CN100367561C - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary battery Download PDFInfo
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- CN100367561C CN100367561C CNB2005100922575A CN200510092257A CN100367561C CN 100367561 C CN100367561 C CN 100367561C CN B2005100922575 A CNB2005100922575 A CN B2005100922575A CN 200510092257 A CN200510092257 A CN 200510092257A CN 100367561 C CN100367561 C CN 100367561C
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- electrolytic battery
- nonaqueous electrolytic
- rechargeable nonaqueous
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- sulfite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
To provide a nonaqueous electrolyte secondary battery with excellent high temperature characteristics and heavy current characteristics. This nonaqueous electrolyte secondary battery is equipped with a packaging material 6, a nonaqueous electrolyte stored in the packaging material 6 and containing chain sulfite, a positive electrode 3 housed in the packaging material 6, being capable of occluding and discharging Li, and a negative electrode 4 housed in the packaging material 6 and containing a conductive agent containing a carbonaceous material and lithium titanate.
Description
The cross reference of relevant application
The application is according to the No.2005-36609 of Japanese patent application formerly that proposes in the No.2004-099383 of Japanese patent application formerly that proposed on March 30th, 2004 and on February 14th, 2005 and require to enjoy its priority, and the whole contents of quoting above-mentioned application here as a reference.
Technical field
The present invention relates to rechargeable nonaqueous electrolytic battery, as lithium rechargeable battery.
Background technology
Rechargeable nonaqueous electrolytic battery is charged and discharge by the migration of lithium ion between negative pole and positive pole.As battery, rechargeable nonaqueous electrolytic battery has been carried out deeply comprehensively research with high-energy-density.
In recent years, require rechargeable nonaqueous electrolytic battery to have various performances.For example, expectation is approximately being used under the 3C discharge as the rechargeable nonaqueous electrolytic battery of digital camera power supply.In addition, expect that the rechargeable nonaqueous electrolytic battery that is used for vehicle such as hybrid electric vehicle is being not less than use under about 10C discharge.In this case, rechargeable nonaqueous electrolytic battery need have high rate capability.In addition, because being used for the rechargeable nonaqueous electrolytic battery of vehicle, expectation under hot environment, uses, so also need to improve the high-temperature behavior of rechargeable nonaqueous electrolytic battery.
Use Li-Ti oxide to drop into practical application as the rechargeable nonaqueous electrolytic battery of negative electrode active material, the cell expansion that reason takes place when being this charging/discharging of secondary cell and shrink for a short time, and because this secondary cell has the long life-span is excellent therefore.Yet the defective of using the rechargeable nonaqueous electrolytic battery of Li-Ti oxide is that the high rate capability of Li-Ti oxide poorly conductive and this battery is poor.
In this case, by use carbonaceous material such as acetylene black or carbon black as conductive agent to attempt to improve high rate capability.Yet, be strong especially to the requirement of high rate capability.Recently satisfy this special requirement if increase the mixing of conductive agent, can reduce the energy density of negative pole so.
Japanese patent gazette (Kokai) No.2003-163029 has proposed a kind of technical scheme of improving high rate capability.Especially, this patent proposes to use the inferior sour ethyl that comprises following chemical formula (1) expression as the propane sultone of additive or following chemical formula (2) the expression nonaqueous electrolyte as additive:
According to the above-mentioned patent of quoting, the low electric conductivity of lithium titanate is derived from and is formed on the lip-deep rutile titanium dioxide phase of lithium titanate.Learn: glycol sulfite or propane sultone have formed the organic film of macroion conductivity in the initial state of charge of secondary cell, thereby cover the rutile titanium dioxide with low electric conductivity, and the result can improve the high rate capability of secondary cell.Yet this technical scheme can not obtain enough high rate capabilities.
Summary of the invention
An object of the present invention is to provide a kind of rechargeable nonaqueous electrolytic battery with excellent high rate capability.
According to a first aspect of the invention, provide a kind of rechargeable nonaqueous electrolytic battery, this battery comprises:
Shell;
Be arranged in shell and comprise the nonaqueous electrolyte of line style sulfite;
Be arranged in the positive pole that shell also can absorb-discharge elemental lithium or lithium ion;
Be arranged in shell and comprise Li-Ti oxide and the negative pole of conductive agent, this conductive agent comprises carbonaceous material;
In addition, according to a second aspect of the invention, provide a kind of rechargeable nonaqueous electrolytic battery, this battery comprises:
Shell;
Be arranged in the nonaqueous electrolyte of shell;
Be arranged in the positive pole that shell also can absorb-discharge elemental lithium or lithium ion;
Be arranged in shell and comprise Li-Ti oxide and the negative pole of conductive agent, this conductive agent comprises carbonaceous material; With the Li that contains that is formed on this negative terminal surface
2SO
3Layer.
Description of drawings
Fig. 1 is the oblique view that shows that the part of rechargeable nonaqueous electrolytic battery structure is according to an embodiment of the invention taken apart; With
Fig. 2 schematically illustrates the surface state of negative pole included in according to an embodiment of the invention the rechargeable nonaqueous electrolytic battery.
Embodiment
As the result of further investigation,, the present inventor reduced the high rate capability of secondary cell thereby having been found that effect that film on the negative terminal surface plays resistive element.Especially, form the stage glycol sulfite and propane sultone shows high reactivity, thereby form coarse, unstable and have high-resistance organic film at film.Therefore, reduced the high rate capability of secondary cell.
In addition, can decompose on the interface between positive pole and the nonaqueous electrolyte thereby the non-oxidizability of glycol sulfite and propane sultone is low, this has caused increasing the danger that gas produces.Under charged state and hot environment, should danger can strengthen.
Should also be noted that glycol sulfite has about 68 ℃ low boiling.Because glycol sulfite gasification under about 80 ℃ to the about 90 ℃ storage tests of carrying out is so use the secondary cell of glycol sulfite to produce the significantly reduced serious problems of memory property at high temperature.
On the other hand, have been found that and in negative pole, comprise in Li-Ti oxide and the rechargeable nonaqueous electrolytic battery of carbonaceous material as conductive agent, under hot environment, produce reaction between carbonaceous material and the electrolyte, damaged various high-temperature behaviors for example high-temperature storage performance and high-temperature charging-discharge cycles performance thereby the result produces a large amount of gases.Yet the material with carbon element that use can absorb-discharge lithium does not have the above-mentioned problem of pointing out as the rechargeable nonaqueous electrolytic battery of negative electrode active material.
As the comparative result of above-mentioned two kinds of situations, have been found that in the charge-discharge cycles of secondary cell as under the situation of negative electrode active material, the surface coverage of material with carbon element has film at material with carbon element.On the other hand, under the situation that negative electrode active material is made by Li-Ti oxide, the surface of Li-Ti oxide and material with carbon element does not have cover film.In this case, can think reasonably that film has played suppresses to react between material with carbon element and the electrolyte gas that is caused and produces.
When not being higher than about 0.8V with respect to the electromotive force of lithium metal, the negative pole electromotive force forms this film.In the following description, except as otherwise noted, this negative pole electromotive force refers to the relative value with lithium metal electromotive force.Especially, form high-quality film under the negative pole electromotive force of about 0.5V being not less than about 0.4V and not being higher than.Lithium absorption-release the electromotive force of the material with carbon element of absorption-release lithium at about 0.1V to about 0.9V scope.And in the initial charge stage, the negative electricity potential drop is low to moderate about 0.1V.Infer thus, thereby be not higher than material with carbon element and electrolyte reaction formation film under about 0.8V negative pole electromotive force, at this moment, it is stable that material with carbon element becomes.On the other hand, the lithium of Li-Ti oxide absorb-release electromotive force at about 1.3V to about 3.0V scope, and it is believed that and do not form film.
