CN100539289C - Battery - Google Patents

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CN100539289C
CN100539289C CNB2007101072844A CN200710107284A CN100539289C CN 100539289 C CN100539289 C CN 100539289C CN B2007101072844 A CNB2007101072844 A CN B2007101072844A CN 200710107284 A CN200710107284 A CN 200710107284A CN 100539289 C CN100539289 C CN 100539289C
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active material
material layer
anode active
surface anode
thickness
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CN101079500A (en
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西山祥一
井上弘
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Murata Northeast China
Murata Manufacturing Co Ltd
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Sony Corp
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

A kind of battery that comprises spiral winding electrode, anodal and negative pole carries out stacked in the mode that has spacer between the two and by screw winding in spiral winding electrode.This spiral winding electrode is connected with at least one lead-in wire on the screw winding central side.Just have: positive electrode collector has a pair of apparent surface; The outer surface anode active material layer is arranged on the screw winding outer surface side of positive electrode collector; And the inner surface anode active material layer, be arranged on the screw winding inner surface side of positive electrode collector.The thickness of inner surface anode active material layer is less than the thickness of outer surface anode active material layer.The outer surface regions of active material that only is provided with the outer surface anode active material layer forms on the screw winding central side of positive pole and overlaps with lead-in wire.

Description

Battery
Cross-reference to related applications
The present invention includes and be involved in the Japanese patent application JP 2006-142723 that was committed to Japan Patent office on May 23rd, 2006 and be committed to the theme of the Japanese patent application JP 2007-064996 of Japan Patent office on March 14th, 2007, its full content is incorporated into this for your guidance.
Technical field
The present invention relates to a kind of battery that comprises spiral winding electrode, wherein anodal and negative pole carries out stacked in the mode that has spacer between the two and by screw winding.
Background technology
In recent years, many portable electron devices have appearred, such as combination camera (video tape recorder), mobile phone and notebook-sized personal computer.For the power supply that is used for these portable electron devices, battery, especially secondary cell (secondary, storage battery) that the development of strong request has the small-sized and lightweight of high-energy-density.As the secondary cell that satisfies this requirement, for example, adopt the lithium secondary battery practical application of lithium as the electrode reaction thing.Yet,, require its capacity higher along with mobile device has in these years become complicated.
Method as realizing high power capacity for example, can improve the amount that is filled in the active material in the battery.For example, in lithium secondary battery, has such structure, promptly wherein, two surfaces of collector body are provided with the positive pole of active material layer and negative pole and carry out stacked in the mode that has spacer between the two and reeled spirally, when the thickness of active material layer increases, collector body and the spacer ratio in battery reduces, and the loading of active material increases, thereby capacity can increase.Yet, when active material
Figure C200710107284D0006105543QIETU
When the thickness of layer increases, a shortcoming is arranged, promptly when lamination during by screw winding at active material
Figure C200710107284D0006105543QIETU
Be easy to generate crack and fracture in the layer.Therefore, for example, for example proposed by the thickness setting of active material layer on the screw winding inner surface side is relaxed stress (for example, with reference to the public announcement of a patent application of Japanese unexamined 8-130035 number) for the thickness less than the active material layer on screw winding outer surface side.
Summary of the invention
Yet,, yet have following shortcoming even during the thickness of the active material layer on reducing the screw winding inner surface side.That is, on the screw winding central side that has minor diameter under the situation of cylinder type secondary battery and under the situation at square battery on bend, be difficult to counter stress and relax fully, and produce crack and fracture.Especially, such shortcoming produces in positive pole easily, and when the high-capacity material such as tin and silicon is used for negative pole, because the increase of the thickness of anode active material layer, so such shortcoming significantly takes place.
Consider above-mentioned situation, in the present invention, expectation provides a kind of battery, even when anodal thickness increases, also do not produce crack and fracture.
According to embodiments of the invention, first battery that comprises spiral winding electrode is provided, in this spiral winding electrode, anodal and negative pole carries out stacked in the mode that has spacer between the two and is reeled spirally, wherein, spiral winding electrode is connected with at least one lead-in wire on the screw winding central side, just have: positive electrode collector has a pair of apparent surface; The outer surface anode active material layer is arranged on the screw winding outer surface side of positive electrode collector; And the anodal active material of inner surface
Figure C200710107284D0006105543QIETU
Layer, be arranged on the screw winding inner surface side of positive electrode collector, the thickness of inner surface anode active material layer is less than the thickness of outer surface anode active material layer, and the outer surface regions of active material that only is provided with the outer surface anode active material layer forms on the screw winding central side of positive pole and overlaps with lead-in wire.
