CN103825012A - Battery active material, non-aqueous electrolyte battery and battery pack - Google Patents
Battery active material, non-aqueous electrolyte battery and battery pack Download PDFInfo
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- CN103825012A CN103825012A CN201410064755.8A CN201410064755A CN103825012A CN 103825012 A CN103825012 A CN 103825012A CN 201410064755 A CN201410064755 A CN 201410064755A CN 103825012 A CN103825012 A CN 103825012A
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- composite oxide
- titanium composite
- oxide
- lithium
- battery
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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
-
- 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
The invention provides a non-aqueous electrolyte battery and a battery pack. The non-aqueous electrolyte battery has an outer packaging material, an anode, a cathode, and a non-aqueous electrolyte, wherein the cathode separated from the anode in space comprises an active material containing a titanium composite oxide. The titanium composite oxide comprises a monoclinic-system beta-type titanium composite oxide as a main phase; when the integrated intensity, measured by a wide-angle X-ray diffraction method with a CuK[alpha] ray as an X-ray source, of a main peak of the monoclinic-system beta-type titanium composite oxide is set as 100, a relative value of the integrated intensity of a main peak appearing at 2[theta]=25.1-25.5 DEG and belonging to at least one secondary phase selected from anatase-form TiO2 and H2Ti8O17 is 30 or less, and moreover, the microcrystalline diameter of the titanium composite oxide is calculated to be 5 nm or more according to the monoclinic-system beta-type titanium composite oxide main peak obtained by the wide-angle X-ray diffraction method.
Description
The application is to be the divisional application of May 28, Chinese application number in 2009 patent application that is 200980158315.6 the applying date.
Technical field
The present invention relates to a kind of active material for battery, nonaqueous electrolyte battery and power brick.
Background technology
In recent years, the titanium oxide that has a monoclinic system β type structure (is designated as TiO
2(B)) as active materials for non-aqueous electrolyte battery attracted attention (with reference to patent documentation 1～3).In the past, always by practical spinel type lithium titanate (Li
4ti
5o
12) the quantity of embed/removal lithium embedded ion of per unit chemical formula be three.Therefore, in every 1 titanium ion, the quantity of can embed/removal lithium embedded ion is 3/5,0.6 to be theoretic maximum.On the other hand, TiO
2(B) in every 1 titanium ion, the quantity of can embed/removal lithium embedded ion is 1.0 to the maximum.Therefore, there is the characteristic of theoretical capacity up to about 335mAh/g.
But, disclosed in patent documentation 1 or patent documentation 2, TiO
2(B) practical electrode capacity is 170～200mAh/g left and right, significantly lower than theoretical capacity.Think this be because: although at TiO
2(B) in crystal structure, there is the site of the multiple Li of becoming main bodys, but because the diffusivity of the Li ion in solid is low thereby effective removable Li ion is few.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-34368 communique
Patent documentation 2: TOHKEMY 2008-117625 communique
Patent documentation 3:WO2009/028553A1
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide the TiO that comprises that a kind of conductibility of lithium ion is improved
2(B) active material for battery, comprise this active material as negative electrode active material and there is the nonaqueous electrolyte battery of high power capacity, excellent large current characteristic and possess the power brick of multiple these nonaqueous electrolyte batteries.
For solving the means of problem
According to a first aspect of the invention, a kind of active material for battery is provided, it comprises titanium composite oxide, wherein, described titanium composite oxide comprises monoclinic system beta titanium composite oxides as principal phase, the integrated intensity of the main peak of the described monoclinic system beta titanium composite oxides that record by the wide-angle x-ray diffraction using CuK alpha ray as x-ray source is set as at 100 o'clock, belong to and be selected from Detitanium-ore-type TiO
2and H
2ti
8o
17in the relative value of integrated intensity of the main peak that appears at 2 θ=25.1～25.5 ° of at least one parafacies be below 30, and the crystallite diameter that described titanium composite oxide is calculated by the main peak of the described monoclinic system beta titanium composite oxides that obtain by described wide-angle x-ray diffraction is more than 5nm.
According to a second aspect of the invention, provide a kind of nonaqueous electrolyte battery, it possesses: housing material; Be accommodated in the positive pole in described housing material; Be accommodated in described housing material and the negative pole spatially separating with described positive pole, comprise the active material that contains titanium composite oxide; And be contained in the nonaqueous electrolyte in described housing material, wherein, described titanium composite oxide comprises monoclinic system beta titanium composite oxides as principal phase, the integrated intensity of the main peak of the described monoclinic system beta titanium composite oxides that record by the wide-angle x-ray diffraction using CuK alpha ray as x-ray source is set as at 100 o'clock, belong to and be selected from Detitanium-ore-type TiO
2and H
2ti
8o
17in the relative value of integrated intensity of the main peak that appears at 2 θ=25.1～25.5 ° of at least one parafacies be below 30, and the crystallite diameter that described titanium composite oxide is calculated by the main peak of the described monoclinic system beta titanium composite oxides that obtain by described wide-angle x-ray diffraction is more than 5nm.
According to a third aspect of the invention we, provide a kind of power brick, it possesses the nonaqueous electrolyte battery of multiple described second aspects, and each battery is electrically connected in the mode of serial or parallel connection or in the mode of series and parallel connections.
Invention effect
According to the present invention, a kind of active material for battery that contributes to high power capacity and excellent large current characteristic is provided, there is the nonaqueous electrolyte battery of high power capacity and excellent large current characteristic and possesses the power brick of multiple these nonaqueous electrolyte batteries.
Accompanying drawing explanation
Fig. 1 is the profile that represents the flat nonaqueous electrolyte battery of execution mode.
Fig. 2 is the amplification profile of the A portion of Fig. 1.
Fig. 3 is the exploded perspective view that represents the power brick of execution mode.
Fig. 4 is the block diagram of the power brick of Fig. 3.
Fig. 5 is the figure that represents the X-ray diffraction pattern of the titanium composite oxide of embodiment 1.
Fig. 6 is the figure that represents the X-ray diffraction pattern of the titanium composite oxide of comparative example 1.
Fig. 7 is the figure that represents the X-ray diffraction pattern of the titanium composite oxide of embodiment 7.
Fig. 8 represents monoclinic system beta titanium oxide (TiO
2(B) schematic diagram of crystal structure).
Embodiment
Below the active material for battery in the present invention, nonaqueous electrolyte battery and power brick are elaborated.