In this case, do not form film on the surface by the negative electrode active material of Li-Ti oxide representative, Li-Ti oxide has than the electromotive force height of the lithium metal lithium absorption-release electromotive force of 1V at least.As a result, can not suppress by producing as the carbonaceous material of conductive agent and the gas that the reaction between the nonaqueous electrolyte causes.
Result as further investigation, the present inventor has been found that, comprise the negative pole that contains Li-Ti oxide and carbonaceous material and comprise under the situation of the nonaqueous electrolyte that contains the line style sulfite at secondary cell, the high-quality thin film of ionic conductivity excellence can be on the surface of negative pole, formed, thereby rechargeable nonaqueous electrolytic battery can be obtained in high-temperature behavior and high rate capability excellence.
Rechargeable nonaqueous electrolytic battery comprises: shell, hold in the enclosure nonaqueous electrolyte, hold in the enclosure anodal and hold in the enclosure negative pole.Comprise Li-Ti oxide in the included negative electrode active material of this negative pole and contain the conductive agent of carbonaceous material.This positive pole plays the effect that absorbs and discharge elemental lithium or lithium ion.In addition, nonaqueous electrolyte comprises at least a additive that is selected from basic dimethyl sulfite, sulfurous acid diethyl ester and sulfurous acid methyl ethyl ester.
Incidentally, rechargeable nonaqueous electrolytic battery can also comprise and places between positive pole and the negative pole and play the barrier film that holds the nonaqueous electrolyte effect.Also can between positive pole and negative pole, place gel-like electrolyte layer or solid electrolyte layer to replace barrier film.
To describe nonaqueous electrolyte, negative pole, positive pole, barrier film and the shell of rechargeable nonaqueous electrolytic battery now in detail.
1) nonaqueous electrolyte:
Nonaqueous electrolyte comprises at least a additive that is selected from dimethyl sulfite, sulfurous acid diethyl ester and sulfurous acid methyl ethyl ester.Dimethyl sulfite has the chemical constitution of following chemical formula (3) expression, and sulfurous acid diethyl ester has the chemical constitution of following chemical formula (4) expression, and the sulfurous acid methyl ethyl ester has the chemical constitution of following chemical formula (5) expression:
Under the about 1.3V of negative pole electromotive force, every kind of above-mentioned additive can form fine and close and stable film on the surface of negative pole.Then, in the general potential range that is present in rechargeable nonaqueous electrolytic battery that unreacted additive is stable.The film that forms is stable in 0V to 5.0V voltage range, and stable especially in the voltage range of 1.0V to 1.5V.The present inventor thinks that the film of Xing Chenging comprises inorganic thin film such as Li thus
2SO
3Film and organic film such as ROSO
2Li (R represents alkyl) film.In fact the present inventor has analyzed film with the surface analysis method.As a result, confirmed that film is formed by inorganic thin film and organic film, this inorganic thin film mainly comprises Li
2SO
3With microcomponent such as LiF, this organic film comprises ROSO
2Li, ROCO
2Li, R-CH
3(CH) CH
2Or R=CH
2-CH
2Incidentally, " R " expression alkyl in the compound of formation organic film.
The property of thin film that is formed on the negative terminal surface is analyzed, comprise the situation of the line style sulfite of dimethyl sulfite, sulfurous acid diethyl ester and sulfurous acid methyl ethyl ester that be selected from of using as additive, with disclosed cyclic sulfite among the aforementioned Japanese patent gazette No.2003-163029 that mentions as the situation of additive, just for example glycol sulfite or propane sultone of this ring-type sulfinic acid ester wherein.Found tangible difference between above-mentioned two kinds of situations.
Fig. 2 has shown that the line style sulfite that is selected from dimethyl sulfite, sulfurous acid diethyl ester and sulfurous acid methyl ethyl ester is as the film that forms under the situation of additive on negative pole 11.As shown in Figure 2, mainly comprise Li
2SO
3Preferably at first be formed on the surface of negative pole 11 with the inorganic thin film 12 of microcomponent such as LiF.Then, comprise as ROSO
2Li, ROCO
2Li, R=CH
3(CH) CH
2Or R=CH
2-CH
2Organic film 13 be formed on slightly on the surface of inorganic thin film 12.
On Li-Ti oxide and carbonaceous material, all form the film on the negative terminal surface.Especially, have been found that, then improved and suppressed the effect that gas produces, thereby make secondary cell have excellent high-temperature charging-discharge cycles performance if film is formed on the surface of the carbonaceous material that can cause that gas generates.And because Li-Ti oxide and line style sulfite moderately react, so reduced the resistance of film itself, this is because the film that forms is fine and close and stable.As a result, the film that on Li-Ti oxide and carbonaceous material surface, forms at the interface, the migration resistance of electric charge becomes very little, thereby has improved high rate capability.In the line style sulfite, using sulfurous acid diethyl ester is desirable as the additive of nonaqueous electrolyte, because sulfurous acid diethyl ester can form densification and the good film of ionic conductivity.
Using under the line style sulfite situation, the film of formation is suppressing effective especially aspect the reaction between negative pole and the gamma-butyrolacton.Infer thus,, can further improve the high-temperature behavior and the high rate capability of rechargeable nonaqueous electrolytic battery by in the nonaqueous electrolyte that comprises the line style sulfite, adding gamma-butyrolacton.
On the other hand, using under cyclic sulfite such as glycol sulfite or the situation of propane sultone as additive, the ternary system compound of Ti-O-S necessarily is formed on the Li as negative electrode active material
4/3Ti
5/3O
4The surface on, described as aforesaid Japanese patent gazette No.2003-163029.Yet the composition that comprises the whole film of this ternary compound belongs to inorganic thin film.Necessarily play the organic film that suppresses gas generation effect resistive element can be provided, thereby greatly suppressed the migration of electric charge.As shown in embodiment described here after a while, organic film has greatly damaged high rate capability.
The above-mentioned big difference of pointing out aspect high rate capability mainly is that the performance difference by additive causes.Additive reduces on the surface of negative pole and decomposes in the charging stage of secondary cell.Can think reasonably that the difference of reaction rate and decomposition potential has changed material and the performance that is formed on the film on the negative terminal surface in the additive reduction reaction.
Should also be noted that: the additive of Shi Yonging has higher boiling point in one embodiment of the invention, is good aspect high-temperature storage performance therefore.For example, about 126 ℃ and the boiling point of sulfurous acid diethyl ester of the boiling point of dimethyl sulfite is about 159 ℃.
The additive of Shi Yonging is good aspect anti-oxidant in one embodiment of the invention.As a result, unreacted additive unlikely on positive pole because oxidation decomposition, therefore, unlikely promote gas to produce.Thereby also unlikely damage overcharge performance, high-temperature charging-discharge cycles performance and high-temperature storage performance.
Based on the amount of nonaqueous electrolyte, operating weight percentage is that 0.1% to 10.0% additive is desirable.
