electron pair.
3. the electrolyte of claim 2, wherein this nitrogen compound comprises and is selected from least a of the cyclic compound shown in cyclic compound shown in the lithium salts shown in hexa, the Chemical formula 1, the Chemical formula 2 and the chemical formula 3,
[Chemical formula 1]
(C
mF
2m+1SO
2)(C
nF
2n+1SO
2)NLi
Wherein m and n represent positive integer,
[Chemical formula 2]
Wherein R1 represents hydrogen or substituting group, and p represents 2 or bigger integer,
[chemical formula 3]
Wherein R2 and R3 represent hydrogen or substituting group, and q represents 2 or bigger integer.
4. the electrolyte of claim 2, wherein the concentration of this nitrogen compound satisfies mathematical expression 1,
[mathematical expression 1]
4-fluoro-1, the concentration (mol/kg) of the 3-dioxolanes-2-ketone/concentration of the quantity of unshared electron pair * 0.4≤nitrogen compound (mol/kg)≤4-fluoro-1 in nitrogen compound, the concentration (mol/kg) of the 3-dioxolanes-2-ketone/quantity of unshared electron pair * 10 in nitrogen compound.
5. electrolyte that comprises six ethylidene tetramines.
6. the electrolyte of claim 5, wherein the content of six ethylidene tetramines is in 0.001 weight %-5 weight % scope.
7. the electrolyte of claim 5 further comprises the electrolytic salt with fluorine atom.
8. battery comprises:
Anodal;
Negative pole; With
Electrolyte,
Wherein this electrolyte comprises 4-fluoro-1,3-dioxolanes-2-ketone and the compound with proton capturing ability.
9. the battery of claim 8, wherein this compound with proton capturing ability comprises the nitrogen compound with unshared electron pair.
10. the battery of claim 9, wherein this nitrogen compound comprises and is selected from least a of the cyclic compound shown in cyclic compound shown in the lithium salts shown in hexa, the chemical formula 4, the chemical formula 5 and the chemical formula 6,
[chemical formula 4]
(C
mF
2m+1SO
2)(C
nF
2n+1SO
2)NLi
Wherein m and n represent positive integer,
[chemical formula 5]
Wherein R1 represents hydrogen or substituting group, and p represents 2 or bigger integer,
[chemical formula 6]
Wherein R2 and R3 represent hydrogen or substituting group, and q represents 2 or bigger integer.
11. the battery of claim 9, wherein the concentration of this nitrogen compound satisfies mathematical expression 2 in this electrolyte,
[mathematical expression 2]
4-fluoro-1, the concentration (mol/kg) of the 3-dioxolanes-2-ketone/concentration of the quantity of unshared electron pair * 0.4≤nitrogen compound (mol/kg)≤4-fluoro-1 in nitrogen compound, the concentration (mol/kg) of the 3-dioxolanes-2-ketone/quantity of unshared electron pair * 10 in nitrogen compound.
12. the battery of claim 8, wherein this negative pole comprises material with carbon element.
13. the battery of claim 8 wherein should positive pole, this negative pole and this electrolyte is accommodated in the membranaceous package member.
14. a battery comprises:
Anodal;
Negative pole; With
Electrolyte,
Wherein this electrolyte comprises six ethylidene tetramines.
15. the battery of claim 14, wherein in this electrolyte the content of six ethylidene tetramines in 0.001 weight %-5 weight % scope.
16. the battery of claim 14, wherein this electrolyte further comprises the electrolytic salt with fluorine atom.
17. the battery of claim 14 wherein should positive pole, this negative pole and this electrolyte is accommodated in the membranaceous package member.
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| KR102501252B1 (en) * | 2019-04-30 | 2023-02-20 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0818563A1 (en) * | 1996-01-30 | 1998-01-14 | Naganoken | Aqueous solution for forming metal complexes, tin-silver alloy plating bath, and process for producing plated object using the plating bath |
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- 2006-02-14 CN CN2009101670495A patent/CN101630759B/en active Active
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| CN111477961A (en) * | 2020-05-29 | 2020-07-31 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery containing non-aqueous electrolyte |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101630759B (en) | 2012-05-30 |
| CN101630759A (en) | 2010-01-20 |
| CN100550506C (en) | 2009-10-14 |
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