Active material for battery in execution mode comprises titanium composite oxide.Titanium composite oxide has following structure: comprise monoclinic system beta titanium composite oxides as principal phase, the integrated intensity of the main peak of the above-mentioned monoclinic system beta titanium composite oxides that record by the wide-angle x-ray diffraction using CuK alpha ray as x-ray source is set as at 100 o'clock, belong to and be selected from Detitanium-ore-type TiO
2and H
2ti
8o
17in the relative value of integrated intensity of the main peak that appears at 2 θ=25.1～25.5 ° of at least one parafacies be below 30., titanium composite oxide has following structure: the integrated intensity of monoclinic system beta titanium composite oxides is set as to I
1, the integrated intensity of at least one parafacies is set as to I
2, by I
1as 100 o'clock, I
2with respect to I
1relative value be below 30.Now, Detitanium-ore-type TiO
2main peak be approximately 25.4 ° at 2 θ and locate to be detected, H
2ti
8o
17main peak be approximately 25.3 ° at 2 θ and locate to be detected.The crystallite diameter that titanium composite oxide is calculated by the main peak of the monoclinic system beta titanium composite oxides that obtain by wide-angle x-ray diffraction is more than 5nm.
Below, above-mentioned wide-angle x-ray diffraction is described.
Titanium composite oxide is pulverized and the powder (sample) that obtains is filled in the retainer (holder) that the degree of depth of glass specimen plate is 0.2mm.Use glass plate fully to press so that be filled in specimen surface the glass specimen plate cunning that flattens from outside with pointing.Now, attention will be filled in retainer part fully by sample, notes avoiding the lack of fill (crackle, space) of sample.Fill in the mode that the degree of depth (0.2mm) of sample size and glass retainer is impartial, note avoiding producing concavo-convex because of the many of loading or the datum level with respect to glass retainer that causes less.
In addition, because the method by being filled into glass specimen plate can be got rid of the skew of diffracted ray peak position or the variation of strength ratio, thereby following method is preferred., by said sample being applied to the pressure of about 250MPa, within 15 minutes, to make diameter be the compacting powder granule that 10mm, thickness are about 2mm, and this particle surface is measured.
Mensuration can be carried out under the condition below for example.
< assay method >
Sample is filled in the normal glass retainer that diameter is 25mm, measures by wide-angle x-ray diffraction.Determinator and condition are as follows.
(1) X-ray diffraction device: Bruker AXS company system, D8ADVANCE(enclose cast)
X-ray source: CuK alpha ray (using Ni filter)
Output: 40kV, 40mA
Slit system: Div.Slit, 0.3 °
Detector: LynxEye(fast detector)
(2) scan mode: 2 θ/θ continuous sweep
(3) measurement range (2 θ): 5～100 °
(4) step-length (2 θ): 0.01712 °
(5) gate time: 1 second/step
The crystallite diameter (crystallite size) of titanium composite oxide can be to the TiO obtaining by wide-angle x-ray diffraction
2(B) the half value width (also referred to as half width) of main peak calculates by Scherrer formula shown below.
[mathematical expression 1]
At this, K=0.9, λ (=0.15406nm), β e: the half value width of diffraction maximum, β o: the correction value (0.07 °) of half value width.
In addition, integrated intensity can be tried to achieve as follows.X-ray diffraction profile diagram after measuring is carried out to smoothing processing and background continuously and remove processing.The profile diagram application Pseudo-Voigt function obtaining is carried out to peak separation, using the peak area of K α 1 as integrated intensity.
The crystal structure of monoclinic system titanium dioxide is designated as to TiO
2(B).TiO
2(B) crystal structure representing mainly belongs to space group C2/m, and it shows the illustrated such tunnel structure of Fig. 8.About TiO
2(B) detailed crystal structure, is recorded in R.Marchand, L.Brohan, and M.Tournoux, in the document of Material Research.
As shown in Figure 8, for TiO
2(B) crystal structure representing, titanium ion 53 and oxide ion 52 form skeleton structure part 51a, and this skeleton structure part 51a has the structure of alternate configurations.Skeleton structure part 51a is formed with gap 51b each other.This gap 51b can become the main body site (host site) of the not embedding of homoatomic kind (insertion).In addition, it is generally acknowledged TiO
2(B) plane of crystal also exists and can embed the not main body site of homoatomic kind of deintercalation.By making lithium ion embedding/deintercalation in these main body sites, TiO
2(B) can reversibly embed/removal lithium embedded ion.
When lithium ion embeds in the 51b of gap, form the Ti of skeleton
4+be reduced to Ti
3+, keep thus the electric neutrality of crystal.TiO
2(B) in every 1 chemical formula, there is a Ti
4+, therefore, can embed at most a lithium ion at interlayer in theory.Therefore, there is TiO
2(B) titanium oxide compound of crystal structure can be by general formula Li
xtiO
2(0≤X≤1) represents.Now, compared with the titanium dioxide of recording in above-mentioned patent documentation 1,2, the theoretical capacity that can obtain approaching 2 times is 335mAh/g.
But, TiO
2(B) the low temperature metastable phase for existing at than approximately 500 ℃ of low temperature, therefore, when synthetic, is selected from Detitanium-ore-type TiO
2and H
2ti
8o
17in at least one parafacies easily sneak into as impurity phase.Due to the diffusion of impurity phase obstruction lithium ion, therefore make TiO
2(B) ionic conductivity of lithium reduces.Consequently, for TiO in the past
2(B), be difficult to stably take out high power capacity more than 240mAh/g.
In addition, TiO
2(B) because of the other reasons different from existing of impurity phase, the diffusion velocity of lithium ion is little, has the conductivity of lower lithium ion.It is generally acknowledged, compared with being for example used as the lithium cobalt composite oxide of positive active material, TiO
2(B) more than the low about double figures of conductivity of lithium ion.Therefore, by TiO
2(B) as negative electrode active material, in the embedding/deintercalation of nonaqueous electrolyte battery that lithium cobalt composite oxide is combined as the positive active material lithium ion between positive pole and negative pole, to TiO
2(B) the low diffusivity of the lithium ion in is carried out speed control, and therefore, large current characteristic reduces.
In addition, the diffusion velocity of lithium ion refers to the diffusion velocity of the intracrystalline diffusion of active material and crystal boundary diffusion merging.
The active material for battery of execution mode comprises titanium composite oxide, and described titanium composite oxide has following structure: comprise monoclinic system beta titanium composite oxides (TiO
2(B)) as principal phase, by the above-mentioned TiO recording by the wide-angle x-ray diffraction using CuK alpha ray as x-ray source
2(B) integrated intensity of main peak is set as at 100 o'clock, belongs to and is selected from Detitanium-ore-type TiO
2and H
2ti
8o
17in at least one parafacies be that the relative value of the integrated intensity at the peak that appears at 2 θ=25.1～25.5 ° of impurity phase is below 30.For such titanium composite oxide, due to hinder lithium ion diffusion impurity phase amount reduce or essence be zero, therefore, can improve the ionic conductivity of lithium.Consequently, can give play to TiO
2(B) intrinsic high capacitance.