If the amount of additive is less than 0.1 weight %, then additive is difficult to the whole surface of coated carbon material, and the result may reduce the effect that gas produces that suppresses.On the other hand, if the consumption of additive, is dissolved in the performance that the additive of the end reaction in the nonaqueous electrolyte may damage nonaqueous electrolyte greater than 10.0 weight %.
Operating weight percentage is that 0.8% to 5.0% additive is more desirable.The consumption of additive can form particularly compact and stable film in above-mentioned scope the time.Especially, if the amount of additive surpasses 5.0 weight %, can enhanced film form the reactivity of reaction, thereby form coarse and unsettled film.In this case, the film of formation provides resistance component, and the result has damaged the high rate capability of secondary cell.
Incidentally, the addition of the above-mentioned additive of mentioning has been represented and carbonaceous material and negative pole words property material combined amount and the corresponding numerical value of specific area separately.
Nonaqueous electrolyte can have with liquid or gel form and adds wherein additive to.Nonaqueous electrolyte comprises organic solvent and the electrolyte that is dissolved in this organic solvent.On the other hand, the gel nonaqueous electrolyte can be for comprising the form of composite of liquid electrolyte and polymeric material.
Can be by for example, electrolyte is dissolved in 0.5 to 2mol/L concentration prepares liquid nonaqueous electrolyte in the organic solvent.
Electrolyte comprises, for example, and LiBF
4, LiPF
6, LiAsF
6, LiClO
4, LiCF
3SO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, Li (CF
3SO
2)
3C and LiB[(OCO)
2]
2Can use these electrolyte individually or with the electrolytical form of mixtures of multiple these variety classeses.
Organic solvent comprises, for example, and cyclic carbonate such as propylene carbonate (PC) and ethylene carbonate (EC); Linear carbonate such as diethyl carbonate (DEC), dimethyl carbonate (DMC) and methyl ethyl carbonate (MEC); Linear ether such as dimethoxy-ethane (DME) and diethoxyethane (DEE); Cyclic ethers such as oxolane (THF) and dioxolanes (DOX); With other organic solvent such as gamma-butyrolacton (GBL), acetonitrile (AN) and sulfolane (SL).These organic molten systems can be used individually or with the form of mixtures of multiple these organic solvents.
In order to obtain at secondary cell all excellent aspect high rate capability and the high-temperature behavior the preferred organic solvent that comprises gamma-butyrolacton that uses.Gamma-butyrolacton and volume of organic solvent ratio should be preferred 30% to 90%, more preferably 50%-75%.
Polymeric material comprises, for example, and Kynoar (PVdF), polyacrylonitrile (PAN) and poly(ethylene oxide) (PEO).
2) negative pole
Negative pole comprises negative collector electrode and is formed on surface of negative collector electrode or two lip-deep negative electrode layers.Negative electrode layer comprises negative electrode active material, conductive agent and binding agent.
Lithium absorption-release the electromotive force of negative electrode active material is compared the high at least 1V of electromotive force of lithium metal.Incidentally, negative electrode active material can absorb and/or discharge elemental lithium or lithium ion.Electromotive force when " the lithium absorption-release electromotive force of negative electrode active material " refers to the negative pole absorption or discharge elemental lithium or lithium ion.
The negative electrode active material that lithium absorption-release electromotive force is higher than 1V comprises, for example, and Li-Ti oxide such as lithium titanate, tungsten oxide, molybdenum oxide, iron sulfide and titanium sulfide.Li-Ti oxide can absorb and/or discharge lithium ion.
Negative electrode active material preferably includes lithium titanate.
Under the situation of Li-Ti oxide as negative electrode active material, the lithium absorption-release electromotive force of negative pole is that about 1.3V is to about 3.0V with respect to golden layer of electromotive force to electrode of lithium.1.0V to the 1.5V potential range of the highly stable existence of the formed film of this potential range and additive is overlapping.And, preferably use Li-Ti oxide as negative electrode active material, this is because Li-Ti oxide has the long-life.
Incidentally, the lithium absorption-release electromotive force of negative pole is according to the crystal structure of Li-Ti oxide and difference.For example, under the situation of spinel type lithium titanate, the lithium absorption-release electromotive force of negative pole is about 1.3V to 2.0V with respect to lithium metal electromotive force.Especially, the lithium absorption-release reaction of lithium titanate takes place about about 1.5V.Under the situation of titanium oxide as negative electrode active material of using Detitanium-ore-type, the lithium absorption-release electromotive force of negative pole is that about 1.5V is to about 3.0V with respect to the electromotive force of lithium metal.Especially, titanium oxide absorbs-release reaction about about 2.0V electromotive force.In addition, using under the situation of ramsdellite (ramsdellite) type lithium titanate as negative electrode active material, the lithium absorption-release electromotive force of negative pole is that about 1.0V is to about 2.3V with respect to the electromotive force of lithium metal.
Preferentially use with chemical formula Li
4+xTi
5O
12The spinel type lithium titanate of (0≤x≤3) expression is as negative electrode active material.
As mentioned above, in comprising the negative pole of spinel type lithium titanate as negative electrode active material, the absorption-release reaction of lithium takes place under the electromotive force of about 1.5V.On the other hand, the film that is formed by additive is stablized under 1.0V to 1.5V electromotive force especially.Therefore, use the lithium titanate with spinel structure during as negative electrode active material, this additive exists with extra high stability, thereby produces special effect.
Use negative electrode active material with granular form.The particle of negative electrode active material preferably has the 1m that is measured by the BET method
2/ g to 30m
2/ g specific area.
If specific area is less than 1m
2/ g helps the effective area of negative electrode active material of electrode reaction just very little, thereby can damage the high rate capability of secondary cell.On the other hand, if above-mentioned specific area greater than 30m
2/ g, interface between negative electrode active material and the nonaqueous electrolyte increases, thereby can increase needing consumption and reducing the high rate capability of secondary cell of additive.
More preferably the specific area of negative electrode active material is at 5m
2/ g to 10m
2In/g the scope.
Incidentally, nonaqueous electrolyte can decompose being not less than under the electromotive force of 5V.Therefore, have in the rechargeable nonaqueous electrolytic battery of about 2V cell voltage in preparation, the higher limit of the lithium absorption-release electromotive force of negative pole is about 3V.Incidentally, cut the negative pole electromotive force by positive electrode potential and obtain cell voltage.
In order to improve the contact resistance of conductivity and reduction and collector electrode, use carbonaceous material as conductive agent.Additive allows to form fine and close and stable film on the surface of carbonaceous material.The film of Xing Chenging has stoped the reaction between carbonaceous material and the nonaqueous electrolyte thus, and the generation of the very effective inhibition gas of this film and effectively improve secondary cell charge discharge cycles performance under the high temperature.Carbonaceous material comprises, for example, and acetylene black, carbon black, coke, carbon fiber and graphite.Especially, consider property of thin film, particularly film resistor wishes that carbonaceous material has character as described below.
Wish (002) surface layer spacing (d of carbonaceous material
002) between 0.344nm to 0.352nm, and the crystallite dimension on the C direction of principal axis (Lc) is not more than 10nm.