In addition, titanium composite oxide is by the TiO obtaining by above-mentioned wide-angle x-ray diffraction
2(B) the crystallite diameter that main peak calculates is more than 5nm, to that is to say, has large crystallite diameter.Consequently, the lithium ion diffusion velocity of titanium composite oxide uprises, thereby can improve the ionic conductivity of lithium.Therefore, while carrying out the embedding/deintercalation of the lithium ion between positive pole and negative pole combining using above-mentioned titanium composite oxide as negative electrode active material, using lithium cobalt composite oxide as positive active material, can utilize the titanium composite oxide with higher lithium ion diffusion velocity to relax the diffusion rate control of negative pole with respect to anodal lithium ion, thereby can improve large current characteristic.
As mentioned above, be more than 5nm by making the crystallite diameter of titanium composite oxide, can improve thus ionic conductivity and the large current characteristic of titanium composite oxide.The crystallite diameter of preferred titanium composite oxide is more than 20nm.On the crystallite diameter of titanium composite oxide, be limited to 300nm.
By the above-mentioned TiO obtaining by wide-angle x-ray diffraction
2(B) integrated intensity of main peak is set as at 100 o'clock, makes to belong to be selected from Detitanium-ore-type TiO
2and H
2ti
8o
17in at least one parafacies be that the relative value of the integrated intensity at the peak that appears at 2 θ=25.1～25.5 ° of impurity phase is below 30, can improve thus the diffusion velocity of the lithium ion of titanium composite oxide, and then can improve ionic conductivity and large current characteristic.The relative value of the integrated intensity at the preferred peak that appears at 2 θ=25.1～25.5 ° that belongs to parafacies is below 10, more preferably below 3.Titanium composite oxide preferably have do not comprise impurity phase, in fact by the TiO as principal phase
2(B) structure forming.Therefore, also to comprise impurity phase be i.e. zero the state of state below detectable limit to titanium composite oxide.
The primary particle size of titanium composite oxide is preferably 30nm～3 μ m.Be 30nm above in the situation that at primary particle size, in industrial production, become easy operation.Be below 3 μ m in the situation that at primary particle size, lithium ion diffusion length in solid shortens, thereby can improve high-rate performance.More preferably primary particle size on be limited to 1 μ m.
The specific area of titanium composite oxide is preferably 5m
2/ g～50m
2/ g.Be 5m in specific area
2in situation more than/g, can fully guarantee embedding/deintercalation site of lithium ion.Be 50m in specific area
2in situation below/g, in industrial production, become easy operation.
Titanium composite oxide is preferably: comprise and be selected from least one element in P and B, and the content of at least one element is counted 0.01 % by weight～3 % by weight with respect to the total amount of titanium composite oxide and at least one element with total amount.The titanium composite oxide that comprises at least one element is preferably: form particle shape, and at least one element is present in the form of oxide in the particle of titanium composite oxide or particle surface.The titanium composite oxide that is selected from comprising like this at least one element in P and B can further reduce sneaking into of impurity phase, thereby can improve crystallinity and increase crystallite diameter.Consequently, can obtain stably taking out the titanium composite oxide of capacity more than 240mAh/g.The content of at least one element during lower than 0.01 % by weight, improves crystalline effect and diminishes.When the content of at least one element exceedes 3 % by weight, likely P
2o
5, B
2o
3impurity phase amount increase, make electric capacity reduce.In at least one element, the above-mentioned effect of P is higher than B, therefore preferably.
The content that is selected from least one element in P and B can be measured by ICP emission spectrometry.The mensuration of the content of the above-mentioned element recording by ICP emission spectrometry can be implemented by for example following method.Under discharge condition, battery is disintegrated, take out electrode (for example negative pole), by this negative electrode layer inactivation in water.Then, extract the titanium composite oxide in negative electrode layer.Extraction process can be undertaken by the conductive agent and the binding agent that utilize for example heat treated in atmosphere to remove in negative electrode layer.In container, take after the titanium composite oxide after extraction, carry out acid-soluble solution or alkali and dissolve, thereby obtain measuring solution.For example, with determinator (エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ ー company system: SPS-1500V) this mensuration solution is carried out the luminous light splitting of ICP and is measured the content of above-mentioned element.
Titanium composite oxide is allowed inevitable impurity in the manufacture except being selected from least one element in P and B containing below 1000 ppm by weight.
Then, the manufacture method of the active material for battery to execution mode describes.
First, Preparation Example is as Na
2ti
3o
7, K
2ti
4o
9, Cs
2ti
5o
12and so on metatitanic acid alkali metal compound as initiation material.For metatitanic acid alkali metal compound, can mix the material that contains Ti and the material that contains the alkali metals such as Na, K, Cs with requirement ratio, and synthesize by common solid reaction process.Synthetic method, the crystal shape do not limit of initiation material.In addition, K
2ti
4o
9potassium titanate also can synthesize with for example flux method.
Initiation material is fully washed with pure water and is removed after impurity from metatitanic acid alkali metal compound, carries out acid treatment, thereby is proton by alkali metal cation-exchanged.Each sodium ion in sodium titanate, potassium titanate and metatitanic acid caesium, potassium ion, cesium ion can be in the situation that not destroying crystal structure and proton exchange.The proton exchange of being undertaken by acid treatment for example can be by adding the hydrochloric acid of concentration 1M and stirring and carry out in initiation material.Till acid treatment preferably proceeds to proton exchange and fully finishes.In the time of proton exchange, also can in solution, add alkaline solution or acid solution regulates pH.After proton exchange finishes, again wash with pure water.
For initiation material, preferably before proton exchange, pulverize with ball mill in advance.This pulverizing can make proton exchange complete smoothly.Can pulverize by following pulverization conditions, that is, and every 100cm
2container use the zirconia ball of diameter 10～15mm left and right, under the rotating speed of 600～1000rpm, make zirconia ball rotation about 1～3 hour.For following pulverizing in 1 hour, because initiation material is not fully pulverized, therefore not preferred.In addition, for above long pulverizing in 3 hours, because meeting promotes that mechanico-chemical reaction is separated as the compound different from target product, therefore not preferred.
For proton exchange, implement on the vibration limit that applies for example ultrasonic wave and so on by limit, can more successfully complete proton exchange, thereby can obtain the proton exchange body of proper states.