At interlamellar spacing d
002Less than 0.344nm and crystallite dimension Lc in the carbonaceous material greater than 10nm, the degree of graphitization height.As a result, on the edge surface of graphite crystal, greatly promoted the reaction with additive, thereby the film that forms is thick on the edge surface of graphite crystal, thereby stops charge migration.Infer thus, be difficult to obtain the high rate capability of secondary cell.On the other hand, at interlamellar spacing d
002In the carbonaceous material greater than 0.352nm, degree of graphitization is low.In addition, remain in lip-deep functional group and can promote and the reaction of additive that reason is that carbonaceous material is that the film that the result forms is thick, thereby has stoped charge migration by low calcining heat preparation.Infer thus, be difficult to obtain enough high rate capabilities.
In this case, wish the interlamellar spacing (d of (002) face of carbonaceous material
002) in 0.344nm to 0.352nm scope and the crystallite dimension on the C direction of principal axis (Lc) be not more than 10nm.The carbonaceous material that satisfies these special requirement comprises, for example graphitized carbon such as coke.And, to wish the lower limit of crystallite dimension Lc is made as 1nm, reason is to have a large amount of functional groups on the surface that has less than the carbonaceous material of 1nm crystallite dimension Lc, the result forms thick film, thereby stops charge migration.
In order to improve conductivity, wish that carbonaceous material has the 10m that is not less than by BET method mensuration
2The specific area of/g.And, suppress the effect that gas produces in order to improve, wish that the specific area of carbonaceous material is not more than 100m
2/ g.
In addition, carbonaceous material is granular.Improve the effect that suppresses the gas generation in order to make carbonaceous material help, wish that the average particulate diameter of carbonaceous material is not less than 0.5 μ m.And, in order to improve conductivity, wish that the average particulate diameter of carbonaceous material is not more than 5 μ m.
Carbonaceous material can be two or more specific areas or the different mixtures of material of particle diameter.
Be used for the binding agent of active material and conductive agent combination is comprised: for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), Viton and butadiene-styrene rubber.
About the mixing ratio of negative electrode active material, conductive agent and binding agent, preferred negative pole content of active substance is 70wt% to 96wt%, and the content of conductive agent is 2wt% to 28wt%, and the content of binding agent is 2wt% to 28wt%.If the content of conductive agent less than 2wt%, then can reduce the conductivity of negative electrode layer, thus the high rate capability of reduction rechargeable nonaqueous electrolytic battery.In addition, if the content of binding agent less than 2wt%, then can be reduced in the complexation strength between negative electrode layer and the negative collector electrode, thereby weakened the charge-discharge cycles performance of rechargeable nonaqueous electrolytic battery.On the other hand, consider the capacity that increases secondary cell, the content of preferred conductive agent and binding agent all is not more than 28%.
Preferably by making negative collector electrode being higher than aluminium foil stable under the potential range of 1V or alloy foil.
For example, by the negative electrode active material that suspends in solvent, conductive agent and binding agent, then the suspended substance with gained is coated on the collector electrode of being made by aluminium foil or alloy foil, subsequently the collector electrode that is coated with suspended substance is carried out drying and compacting, prepares negative pole.
3) positive pole
Positive pole comprises positive collector electrode and is formed on face of positive collector electrode or the anodal layer on two faces.Anodal layer comprises positive active material, conductive agent and binding agent.
Positive active material for example comprises, oxide, sulfide and polymer.Oxide for example comprises, absorbs the manganese dioxide (MnO of elemental lithium or lithium ion
2), iron oxide, cupric oxide, nickel oxide, complex Li-Mn-oxide such as Li
xMn
2O
4Perhaps Li
xMnO
2, lithium nickel composite oxide such as Li
xNiO
2, lithium cobalt composite oxide such as Li
xCoO
2, lithium/nickel/cobalt composite oxide such as Li
xNi
1-yCo
yO
2, lithium manganese cobalt composite oxide such as Li
xMn
yCo
1-yO
2, spinel type lithium mn-ni compound oxide Li
xMn
2-yNi
yO
4, have the Lithium Phosphor Oxide such as the Li of olivine structural
xFePO
4, Li
xFe
1-yMn
yPO
4And Li
xCoPO
4, ferric sulfate such as Fe
2(SO
4)
3And vanadium oxide such as V
2O
5
Polymer for example comprises, conducting polymer materials such as polyaniline and polypyrrole and based on the disulphide polymeric material.In addition, can use sulphur (S) and fluorocarbons as positive active material.
Desirable positive active material for example comprises, complex Li-Mn-oxide such as Li
xMn
2O
4, lithium nickel composite oxide such as Li
xNiO
2, lithium cobalt composite oxide such as Li
xCoO
2, lithium/nickel/cobalt composite oxide such as Li
xNi
1-yCo
yO
2, spinel type lithium mn-ni compound oxide such as Li
xMn
2-yNi
yO
4, lithium manganese cobalt composite oxide such as Li
xMn
yCo
1-yO
2, Lithium Phosphor Oxide such as Li
xFePO
4It should be noted that the above-mentioned material that exemplifies can obtain high cathode voltage.Incidentally, x in the preferred above-mentioned chemical formula and y are in 0 to 1 scope.
Incidentally, nonaqueous electrolyte can decompose being not less than under the electromotive force of 5V.Thereby preferred anodal lithium absorbs-releases electromotive force and is about 5V to the maximum.
The conductive agent that effectively improves the contact resistance of conductivity and inhibition and collector electrode for example comprises acetylene black, carbon black and graphite.
The binding agent of active material and conductive agent of being used to bond for example comprises polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF) and Viton.
When relating to the blending ratio of positive active material, conductive agent and binding agent, the content of wishing positive active material is 80wt% to 95wt%, and the content of conductive agent is 3wt% to 18wt%, and the content of binding agent is 2wt% to 17wt%.When the content of conductive agent is not less than 3wt%, can obtain above-mentioned effect.And, when the content of conductive agent is not more than 18wt%, in hot environment storage secondary cell process, can suppress nonaqueous electrolyte in the lip-deep decomposition of conductive agent.In addition, when the content of binding agent is not less than 2wt%, can obtain enough pole strengths.And the content of binding agent is not more than at 17% o'clock, thereby the content that can reduce insulating material in the electrode reduces interior resistance.
Wish that positive collector electrode made by aluminium foil or alloy foil.
For example, by in the solvent that is fit to, disperseing positive active material, conductive agent and binding agent with the preparation suspended substance, then the suspended substance with gained is coated on the collector electrode that is made of aluminium foil or alloy foil and the dry and compacting to the collector electrode that is coated with suspended substance subsequently, thereby preparation is anodal.
4) barrier film
Barrier film is made by for example synthetic resin nonwoven fabrics, polyethylene porous membrane or polypropylene porous membrane.
5) shell
Shell for example comprises, is the container that 0.2mm or thinner laminate film are made by thickness, and perhaps thickness is not more than the canister of 0.5mm.The thickness of preferred shell is not more than 0.2mm.About shape, this shell is platypelloid type, prismatic, column type, Coin shape, button type, sheet type or cascade type.Incidentally, rechargeable nonaqueous electrolytic battery can be the compact battery and the large-sized battery that is installed on the motor vehicle that is installed in the portable electronic equipment.
Wish that this laminate film is the plural layers that comprise metal level and cover the resin bed on the metal level.In order to reduce the weight of secondary cell, preferably use aluminium foil or alloy foil as metal level.The resin bed that is used for the reinforcement metal layer can be made by polymer such as polypropylene (PP), polyethylene (PE), nylon or PETG (PET).Use the thermal welding sealing that laminate film is formed container and seals this container.