Then, by the product of the proton exchange that is through with being washed and is dried the proton exchange body synthesizing as intermediate product.Then, by being carried out to heat treated, manufactures with TiO proton permutoid
2(B) be the titanium composite oxide of principal phase.
Preferred heating-up temperature is 250 ℃～500 ℃.While making heating-up temperature lower than 250 ℃, crystallinity significantly reduces, H
2ti
8o
17impurity phase mixed volume increase, electric capacity reduce.On the other hand, when heating-up temperature exceedes 500 ℃, although crystallinity improves, as the H of impurity phase
2ti
8o
17also reduce mutually, but as other the Detitanium-ore-type TiO of impurity phase
2the mixed volume of phase increases, and electric capacity likely reduces.Preferred heating-up temperature is 300 ℃～400 ℃.
The time of heat treated carries out about 30 minutes～24 hours.The time of preferred heat treated is: at the temperature of 300 ℃～400 ℃, be 1 hour～3 hours.
In addition, also can use in above-mentioned metatitanic acid alkali metal compound to add and be selected from material that at least one element in P and B forms as initiation material.As this initiation material, can mix as the material of above-mentioned at least one element, the material that contains Ti and the material that contains the alkali metals such as Na, K, Cs using requirement ratio, and utilize common solid reaction process to synthesize.With respect to the total amount of the titanium composite oxide obtaining and above-mentioned at least one element, the addition of at least one element is preferably counted 0.01 % by weight～3 % by weight with total amount.
Above-mentioned at least one element works as sintering aid in the time of heat treated, is difficult to residual H
2ti
8o
17and so on impurity phase.Consequently, can obtain the titanium composite oxide that crystallite diameter is large and impurity phase is few.
Which one no matter the active material for battery of execution mode not only can, for negative pole described later, also can, for positive pole, be applied to, and all contributes to the high capacity of active material, and when for battery, contribute to the raising of large current characteristic.
In the case of by the active material for battery in execution mode for anodal, can use the carbon-based materials such as lithium metal, lithium alloy or graphite, coke as the active material of the negative pole to electrode.
Then, the nonaqueous electrolyte battery in execution mode is described.
Nonaqueous electrolyte battery in execution mode possesses: housing material; Be accommodated in the positive pole in housing material; In housing material, spatially separate with positive pole, negative pole that be for example contained across barrier film, that comprise active material; And be filled in the nonaqueous electrolyte in housing material.
Below, the housing material to the component parts as nonaqueous electrolyte battery, negative pole, positive pole, barrier film and nonaqueous electrolyte are elaborated.
1) housing material
Housing material is that laminated film below 0.5mm forms by thickness.In addition, housing material can used thickness be the metal container made below 1.0mm.The thickness of metal container made is more preferably below 0.5mm.
The shape of housing material can list pancake (thin type), square, cylindrical shape, coin (coin) shape, button (button) shape etc.Housing material for example can be enumerated housing material compact battery for that carries on portable electric appts etc., take turns to the large-sized battery housing material of lift-launch on four-wheel automobile etc. two according to battery size.
Laminated film uses the plural layers that accompany metal level between resin bed.For lightweight, the preferred aluminium foil of metal level or alloy foil.Resin bed can use the macromolecular materials such as such as polypropylene (PP), polyethylene (PE), nylon, PETG (PET).Thereby laminated film can be by the bonding shape that is configured as housing material that seals of heat fusing.
Metal container made can be by making such as aluminum or aluminum alloy.Aluminium alloy is preferably the alloy of elements such as comprising magnesium, zinc, silicon.The in the situation that of comprising the transition metal such as iron, copper, nickel, chromium in alloy, its amount is preferably below 100ppm.
2) negative pole
Negative pole possesses: collector body and the negative electrode layer that is formed at the one or both sides of this collector body and comprises active material, conductive agent and binding agent.
Active material can use the above-mentioned active material for battery that comprises titanium composite oxide.Titanium composite oxide has following composition: comprise monoclinic system beta titanium composite oxides as principal phase, the integrated intensity of the main peak of the above-mentioned monoclinic system beta titanium composite oxides that record by the wide-angle x-ray diffraction using CuK alpha ray as x-ray source is set as at 100 o'clock, belong to and be selected from Detitanium-ore-type TiO
2and H
2ti
8o
17in the relative value of integrated intensity of the main peak that appears at 2 θ=25.1～25.5 ° of at least one parafacies be below 30.The crystallite diameter that titanium composite oxide is calculated by the main peak of the monoclinic system beta titanium composite oxides that obtain by wide-angle x-ray diffraction is more than 5nm.
As mentioned above, such active material has high lithium ion diffusion velocity and high lithium-ion-conducting.Consequently, the nonaqueous electrolyte battery that the negative pole that has possessed the negative electrode layer that comprises this active material is housed can improve large current characteristic.
Conductive agent improves the current collection performance of active material, suppresses the contact resistance with collector body.The example of conductive agent comprises acetylene black, carbon black, graphite.
Binding agent can bond active material and conductive agent.The example of binding agent comprises polytetrafluoroethylene (PTFE), Kynoar (PVdF), fluorine-containing rubber, butadiene-styrene rubber.
Active material, conductive agent and binding agent in negative electrode layer preferably coordinates with the ratio of 70 % by weight～96 % by weight, 2 % by weight～28 % by weight and 2 % by weight～28 % by weight respectively.The amount of conductive agent is during lower than 2 % by weight, and likely the current collection performance of negative electrode layer reduces, the large current characteristic of nonaqueous electrolyte battery reduces.In addition, the amount of binding agent is during lower than 2 % by weight, and likely the caking property of negative electrode layer and collector body reduces, cycle characteristics reduces.On the other hand, be respectively below 28 % by weight seeking preferred conductive agent and binding agent aspect high capacity.
The alloy foil of the element that collector body is preferably the aluminium foil stable at the potential range electrochemistry more expensive than 1.0V or comprises Mg, Ti, Zn, Mn, Fe, Cu, Si and so on.
Negative pole is for example made as follows: active material, conductive agent and binding agent are suspended in general solvent and prepare slurry, this slurry is coated on collector body and is dried, then pressurize, make thus negative pole.Negative pole also can be made as follows: active material, conductive agent and binding agent are formed as to graininess and make negative electrode layer, and be formed on collector body, make thus negative pole.
3) positive pole
Positive pole possesses: collector body and the anodal layer that is formed at the one or both sides of this collector body and comprises active material, conductive agent and binding agent.
Active material for example can use oxide, polymer etc.
Oxide can use and for example embed the manganese dioxide (MnO that has lithium
2), iron oxide, cupric oxide, nickel oxide and complex Li-Mn-oxide (for example Li
xmn
2o
4or Li
xmnO
2), lithium nickel composite oxide (for example Li
xniO
2), lithium cobalt composite oxide (Li
xcoO
2), lithium/nickel/cobalt composite oxide (for example LiNi
1-yco
yo
2), lithium manganese cobalt composite oxide (for example Li
xmn
yco
1-yo
2), spinel type lithium mn-ni compound oxide (Li
xmn
2-yni
yo
4), there is Lithium Phosphor Oxide (for example Li of olivine structural
xfePO
4, Li
xfe
1-ymn
ypO
4, Li
xcoPO
4), ferric sulfate (Fe
2(SO
4)
3) or vanadium oxide (for example V
2o
5).At this, x, y are preferably 0 < x≤1,0≤y≤1.
Polymer can use conductive polymer material or the disulphide based polymer material of for example polyaniline or polypyrrole and so on.Sulphur (S), fluorocarbons also can be used as active material.
As preferred active material, can list the complex Li-Mn-oxide (Li that cathode voltage is high
xmn
2o
4), lithium nickel composite oxide (Li
xniO
2), lithium cobalt composite oxide (Li
xcoO
2), lithium/nickel/cobalt composite oxide (Li
xni
1-yco
yo
2), spinel type lithium mn-ni compound oxide (Li
xmn
2-yni
yo
4), lithium manganese cobalt composite oxide (Li
xmn
yco
1-yo
2) or LiFePO4 (Li
xfePO
4).At this, x, y are preferably 0 < x≤1,0≤y≤1.
Further preferred active material is lithium cobalt composite oxide or complex Li-Mn-oxide.These active materials are because ionic conductivity is high, therefore, with the combination of above-mentioned negative electrode active material in, the diffusion of the lithium ion in positive active material is difficult to become rate determining step.Therefore, the adaptability excellence of the lithium-titanium composite oxide in above-mentioned active material and above-mentioned negative electrode active material.
Conductive agent improves the current collection performance of active material, suppresses the contact resistance with collector body.The example of conductive agent comprises the Carbonaceous matters such as acetylene black, carbon black, graphite.
Binding agent makes active material and conductive agent bonding.The example of binding agent comprises polytetrafluoroethylene (PTFE), Kynoar (PVdF), fluorine-containing rubber.
Active material, conductive agent and binding agent in anodal layer preferably coordinate with the ratio of 80 % by weight～95 % by weight, 3 % by weight～18 % by weight and 2 % by weight～17 % by weight respectively.Be amounts more than 3 % by weight by making conductive agent, can bring into play above-mentioned effect.Be the amount below 18 % by weight by making conductive agent, can be reduced in the decomposition of the nonaqueous electrolyte on the conductive agent surface under High temperature storage.Be amounts more than 2 % by weight by making binding agent, can obtain fully positive pole strength.Be the amount below 17 % by weight by making binding agent, can reduce the use level as the binding agent of the insulating material in positive pole, thereby reduce internal resistance.
The alloy foil of the element that collector body is for example preferably aluminium foil or comprises Mg, Ti, Zn, Mn, Fe, Cu, Si and so on.
Positive pole is for example made as follows: active material, conductive agent and binding agent are suspended in general solvent and prepare slurry, this slurry is coated on collector body and is dried, then pressurize, make thus anodal.In addition, positive pole also can be made as follows: active material, conductive agent and binding agent are formed as to graininess and make negative electrode layer, be formed on collector body, make thus anodal.
4) nonaqueous electrolyte
As nonaqueous electrolyte, the gel nonaqueous electrolyte that for example can list aqueous nonaqueous electrolyte by electrolyte dissolution is prepared in organic solvent or aqueous electrolyte and macromolecular material Composite are formed.
Aqueous nonaqueous electrolyte is preferably dissolved in electrolyte in organic solvent with the concentration of 0.5M～2.5M.
Electrolytical example comprises lithium perchlorate (LiClO
4), lithium hexafluoro phosphate (LiPF
6), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), trifluoromethanesulfonic acid lithium (LiCF
3sO
3), two (fluoroform sulphonyl) imine lithium [LiN(CF
3sO
2)
2] lithium salts or the mixture that comprises these.Even if electrolyte is also not oxidizable material under high potential preferably, most preferably LiPF
6.
The example of organic solvent comprises the cyclic carbonate of propylene carbonate (PC), ethylene carbonate (EC), vinylene carbonate and so on; The linear carbonate of diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (MEC) and so on; The cyclic ether of oxolane (THF), 2-methyltetrahydrofuran (2MeTHF), dioxolane (DOX) and so on; The chain ether of dimethoxy-ethane (DME), diethoxyethane (DEE) and so on; Or gamma-butyrolacton (GBL), acetonitrile (AN), sulfolane (SL).These organic solvents can use separately or with the form of mixed solvent.
The example of macromolecular material comprises Kynoar (PVdF), polyacrylonitrile (PAN), poly(ethylene oxide) (PEO).
Preferred organic solvent is by least two or more mixed solvents that mix in the group of propylene carbonate (PC), ethylene carbonate (EC) and (diethyl carbonate (DEC)) formation or the mixed solvent that comprises gamma-butyrolacton (GBL).
5) barrier film
As barrier film, can enumerate the porous film or the synthetic resin nonwoven fabrics processed that contain for example polyethylene, polypropylene, cellulose or Kynoar (PVdF).Preferred porous film is made by polyethylene or polypropylene, because electric current is blocked in its melting at a certain temperature, therefore, can improve fail safe.
Then, with reference to Fig. 1, Fig. 2, the nonaqueous electrolyte battery to execution mode (flat nonaqueous electrolyte battery that for example housing material is made up of laminated film) carries out more specific description.Fig. 1 is the profile of thin type nonaqueous electrolyte battery, the amplification profile of the A portion that Fig. 2 is Fig. 1.In addition, each figure is explanation for promoting invention and the schematic diagram of understanding thereof, and its shape and size, ratio etc. have the place different from actual device, but these can suitably carry out design alteration with reference to explanation and known technology below.