Canister is by for example, and aluminum or aluminum alloy is made.Wish that aluminium alloy comprises, for example magnesium, zinc or silicon.On the other hand, wish that the transition metal in the aluminum or aluminum alloy such as the content of iron, copper, nickel or chromium are not more than 100ppm.
Incidentally, the shell of being made by flexible material such as laminate film can produce and significantly expansion along with gas, thereby produces outstanding effect.
Fig. 1 has shown according to the present invention the structure of the platypelloid type rechargeable nonaqueous electrolytic battery of an embodiment of rechargeable nonaqueous electrolytic battery.More concrete, Fig. 1 is the oblique view that take apart the part, has shown platypelloid type lithium rechargeable battery structure of the present invention.
As shown in the figure, convoluted flat electrode group is contained in the bag shape shell 6 that is formed by thin-film material.Prepare convoluted flat electrode group by helical coil coiled flat pattern, this stepped construction comprises positive pole 3, negative pole 4 and the barrier film 5 between positive pole 3 and negative pole 4.Nonaqueous electrolyte is contained in the electrode group.Banded positive terminal 2 is electrically connected with positive pole 3, and the end of positive terminal 2 is extracted into the outside from the inside of shell 6.On the other hand, banded negative terminal 1 is electrically connected with negative pole 4, and the end of negative terminal 1 is extracted into the outside from the inside of shell 6.
What describe below is embodiments of the invention.Self-evident, technical scope of the present invention is not limited to following embodiment.
(embodiment 1 to 11 and comparative examples 1 to 3)
Be prepared as follows the rechargeable nonaqueous electrolytic battery in embodiment 1 to 11 and the comparative examples 1 to 3.
＜preparation negative pole 〉
In N-methyl pyrrolidone (NMP), add the Li of 90wt% as negative electrode active material
4Ti
5O
12, 5wt% makes slurry as the acetylene black and the 5wt% polyvinylidene fluoride (PVdF) of conductive agent, wherein the specific area of this negative electrode active material is 9m
2/ g, the specific area of this acetylene black is 10m
2/ g, d
002Interlamellar spacing is that 0.3553nm and crystallite dimension Lc are 1.12nm.Then, thus obtained slurry is coated on the aluminium foil that thickness is 15 μ m, then dry, compacting is coated with the aluminium foil of slurry then, thereby the preparation electrode density is 3.0g/cm
3And electrode specific surface area is 5.0cm
2The negative pole of/g.
＜preparation is anodal 〉
In N-methyl pyrrolidone (NMP), add the lithium and cobalt oxides (LiCoO of 90wt% as positive active material
2) powder, 3wt% acetylene black, 3wt% graphite and 4wt% polyvinylidene fluoride (PVdF) make slurry.Then, the slurry of preparation thus is coated with on two faces carrying out collector body, this collector body is that the aluminium foil of 15 μ m is made by thickness, and is then dry, and compacting is coated with the collector body of slurry then, thereby the preparation electrode density is 3.0g/cm
3Positive pole.
＜preparation electrode group 〉
The laminated construction that barrier film, above-mentioned negative pole and another barrier film made by above-mentioned positive pole, polyethylene porous membrane that 25 μ m are thick are formed carries out screw winding, then suppressing the stepped construction of this coiling, is that 30mm and thickness are the pancake electrode group of 3.0mm thereby obtain width.Thus obtained electrode group is placed in the packing that is formed by laminate film, and this laminate film thickness is 0.1mm and comprises that thickness is the aluminium foil of 40 μ m and is formed on two lip-deep polypropylene layers of aluminium foil.Under about 80 ℃ with this packing vacuumize 24 hours of hold electrodes group.
＜prepare liquid nonaqueous electrolyte 〉
Prepare nonaqueous solvents with 25: 75 mixed carbonic acid ethyls (EC) of volume ratio and gamma-butyrolacton (GBL), then mix in nonaqueous solvents amount dissolving LiBF4 (LiBF with 1.5mol/L at this
4) to obtain solution.Then, in the solution of preparation thus line style sulfite shown in the interpolation table 1 or cyclic sulfite to prepare liquid nonaqueous electrolyte.Incidentally, in Comparative Examples 3, do not add any in line style sulfite and the cyclic sulfite.
Liquid nonaqueous electrolyte is injected the laminate film packing of having held the electrode group, then pack to prepare the rechargeable nonaqueous electrolytic battery of structure as shown in Figure 1 by heat seal.Zhi Bei rechargeable nonaqueous electrolytic battery width is that 35mm, thickness are 3.2mm and highly are 65mm thus.
In order to detect the high rate capability of secondary cell, the discharge capacity of measuring the rechargeable nonaqueous electrolytic battery of each in embodiment 1 to 11 and the comparative examples 1 to 3 is than 3C/0.2C and 10C/0.2C.
Then, in order to detect the charge-discharge cycles performance of secondary cell at high temperature, under high temperature (45 ℃), carry out the charge-discharge cycles test.Carry out loop test with being set in 1C mA current value, and repeat charge-discharge cycles with the cell voltage that is set in 1 to the 3V scope.The number of times that is reduced to 80% charge-discharge cycles of initial capacity up to discharge capacity is counted as the charge-discharge cycles life-span.
At last, in order to detect charge-discharge cycles performance at high temperature, particularly, under hot environment, give birth to, adopt the cell thickness after the charge-discharge cycles test under the vernier caliper measurement high temperature by the caused gas of the reaction between carbonaceous material and the nonaqueous electrolyte.Utilize the cell thickness of measuring thus, obtain the rate of change X (%) of cell thickness after 45 ℃ of charge-discharge cycles tests by the following formula that provides (I):
X(％)＝100×{(T
1-T
2)/T
2}(I)
T wherein
1Representative thickness of battery behind the loop test under hot environment, T
2Representative thickness of battery before the loop test under hot environment.
Table 1 has shown the measurement result of discharge capacitance and loop test under hot environment.
In addition, the secondary cell that is charged to 3.0V was stored 24 hours under 85 ℃ of environment, to measure the variation of the caused secondary cell thickness of storage under hot environment.Table 1 has also shown this result.
Table 1
| Additive | The high rate capability test | The high temperature cyclic performance test | High-temperature storage performance | ||||
| The compound title | Addition | 3C/0.2C discharge capacity ratio | 10C/0.2C discharge capacity ratio | High temperature (45 ℃) charge-discharge cycles life-span (number of times) | The variation of cell thickness behind the loop test | The variation of cell thickness after 85 ℃ of storages | |
| Embodiment 1 | DES | 0.05wt％ | 80 | 40 | 350 | 100％ | 20％ |
| Embodiment 2 | DES | 0.10wt％ | 88 | 50 | 850 | 3％ | Be less than or equal to+2% |
| Embodiment 3 | DES | 0.30wt％ | 90 | 60 | 900 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 4 | DES | 0.50wt％ | 91 | 65 | 1000 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 5 | DES | 1.0wt％ | 93 | 87 | 1100 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 6 | DES | 3.0wt％ | 93 | 85 | 1000 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 7 | DES | 5.0wt％ | 93 | 80 | 950 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 8 | DES | 10.0wt％ | 84 | 50 | 850 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 9 | DES | 20.0wt％ | 60 | 40 | 500 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 10 | MES | 1.0wt％ | 92 | 85 | 1100 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 11 | DMS | 1.0wt％ | 92 | 80 | 1100 | Be less than or equal to 2% | Be less than or equal to+2% |
| Comparative examples 1 | PS | 1.0wt％ | 85 | 30 | 900 | Be less than or equal to+2% | More than or equal to 100% |
| Comparative examples 2 | ES | 1.0wt％ | 80 | 15 | 900 | Be less than or equal to+2% | More than or equal to 100% |
| Comparative examples 3 | LiBF 4 | 1.5 (mol/L) | 75 | 10 | 300 | 400％ | More than or equal to 100% |
| Comparative examples 4 | DES | 1.0wt％ | 70 | 10 | 100 | 200％ | More than or equal to 100% |
Annotate: DES: sulfurous acid diethyl ester;
MES: sulfurous acid methyl ethyl ester;
DMS: dimethyl sulfite;
PS: the inferior propyl ester of sulfurous acid
ES: glycol sulfite;
As shown in table 1, the 3C/0.2C discharge capacity than and aspect the 10C/0.2C discharge capacity compares, the rechargeable nonaqueous electrolytic battery of each is included in the nonaqueous electrolyte that has wherein added the line style sulfite among the embodiment 2 to 11, this rechargeable nonaqueous electrolytic battery all generally is better than in the comparative examples 1 to 3 rechargeable nonaqueous electrolytic battery of each, and this has proved excellent high rate capability.And the rechargeable nonaqueous electrolytic battery among each embodiment at high temperature demonstrates the long charge-discharge cycles life-span, and this has proved excellent high-temperature charging-discharge cycles performance.
In embodiment 5,10 and 11, use sulfurous acid diethyl ester (DES), sulfurous acid methyl ethyl ester (MES) and dimethyl sulfite (DMS) as additive respectively.On the other hand, inferior propyl ester (PS) of sulfurous acid and glycol sulfite (ES) are respectively applied in comparative examples 1 and 2.From table 1, obviously find out, discharge capacity than 3C/0.2C, discharge capacity than 10C/0.2C and the high-temperature charging-either side of discharge cycles in the life-span, embodiment 5,10 and 11 secondary cell all are better than the secondary cell in comparative examples 1 and 2.Infer thus, the additive that uses among the present invention can improve the charge-discharge cycles performance of the secondary cell under high rate capability and the high temperature.Particularly, in any 3C/0.2C discharge capacity ratio and 10C/0.2C discharge capacity ratio, make DES be better than using the secondary cell of MES among the embodiment 10 among the embodiment 5, and be better than using among the embodiment 11 secondary cell of DMS as additive as additive as the secondary cell of additive.
Incidentally, in using inferior propyl ester (PS) of sulfurous acid or the secondary cell of glycol sulfite (ES) as additive, compare 3C/0.2C discharge capacity ratio, the 10C/0.2C discharge capacity is than significantly reducing.Can think reasonably that the coarse and unsettled film guiding discharge capacity ratio 10C/0.2C that inferior propyl ester (PS) of sulfurous acid or glycol sulfite (ES) form significantly reduces.
In embodiment 1 to 9, add the sulfurous acid diethyl ester of 0.1wt% to 10.0wt%.In these cases, the charge-discharge cycles life-span of secondary cell further prolongs under the high temperature, thereby finds that secondary cell has charge-discharge cycles performance under the excellent especially high temperature.Test data proves: if the consumption of additive is not less than 0.1wt%, then the surface of carbonaceous material can be coated with additive fully.And when the additive of use was not more than 10.0wt%, the battery performance that can suppress to be caused by unreacted additive worsened.
The test data of embodiment 1 to 9 proves: if sulfurous acid diethyl ester adds with the amount of 1.0wt% to 5.0wt% so that the high rate capability excellence of secondary cell, 10C/0.2C discharge capacity ratio height so.Infer thus, if the additive that uses can form particularly compact and stable film in above-mentioned scope.
The film that forms on the negative terminal surface of the secondary cell that following surface analysis embodiment 1 to 11 prepares in each is formed.At first, rechargeable nonaqueous electrolytic battery is put into argon gas glove box with-70 ℃ of dew points of pact, wherein this rechargeable nonaqueous electrolytic battery at room temperature charges to 3.0V under the 0.2C electric current, then, takes apart with a part (1cm is square) of taking out negative pole as the negative pole sample.Form by the film that X-ray electric light molecular spectroscopic analysis negative pole sample surfaces forms.
Find that film comprises by Li
2SO
3The inorganic layer that forms with LiF is selected from ROSO with containing
2Li, ROCO
2Li, R=CH
3(CH) CH
2And R=CH
2-CH
2In the organic layer of at least a compound.
The storage carried out under 85 ℃ test proof: embodiment 1 to 11 uses the expansion rate of secondary cell under 85 ℃ that contains line style sulfite nonaqueous electrolyte in each, and the secondary cell of comparing in each comparative examples 1 to 3 is lower.This shows the excessive line style sulfite stable existence in battery that remains in the nonaqueous electrolyte.
On the other hand, in the comparative examples 1 of using inferior propyl ester (PS) of cyclic sulfite such as sulfurous acid or glycol sulfite (ES) and 2 each secondary cells, the cyclic sulfite that remains under 85 ℃ of hot environments in the nonaqueous electrolyte is easy to gasification, and expansion rate is increased to 100% or more as a result.In addition, when relating to the secondary cell in the comparative examples 3, do not comprise any line style sulfite and cyclic sulfite in the nonaqueous electrolyte of this secondary cell, LiBF
4Be used as the effect that electrolyte plays film forming additive, the result forms the inorganic thin film of being made up of LiF on negative terminal surface.The inorganic thin film of Xing Chenging can not produce the effect of reacting between inhibition nonaqueous electrolyte and the negative pole fully thus, and is shown as the test data about cell thickness variation behind the loop test that provides from table 1.In this case, expansion rate is increased to 100% or more in the storage of 85 ℃ in the Comparative Examples 3 test.
(comparative examples 4)
The identical rechargeable nonaqueous electrolytic battery of structure of secondary cell among preparation and the embodiment 5, the FeS that just is used as negative electrode active material have by the BET method and record 1.2m
2The specific area of/g.Lithium absorption-release electromotive force with respect to lithium metal electromotive force FeS is 1.8V.
The rechargeable nonaqueous electrolytic battery of comparative examples 4 preparations carries out high rate capability test, high-temperature charging-discharge cycles performance test and high temperature storage test under the condition identical with aforementioned battery.Table 1 also shows the result.
As shown in table 1, the rechargeable nonaqueous electrolytic battery of comparative examples 4 aspect high rate capability, high-temperature charging-discharge cycles performance and high-temperature storage performance in all than embodiment 1 to 11 any nonaqueous electrolyte battery poor.It should be noted that about this point the electromotive force height that the lithium absorption-release electromotive force of the negative electrode active material that uses in the comparative examples 4 is compared the lithium metal is 1V at least.Yet,, do not comprise Li so in comparative examples 4, form because negative pole words property material is not to be made by Li-Ti oxide
2SO
3Inorganic thin film, cause aforesaid bad battery performance.
As what from experimental data above-mentioned, obviously seen, embodiment 1 to 11 secondary cell in each has all improved the discharge performance under the 10C high magnification and has not had to weaken charge-discharge cycles life-span under 45 ℃, suppressed simultaneously the expansion of secondary cell in loop test and 85 ℃ of storages, wherein the secondary cell of embodiment 1 to 11 comprises the negative pole that contains Li-Ti oxide and carbonaceous material and comprises the nonaqueous electrolyte that contains the line style sulfite.