The rolled electrode group 1 of flat is accommodated in the bag-shaped housing material 2 being made up of the laminated film that accompanies aluminium foil between 2 resin beds.The rolled electrode group 1 of flat forms as follows: the sandwich forming according to negative pole 3, barrier film 4, positive pole 5, the sequential cascade of barrier film 4 from outside is wound into vortex shape, and carries out extrusion forming.The negative pole 3 of outermost shell has as shown in Figure 2 the structure that is formed with negative electrode layer 3b in the one side of the inner face side of negative electrode collector 3a.Other negative pole 3 is form negative electrode layer 3b and form on the two sides of negative electrode collector 3a.Active material in negative electrode layer 3b comprises titanium composite oxide.Titanium composite oxide has following composition: comprise monoclinic system beta titanium composite oxides as principal phase, the integrated intensity of the main peak of the above-mentioned monoclinic system beta titanium composite oxides that record by the wide-angle x-ray diffraction using CuK alpha ray as x-ray source is set as at 100 o'clock, belong to and be selected from Detitanium-ore-type TiO
2and H
2ti
8o
17in the relative value of integrated intensity of the main peak that appears at 2 θ=25.1～25.5 ° of at least one parafacies be below 30.The crystallite diameter that titanium composite oxide is calculated by the main peak of the monoclinic system beta titanium composite oxides that obtain by wide-angle x-ray diffraction is more than 5nm.Anodal 5 is on the two sides of positive electrode collector 5a, to form anodal layer 3b and form.
Near the outer circumference end of rolled electrode group 1, negative terminal 6 is connected with the negative electrode collector 3a of the negative pole 3 of outermost shell, and positive terminal 7 is connected with the positive electrode collector 5a of the positive pole 5 of inner side.These negative terminals 6 and positive terminal 7 extend to outside from the peristome of bag-shaped housing material 2.For example aqueous nonaqueous electrolyte injects from the peristome of bag-shaped housing material 2.By the peristome of bag-shaped housing material 2 is carried out to heat seal in the mode that clips negative terminal 6 and positive terminal 7, thereby rolled electrode group 1 and aqueous nonaqueous electrolyte are sealed completely.
Negative terminal is made by the material that possesses electrical stability and conductivity in the scope that is for example 1.0V～3.0V at the current potential with respect to lithium ion metal.The aluminium alloy that particularly, can list aluminium or comprise the elements such as Mg, Ti, Zn, Mn, Fe, Cu, Si.In order to reduce and the contact resistance of negative electrode collector, negative terminal is preferably the material identical with negative electrode collector.
Positive terminal is made by the material that possesses electrical stability and conductivity in the scope that is 3.0～4.25V at the current potential with respect to lithium ion metal.The aluminium alloy that particularly, can list aluminium or comprise the elements such as Mg, Ti, Zn, Mn, Fe, Cu, Si.In order to reduce and the contact resistance of positive electrode collector, positive terminal is preferably the material identical with positive electrode collector.
Then, the power brick of execution mode is elaborated.
The power brick of execution mode has multiple above-mentioned nonaqueous electrolyte batteries (monocell), and each monocell electricity is electrically connected and is configured in the mode of serial or parallel connection or in the mode of series and parallel connections.
Such power brick has excellent cycle characteristics.
Due to the impurity phase of titanium composite oxide contained in negative electrode active material sneak into less and crystallinity high, therefore, used the nonaqueous electrolyte battery of this titanium composite oxide can improve large current characteristic and charge-discharge performance.Consequently, even when the power brick of multiple such batteries is housed carries out discharging and recharging under large electric current, also can improve charge-discharge performance.
Then, with reference to Fig. 3 and Fig. 4, the power brick in execution mode is specifically described.Monocell can use flat-shaped non-aqueous electrolyte battery as shown in Figure 1.
Printed wiring board 24 relatively configures with monocell 21 sides of extending negative terminal 6 and positive terminal 7.As shown in Figure 4, on printed wiring board 24, be equipped with thermistor 25, protective circuit 26 and the terminal 27 for energising to the energising of external equipment.In addition, for fear of there is unnecessary being connected with the distribution of Battery pack 23, insulation board (without diagram) is installed on the face of the protective circuit substrate 24 relative with Battery pack 23.
Side of the positive electrode lead-in wire 28 is connected with the undermost positive terminal 7 that is positioned at Battery pack 23, and its front end is inserted in the side of the positive electrode connector 29 of printed wiring board 24 and is electrically connected.Negative side lead-in wire 30 is connected with the negative terminal 6 of the superiors that are positioned at Battery pack 23, and its front end is inserted in the negative side connector 31 of printed wiring board 24 and is electrically connected.These connectors 29,31 are connected with protective circuit 26 by the distribution 32,33 being formed on printed wiring board 24.
On three sides of the Battery pack 23 except positive terminal 7 and the outstanding side of negative terminal 6, dispose respectively the protection sheet material 36 being formed by rubber or resin.
In addition, for fixing of Battery pack 23, also can use thermal contraction to bring and replace jointing tape 22.In this case, at two side configuration protection sheet materials of Battery pack, and with after shrink belt pitch of the laps, make shrink belt carry out thermal contraction and Battery pack is tied up.
Fig. 3, Fig. 4 show the form that monocell 21 is connected in series, but in order to increase battery capacity, also can connect in parallel or also can combined serial connect and be connected in parallel.Also the power brick assembling further can be connected in the mode of series, parallel.
In addition, the form of power brick can be according to the suitable change of purposes.The purposes of power brick preferably demonstrates excellent cycle characteristics in the time taking out large electric current.The power supply that particularly, can list digital camera with or two take turns to the hybrid vehicle, two of four-wheel and take turns the vehicle mounted such as electric motor car, moped to four-wheel.Particularly preferably vehicle mounted.
As mentioned above, comprise at least two or more mixed solvents that mix in the group of propylene carbonate (PC), ethylene carbonate (EC) and diethyl carbonate (DEC) formation or the nonaqueous electrolyte of gamma-butyrolacton (GBL) by use, can obtain the nonaqueous electrolyte battery of hot properties excellence.The power brick that possesses the Battery pack with multiple such nonaqueous electrolyte batteries is particularly suitable for vehicle mounted.
Below, embodiment is described.In addition, only otherwise exceed purport of the present invention, be just not limited to the embodiment of following record.
(embodiment 1)
The making > of < positive pole
First, in 1-METHYLPYRROLIDONE (NMP), add the lithium nickel composite oxide (LiNi as positive active material
0.82co
0.15al
0.03o
2) powder 90 % by weight, as acetylene black 5 % by weight of conductive agent and Kynoar (PVdF) 5 % by weight and mix, thereby make slurry, after this slurry is coated on the two sides of the collector body being made up of aluminium foil that thickness is 15 μ m, be dried, pressurize, making thus electrode density is 3.15g/cm
3positive pole.