(embodiment 12 to 23)
The rechargeable nonaqueous electrolytic battery that preparation is similar to embodiment 1 to 11 only is to use acetylene black in the coke alternative embodiment 1 to 11 as conductive agent, and this coke has the 80m that is recorded by the BET method
2The specific area of/g, interlamellar spacing d
002For 0.3504nm and crystallite dimension Lc are 1.89nm.Estimate these nonaqueous electrolyte batteries with the method among the embodiment 1 to 11.Table 2 has shown this result.
(embodiment 24 to 35)
The rechargeable nonaqueous electrolytic battery that preparation is similar to embodiment 1 to 11 only is to use acetylene black in the graphite alternative embodiment 1 to 11 as conductive agent, and this graphite has the 10m that the BET method records
2/ g specific area, interlamellar spacing d
002For 0.3356nm and crystallite dimension Lc are 100nm.Estimate these nonaqueous electrolyte batteries with the method among the embodiment 1 to 11.Table 3 has shown this result.
The film that forms on the negative terminal surface with the methods analyst embodiment among the embodiment 1 12 to 35 secondary cell in each is formed.Another film of finding these embodiment all comprises by Li
2SO
3The inorganic layer that forms with LiF is selected from ROSO with containing
2Li, ROCO
2Li, R=CH
3(CH) CH
2And R=CH
2-CH
2The organic layer of at least a compound.
Table 2
| Additive | The high rate capability test | The high temperature cyclic performance test | High-temperature storage performance | ||||
| The compound title | Addition | 3C/0.2C discharge capacity ratio | 10C/0.2C discharge capacity ratio | High temperature (45 ℃) charge-discharge cycles life-span (number of times) | The variation of cell thickness behind the loop test | The variation of cell thickness after 85 ℃ of storages | |
| Embodiment 12 | DES | 0.05wt％ | 84 | 52 | 500 | 5％ | Be less than or equal to+2% |
| Embodiment 13 | DES | 0.10wt％ | 90 | 65 | 1000 | 3％ | Be less than or equal to+2% |
| Embodiment 14 | DES | 0.30wt％ | 92 | 75 | 1200 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 15 | DES | 0.50wt％ | 94 | 82 | 1300 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 16 | DES | 0.80wt％ | 95 | 90 | 1400 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 17 | DES | 1.0wt％ | 96 | 92 | 1450 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 18 | DES | 3.0wt％ | 96 | 90 | 1400 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 19 | DES | 5.0wt％ | 95 | 87 | 1350 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 20 | DES | 10.0wt％ | 88 | 65 | 1150 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 21 | DES | 20.0wt％ | 72 | 52 | 700 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 22 | MES | 1.0wt％ | 94 | 90 | 1450 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 23 | DMS | 1.0wt％ | 94 | 88 | 1450 | Be less than or equal to 2% | Be less than or equal to+2% |
Annotate: DES: sulfurous acid diethyl ester;
MES: sulfurous acid methyl ethyl ester;
DMS: dimethyl sulfite;
Table 3
| Additive | The high rate capability test | The high temperature cyclic performance test | High-temperature storage performance | ||||
| The compound title | Addition | 3C/0.2C discharge capacity ratio | 10C/0.2C discharge capacity ratio | High temperature (45 ℃) charge-discharge cycles life-span (number of times) | The variation of cell thickness behind the loop test | The variation of cell thickness after 85 ℃ of storages | |
| Embodiment 24 | DES | 0.05wt％ | 82 | 45 | 370 | 70％ | 15％ |
| Embodiment 25 | DES | 0.10wt％ | 89 | 55 | 880 | 3％ | Be less than or equal to+2% |
| Embodiment 26 | DES | 0.30wt％ | 90 | 65 | 950 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 27 | DES | 0.50wt％ | 92 | 70 | 1000 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 28 | DES | 0.80wt％ | 93 | 84 | 1050 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 29 | DES | 1.0wt％ | 94 | 88 | 1100 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 30 | DES | 3.0wt％ | 94 | 86 | 1050 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 31 | DES | 5.0wt％ | 94 | 82 | 1000 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 32 | DES | 10.0wt％ | 86 | 55 | 870 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 33 | DES | 20.0wt％ | 68 | 45 | 600 | Be less than or equal to+2% | Less than or in+2% |
| Embodiment 34 | MES | 1.0wt％ | 93 | 86 | 1150 | Be less than or equal to+2% | Be less than or equal to+2% |
| Embodiment 35 | DMS | 1.0wt％ | 93 | 82 | 1100 | Be less than or equal to+2% | Be less than or equal to+2% |
Annotate:
DES: sulfurous acid diethyl ester;
MES: sulfurous acid methyl ethyl ester;
DMS: dimethyl sulfite;
Can understand by comparison sheet 1 to 3: compare among the embodiment 1 to 11 acetylene black as graphite among conductive agent and the embodiment 24 to 35 as conductive agent, among the embodiment 12 to 23 coke as conductive agent improved the 10C/0.2C discharge capacity than and the charge-discharge cycles life-span.Should also be noted that when the addition of line style sulfite hour though the specific area of coke big than acetylene black and graphite, the coke of use has suppressed expansion rate the most significantly in embodiment 12 to 23.
Incidentally, the identical rechargeable nonaqueous electrolytic battery of structure of the rechargeable nonaqueous electrolytic battery that preparation and embodiment 1 to 11 prepare in each only is to use the specific area 70m that is recorded by the BET method
2The acetylene black of/g is as conductive agent.Thus Zhi Bei rechargeable nonaqueous electrolytic battery with aforementioned battery the same terms under carry out high rate capability test, high-temperature charging-discharge cycles performance test and high temperature storage test.Compare the secondary cell of embodiment 1 to 11, the high rate capability of this secondary cell is improved really.Yet, and use coke different as the situation of conductive agent, find the charge-discharge cycles life-span, behind loop test cell thickness rate of change and after 85 ℃ of storages the thickness change of battery worsen.
Suitably to interlamellar spacing d
002In the scope between 0.344nm to 0.352nm and crystallite dimension Lc be that graphitized carbon such as the coke that is less than or equal to 10nm carries out crystallization.Thereby, using under the situation of coke as conductive agent, can improve high rate capability, high-temperature charging-discharge performance and the high-temperature storage performance of rechargeable nonaqueous electrolytic battery.On the other hand, conductive agent such as acetylene black or graphite can not satisfy above-mentioned interlamellar spacing d
002Condition with crystallite dimension Lc.In this case, compare and use acetylene black and graphite secondary cell, use coke to improve the above-mentioned performance of battery, find out as from experimental data, knowing as the secondary cell of conductive agent as conductive agent.
Specific area, the interlamellar spacing d of the conductive agent that uses in following measurement the foregoing description
002With crystallite dimension Lc.
＜measure the specific area of conductive agent by the BET method 〉
Use Autosorb (by the trade name of the measuring instrument of Yuasa Ionics Inc. preparation) to measure the specific area of conductive agent by the BET method.Sample size is set at about 0.5g.And, at 120 ℃ sample is carried out the degassing in 15 minutes and handle as preliminary treatment.
The interlamellar spacing d of (002) face of＜measurement conductive agent
002
Obtain the interlamellar spacing d of (002) face by point methods among the FWHM (full width at half maximum (FWHM) degree) of powder x-ray diffraction spectrum
002In order to obtain the interlamellar spacing d of (002) face
002, do not carry out the correction of scatter correction such as Lorentz scattering.
The crystallite dimension Lc of＜measurement conductive agent 〉
Measure crystallite size Lc by the X-ray diffraction method.When measuring, use CuK α, use HIGH-PURITY SILICON as standard substance as X-ray source by the X-ray diffraction method.Position and half-breadth by each diffraction maximum obtain crystallite dimension Lc.Use the middle point methods of FWHM (full width at half maximum (FWHM) degree) as computational methods.
The method of measurement of line style sulfite content in the secondary cell of the foregoing description is described on the basis of embodiment 5 now.
After initial charging-discharge step, with the circuit maintenance open-circuit condition 5 hours or more of secondary cell among the embodiment 5 so that stablize the electromotive force of secondary cell fully.Then, with secondary cell argon concentration more than or equal to 99.9% and dew point be not higher than in-50 ℃ the glove box and take apart so that take out the electrode group.Then, the electrode group is put into centrifuge tube, and with dimethyl sulfoxide (DMSO) (DMSO)-d
6Add centrifuge tube, seal centrifuge tube then.Further, centrifuge tube is taken out from glove box and carry out centrifugation.In next step, in glove box, from centrifuge tube, take out by liquid electrolyte and DMSO-d
6The mixed solution of forming.Approximately the mixed solution of 0.5mL amount is put into the NMR testing tube of 5mm Ф to carry out the NMR test.Use the instrument " JNM-LA400WB " of JEOL.Ltd preparation to carry out the NMR test.The atomic nucleus of observation is
1H, observing frequency is 400MHZ, utilizes at dimethyl sulfoxide (DMSO) (DMSO)-d
6In faint (2.5ppm) remaining proton signal that comprises as interior mark.Measure temperature and be made as 25 ℃.
1In the H NMR spectrum, observe and the corresponding peak of EC (ethylene carbonate) closing on the 4.5ppm place, and observe and the corresponding peak of DES (sulfurous acid diethyl ester) closing on 1.3ppm, 3.97ppm and 4.03ppm place.Experimental data proves: the nonaqueous electrolyte after initial charging-discharge step in the secondary cell of embodiment contains DES.
In addition, by
1The ratio of the NMR integrated intensity of the DES that obtains in the H NMR spectrum and the NMR integrated intensity of EC can calculate DES amount remaining in the nonaqueous electrolyte.
Those skilled in the art can be easy to expect other advantage and change, and therefore, the present invention is not limited to detail and representative embodiment shown and that describe here aspect widely.Therefore, under the purport and scope that do not break away from inventive concept as accessory claim and equivalent thereof limit, can carry out multiple change.
Claims (10)
1. rechargeable nonaqueous electrolytic battery comprises:
Shell;
Be arranged in shell and contain the nonaqueous electrolyte of line style sulfite;
Be arranged in the positive pole that shell also can absorb-discharge elemental lithium or lithium ion; With
Be arranged in the negative pole of shell, this negative pole comprises Li-Ti oxide and contains the conductive agent of carbonaceous material,
Wherein this line style sulfite comprises at least a compound that is selected from dimethyl sulfite, sulfurous acid diethyl ester and the sulfurous acid methyl ethyl ester.
2. according to the rechargeable nonaqueous electrolytic battery of claim 1, wherein the content of this line style sulfite in nonaqueous electrolyte is 0.8wt% to 5wt%.
3. according to the rechargeable nonaqueous electrolytic battery of claim 1, wherein this nonaqueous electrolyte contains the nonaqueous solvents that comprises gamma-butyrolacton, and gamma-butyrolacton is 30% to 90% with the volume of organic solvent ratio.
4. according to the rechargeable nonaqueous electrolytic battery of claim 1, the interlamellar spacing d of this carbonaceous material (002) face wherein
002Between 0.344nm to 0.352nm, and the crystallite dimension Lc on the C direction of principal axis is smaller or equal to 10nm.
5. according to the rechargeable nonaqueous electrolytic battery of claim 1, wherein this carbonaceous material comprises graphitized carbon, the interlamellar spacing d of this graphitized carbon (002) face
002Between 0.344nm to 0.352nm, and the crystallite dimension Lc on the C direction of principal axis is smaller or equal to 10nm.
6. according to the rechargeable nonaqueous electrolytic battery of claim 5, wherein provide this graphitized carbon by coke.
7. according to the rechargeable nonaqueous electrolytic battery of claim 5, wherein the specific area that recorded by the BET method of this graphitized carbon is 10m
2/ g to 100m
2/ g.
8. according to the rechargeable nonaqueous electrolytic battery of claim 1, wherein this Li-Ti oxide has spinel structure.
9. according to the rechargeable nonaqueous electrolytic battery of claim 1, wherein this Li-Ti oxide is by chemical formula Li
4+xTi
5O
12Expression, wherein 0≤x≤3.
10. according to the rechargeable nonaqueous electrolytic battery of claim 1, this battery comprises the barrier film that places between positive pole and the negative pole in addition.
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| JP4709710B2 (en) | 2006-08-04 | 2011-06-22 | 株式会社東芝 | Non-aqueous electrolyte battery, battery pack and automobile |
| CN101174681B (en) | 2006-10-30 | 2010-05-12 | 比亚迪股份有限公司 | Pole piece complex body, electric core and lithium ion battery |
| JP5184846B2 (en) | 2007-08-28 | 2013-04-17 | 株式会社東芝 | Nonaqueous electrolyte battery and battery pack |
| CN101453002A (en) | 2007-11-29 | 2009-06-10 | 比亚迪股份有限公司 | Battery and method for preparing the same |
| CN201146200Y (en) | 2007-12-18 | 2008-11-05 | 比亚迪股份有限公司 | Casing for battery and battery set including the same |
| US20090162738A1 (en) | 2007-12-25 | 2009-06-25 | Luxia Jiang | Battery system with heated terminals |
| US8276695B2 (en) | 2007-12-25 | 2012-10-02 | Byd Co. Ltd. | Battery electrode sheet |
| US20090159354A1 (en) | 2007-12-25 | 2009-06-25 | Wenfeng Jiang | Battery system having interconnected battery packs each having multiple electrochemical storage cells |
| CN101515640B (en) | 2008-02-22 | 2011-04-20 | 比亚迪股份有限公司 | Cathode and lithium ion secondary battery containing same |
| DE102009018804A1 (en) * | 2009-04-24 | 2010-10-28 | Li-Tec Battery Gmbh | Electrochemical cell with lithium titanate |
| US9337484B2 (en) * | 2009-05-13 | 2016-05-10 | GM Global Technology Operations LLC | Electrodes having a state of charge marker for battery systems |
| CN102185156A (en) * | 2011-04-13 | 2011-09-14 | 北京理工大学 | Electrolyte |
| CN102306834A (en) * | 2011-08-22 | 2012-01-04 | 诺莱特科技(苏州)有限公司 | Electrolyte solution capable of improving air expansion of soft roll lithium manganese battery |
| CN103066242A (en) * | 2012-12-16 | 2013-04-24 | 青岛天鹅针织有限公司 | Cathode for rechargeable lithium battery and rechargeable lithium battery with cathode |
| KR20210043668A (en) * | 2018-08-20 | 2021-04-21 | 캐보트 코포레이션 | Composition containing conductive additives, related electrodes and related batteries |
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