The making > of < titanium composite oxide
First, mixed carbonic acid potassium (K
2cO
3) and anatase-type titanium oxide (TiO
2), at 1000 ℃, burn till 24 hours, thus synthetic K
2ti
4o
9.With zirconium oxide bead to the K obtaining
2ti
4o
9carry out dry type pulverizing and adjust granularity, then with pure water washing, thereby make proton exchange precursor.Obtained proton exchange precursor is put in the hydrochloric acid solution of 1M concentration, and the ultrasonic wave carrying out under the environment of 25 ℃ 1 hour stirs.Repeat 12 these operations, all exchange hydrochloric acid at every turn, then washing, thus obtain proton exchange body.Then, in atmosphere, at 350 ℃, the proton exchange body obtaining is implemented to 3 hours burning till, manufacture thus titanium composite oxide.
The titanium composite oxide obtaining is carried out to the mensuration of the strength ratio of crystallite diameter and main peak.
, utilize said determination method to obtain the wide-angle x-ray diffraction pattern of the use Cu-K α of titanium composite oxide.Obtained X-ray diffraction pattern is shown in to Fig. 5.
For the crystallite diameter of titanium composite oxide, the half value width at the X-ray diffraction peak of its (110) face that is approximately 24.8 ° by the angle of diffraction (2 θ) of monoclinic system beta titanium composite oxides by above-mentioned computational methods is obtained.The crystallite diameter of titanium composite oxide is 15nm.In addition, in the calculating of the half value width of diffraction maximum, need to revise according to the live width of the optics system of diffraction instrument, in this correction, use standard silicon powder.
Using the monoclinic system beta titanium composite oxides that calculate with said method X-ray diffraction pattern as shown in Figure 5 as main peak
the peak integrated intensity of (2 θ: 24.8 °) is set as at 100 o'clock, belongs to respectively Detitanium-ore-type TiO
2and H
2ti
8o
17the relative value of integrated intensity of the main peak that appears at 2 θ=25.1～25.5 ° be 23.
The making > of < negative pole
In 1-METHYLPYRROLIDONE (NMP), add obtained titanium composite oxide powder 90 % by weight, acetylene black 5 % by weight and Kynoar (PVdF) 5 % by weight and mix, thereby making slurry.By this slurry be coated on thickness be 15 μ m the collector body being formed by aluminium foil two sides and dry after, pressurize, making thus electrode density is 2.0g/cm
3negative pole.
The making > of < electrode group
After being the sequential cascade of the barrier film, negative pole and the barrier film that are formed by polyethylene porous film processed of 25 μ m according to anodal, thickness, be wound into vortex shape.It is heated at 90 ℃ to pressurization, making thus width is the flat electrode group that 30mm, thickness are 3.0mm.The electrode group obtaining is accommodated in the package body being made up of laminated film, at 80 ℃, implements vacuumize in 24 hours.The two sides that laminated film is is the aluminium foil of 40 μ m at thickness forms polypropylene layer and forms, and the thickness of entirety is 0.1mm.
The preparation > of the aqueous nonaqueous electrolyte of <
According to the volume ratio mixed carbonic acid ethyl (EC) of 1:2 and ethylene methyl esters (EMC) and make mixed solvent.In this mixed solvent, dissolve the electrolytical LiPF of conduct of 1M
6, prepare thus aqueous nonaqueous electrolyte.
The manufacture > of < rechargeable nonaqueous electrolytic battery
In the package body of laminated film of receiving electrode group, inject aqueous nonaqueous electrolyte.Then, by heat seal, package body is completely airtight, manufacture that to have the structure shown in above-mentioned Fig. 1 and width be that 35mm, thickness are 3.2mm, highly are the rechargeable nonaqueous electrolytic battery of 65mm.
(embodiment 2～6 and comparative example 1)
Except the firing temperature of proton exchange body is become the temperature shown in following table 1, with the synthetic titanium composite oxide of method similarly to Example 1.Except these titanium composite oxides are used as negative electrode active material, utilize method similarly to Example 1 to manufacture rechargeable nonaqueous electrolytic battery.In addition, make similarly to Example 1 the wide-angle x-ray diffraction pattern that has used Cu-K α, calculated relative value and the crystallite diameter of the integrated intensity of the titanium composite oxide using in the embodiment 2～6 shown in following table 1 and comparative example 1 by this diffraction pattern.The X-ray diffraction pattern of the titanium composite oxide using in comparative example 1 is shown in to Fig. 6.
To each battery of embodiment 1～6 and comparative example 1, under the environment of 25 ℃, measure 0.2C discharge capacity and 2C discharge capacity, 2C discharge capacity is obtained as capacity dimension holdup (%) with respect to the ratio (%) of 0.2C discharge capacity.The results are shown in following table 1.
In addition, the negative pole using in the battery by embodiment 1～6 and comparative example 1 and formed by lithium metal to electrode fabrication single electrode.By unipolar negative pole with 0.1mA/cm
2current value make lithium ion embed (charging) to 1V(Li/Li
+) after, with 0.1mA/cm
2current value make lithium ion deintercalation (electric discharge) to 3V(Li/Li
+).Discharge electricity amount is now scaled as the electric weight of the per unit weight of the lithium titanate of negative electrode active material.Value after converting is shown in following table 1 as capacity of negative plates.
Table 1
Shown by table 1, known is below 30 by the relative value of integrated intensity and crystallite diameter is more than 5nm titanium composite oxide as the battery of the embodiment 1～6 of negative electrode active material and the titanium composite oxide that any one in the relative value of above-mentioned integrated intensity and crystallite diameter is departed to above-mentioned scope as compared with the battery of the comparative example 1 of negative electrode active material, demonstrates high capacity of negative plates and high power capacity sustainment rate (good high-rate performance).
(embodiment 7)
Except by being used as negative electrode active material with the synthetic titanium composite oxide of following method, make similarly to Example 1 rechargeable nonaqueous electrolytic battery.
Mixed oxidization phosphorus (P
2o
5), boron oxide (B
2o
3), potash (K
2cO
3) and anatase-type titanium oxide (TiO
2), at 1000 ℃, burn till 24 hours, obtain thus the K that comprises P and B
2ti
4o
9.With zirconium oxide bead to the K obtaining
2ti
4o
9carry out dry type pulverizing and adjust after granularity, with pure water washing, thereby obtaining proton exchange precursor.Obtained proton exchange precursor is put in the hydrochloric acid solution of 1M concentration, and the ultrasonic wave carrying out under the environment of 25 ℃ 1 hour stirs.Repeat 12 these operations, all exchange hydrochloric acid at every turn, then washing, thus obtain proton exchange body.Then, in atmosphere, at 350 ℃, the proton exchange body obtaining is implemented to 3 hours burning till, synthetic titanium composite oxide.
Utilize above-mentioned icp analysis to measure the amount of the P in obtained titanium composite oxide and B.Consequently, the amount of P and B is respectively 0.230 % by weight, 0.010 % by weight.By the use of obtained titanium composite oxide the wide-angle x-ray diffraction pattern of Cu-K α be shown in Fig. 7.By this wide-angle x-ray diffraction pattern try to achieve similarly to Example 1 using monoclinic system beta titanium composite oxides as main peak
the peak integrated intensity of (2 θ: 24.8 °) sets at 100 o'clock, belongs to respectively Detitanium-ore-type TiO
2and H
2ti
8o
17the relative value of integrated intensity and the crystallite diameter of titanium composite oxide of the main peak that appears at 2 θ=25.1～25.5 °.Consequently, the relative value of integrated intensity and crystallite diameter be respectively below 3,25nm.
(embodiment 8～16 and comparative example 2)
Except making the amount (with respect to the amount of the total amount of titanium composite oxide and P and B) of P and B for the ratio shown in following table 2, with the synthetic titanium composite oxide of method similarly to Example 7.Except these titanium composite oxides are used as negative electrode active material, utilize method similarly to Example 1 to manufacture rechargeable nonaqueous electrolytic battery.In addition, make similarly to Example 1 the wide-angle x-ray diffraction pattern that has used Cu-K α, calculated relative value and the crystallite diameter of the integrated intensity of the titanium composite oxide using in the embodiment 8～16 shown in following table 2 and comparative example 2 by this diffraction pattern.
To each battery of embodiment 7～16 and comparative example 2, under the environment of 25 ℃, measure 0.2C discharge capacity and 2C discharge capacity, 2C discharge capacity is obtained as capacity dimension holdup (%) with respect to the ratio (%) of 0.2C discharge capacity.The results are shown in following table 2.
In addition, the negative pole using in the battery by embodiment 7～16 and comparative example 2 and formed by lithium metal to electrode fabrication single electrode.By unipolar negative pole with 0.1mA/cm
2current value make lithium ion embed (charging) to 1V(Li/Li
+) after, with 0.1mA/cm
2current value make lithium ion deintercalation (electric discharge) to 3V(Li/Li
+).Discharge electricity amount is now converted into as the electric weight of the per unit weight of the lithium titanate of negative electrode active material.Value after converting is shown in following table 2 as capacity of negative plates.
Shown by table 2, known by the relative value that is selected from least one element in P and B and integrated intensity that contains ormal weight be below 30, to be more than 5nm titanium composite oxide be used as compared with the battery of comparative example 2 of negative electrode active material as the battery of the embodiment 7～16 of negative electrode active material and the titanium composite oxide that the content of above-mentioned element (P) is exceeded to 3 % by weight crystallite diameter, demonstrates high capacity of negative plates and high power capacity sustainment rate (good high-rate performance).In addition, the battery of known embodiment 7～16 with not containing compared with the battery of the embodiment 1～6 of above-mentioned element (P, B), demonstrate higher capacity dimension holdup (good high-rate performance).
Above, embodiments of the present invention are illustrated, but the invention is not restricted to these, in the category of the main idea of the invention that can record at claims, carry out various changes.In addition, the present invention implementation phase can in the scope that does not exceed its main idea, carry out various distortion.And then, can also be by forming various inventions by appropriately combined disclosed multiple inscapes in above-mentioned execution mode.
Claims (5)
1. a nonaqueous electrolyte battery, it possesses:
Housing material;
Be accommodated in the positive pole in described housing material, the anodal layer that described positive pole possesses collector body and is formed at the one or both sides on described collector body and comprises active material, conductive agent and binding agent;
Spatially be accommodated in separatedly the negative pole in described housing material with described positive pole, the negative electrode layer that described negative pole possesses collector body and is formed at the one or both sides on described collector body and comprises the active material, conductive agent and the binding agent that contain titanium oxide or titanium composite oxide; And
Be contained in the nonaqueous electrolyte in described housing material,
Wherein, described titanium oxide or titanium composite oxide comprise monoclinic system beta titanium composite oxides as principal phase, the integrated intensity of the main peak of the described monoclinic system beta titanium composite oxides that record by the wide-angle x-ray diffraction using CuK alpha ray as x-ray source is set as at 100 o'clock, belong to and be selected from Detitanium-ore-type TiO
2and H
2ti
8o
17in the relative value of integrated intensity of the main peak that appears at 2 θ=25.1～25.5 ° of at least one parafacies be below 30, and the crystallite diameter that described titanium oxide or titanium composite oxide are calculated by the main peak of the described monoclinic system beta titanium composite oxides that obtain by described wide-angle x-ray diffraction is more than 5nm.
2. nonaqueous electrolyte battery according to claim 1, wherein, the described active material containing in described anodal layer is to embed manganese dioxide, iron oxide, cupric oxide, nickel oxide and the complex Li-Mn-oxide, lithium nickel composite oxide, lithium cobalt composite oxide, lithium/nickel/cobalt composite oxide, lithium manganese cobalt composite oxide, spinel type lithium mn-ni compound oxide, the Lithium Phosphor Oxide with olivine structural, ferric sulfate or the vanadium oxide that there are lithium.
3. nonaqueous electrolyte battery according to claim 1 and 2, wherein, described housing material is formed by laminated film.
4. a power brick, it possesses in multiple claims 1～3 nonaqueous electrolyte battery described in any one, and each battery is electrically connected in the mode of serial or parallel connection or in the mode of series and parallel connections.
5. power brick according to claim 4, it further possesses the protective circuit of the voltage that can detect each nonaqueous electrolyte battery.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1838471A (en) * | 2005-03-24 | 2006-09-27 | 株式会社东芝 | Battery pack and vehicle |
| CN101179140A (en) * | 2006-11-10 | 2008-05-14 | 株式会社东芝 | Nonaqueous electrolyte battery, lithium titanium composite oxide and battery pack |
| JP2008117625A (en) * | 2006-11-02 | 2008-05-22 | National Institute Of Advanced Industrial & Technology | Lithium secondary battery active material, its manufacturing method, and lithium secondary battery using it |
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2009
- 2009-05-28 CN CN201410064755.8A patent/CN103825012A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1838471A (en) * | 2005-03-24 | 2006-09-27 | 株式会社东芝 | Battery pack and vehicle |
| JP2008117625A (en) * | 2006-11-02 | 2008-05-22 | National Institute Of Advanced Industrial & Technology | Lithium secondary battery active material, its manufacturing method, and lithium secondary battery using it |
| CN101179140A (en) * | 2006-11-10 | 2008-05-14 | 株式会社东芝 | Nonaqueous electrolyte battery, lithium titanium composite oxide and battery pack |
| US20080113264A1 (en) * | 2006-11-10 | 2008-05-15 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte battery, lithium titanium composite oxide and battery pack |
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