According to one embodiment of present invention, second battery that comprises spiral winding electrode is provided, in this spiral winding electrode, anodal and negative pole is stacked and reeled spirally in the mode that has spacer between the two, wherein, spiral winding electrode has flat shape, and it comprises a pair of relative bend and is arranged on par between this a pair of relative bend, just have: positive electrode collector has a pair of apparent surface; The outer surface anode active material layer is arranged on the screw winding outer surface side of positive electrode collector; And the anodal active material of inner surface
Figure C200710107284D0006105543QIETU
Layer, be arranged on the screw winding inner surface side of positive electrode collector, the thickness of inner surface anode active material layer is less than the thickness of outer surface anode active material layer, and on the screw winding central side of positive pole, the outer surface regions of active material that only is provided with the outer surface anode active material layer is formed in the bend.
According to first battery of the embodiment of the invention, only be provided with the anodal active material of outer surface
Figure C200710107284D0006105543QIETU
The active material of the outer surface of layer
Figure C200710107284D0006105543QIETU
The zone is arranged on the anodal screw winding central side and overlaps with lead-in wire.In addition, according to second battery of the embodiment of the invention, on the screw winding central side of positive pole, the active material of outer surface
Figure C200710107284D0006105543QIETU
The zone is arranged in the bend.Therefore, the end difference or the bending in the bend that produce owing to lead-in wire are relaxed by the outer surface anode active material layer, and can reduce the anodal active material of inner surface
Figure C200710107284D0006105543QIETU
The influence of layer.Like this, even when anodal thickness increases, also can prevent from the screw winding central lateral plane, to produce crack or fracture.Thereby, can improve capacity.
Of the present invention other will become more apparent by following description with further purpose, feature and advantage.
Description of drawings
Fig. 1 is the sectional view that illustrates according to the structure of the secondary cell of first embodiment of the invention;
Fig. 2 is the sectional view that illustrates along the structure of the line II-II of spiral winding electrode shown in Figure 1 intercepting;
Fig. 3 is the sectional view that the amplifier section of spiral winding electrode shown in Figure 2 is shown;
Fig. 4 is the sectional view that illustrates according to the structure of the secondary cell of second embodiment of the invention;
Fig. 5 is the sectional view that illustrates along the structure of the line V-V of spiral winding electrode shown in Figure 4 intercepting;
Fig. 6 is the sectional view that the amplifier section of spiral winding electrode shown in Figure 5 is shown;
Fig. 7 is the sectional view that the screw winding structure of comparative example 3 is shown; And
Fig. 8 is the performance plot that the relation between porosity (porosity) and the high capacity discharge capacity is shown.
Embodiment
Embodiments of the present invention is described in detail below with reference to accompanying drawings.
First embodiment
Fig. 1 shows the structure according to the secondary cell of first embodiment of the invention.This secondary cell is so-called cylindrical battery, and has spiral winding electrode 20 in battery case 11 inside of approximate hollow cylindrical.Battery case 11 is to be made by the iron that for example is coated with nickel (Ni) (Fe).One end of battery case 11 seals, and the other end is an opening.In battery case 11 inside, a pair of insulation board 12 and 13 is arranged perpendicular to the coiling peripheral surface respectively, makes screw winding cell body 20 be clipped between insulation board 12 and 13.
In the open end of battery case 11, battery cover 14 and the relief valve mechanism 15 that is arranged in the battery cover 14 are connected by embedding packing ring 17 with PTC (positive temperature coefficient) device 16.The inside of battery case 11 seals with being sealed.Battery cover 14 by for example with battery case 11 materials Similar material Make.Relief valve mechanism 15 is electrically connected to battery cover 14 by PTC device 16.When the internal pressure of battery reaches certain level owing to internal short-circuit, external heat etc. or when higher, plectane 15A upsprings (flip) to cut off being electrically connected between battery cover 14 and the spiral winding electrode 20.When temperature raise, PTC device 16 limited electric current by increasing resistance value, with the abnormal heat that prevents to produce owing to big electric current.Packing ring 17 is made by for example insulating material, and its surface-coated has pitch.
Fig. 2 shows along the cross section structure of the line II-II intercepting of spiral winding electrode shown in Figure 1 20.In spiral winding electrode 20, banded (strip-shapped) anodal 21 and banded negative pole 22 carries out stacked in the mode that has spacer 23 between the two and with cylinder mode screw winding.Centrepin 24 is inserted in the center of spiral winding electrode 20.In Fig. 2, omitted spacer 23.The lead-in wire of being made by aluminium (Al) etc. 25 is electrically connected to anodal 21.The lead-in wire of being made by nickel etc. 26 is electrically connected to negative pole 22.Lead-in wire 25 is electrically connected to battery cover 14 by being connected to relief valve mechanism 15.Lead-in wire 26 is attached to and is electrically connected to battery case 11.
As an example, anodal 21 have: positive electrode collector 21A, and it has a pair of apparent surface; Outer surface anode active material layer 21B is arranged on the screw winding outer surface side of positive electrode collector 21A; And inner surface anode active material layer 21C, be arranged on the screw winding inner surface side of positive electrode collector 21A.In anodal 21, be formed with two surface activity materials Zone 21D, this zone is provided with outer surface anode active material layer 21B and the anodal active material of inner surface Layer 21C.The thickness of inner surface anode active material layer 21C is less than the anodal active material of outer surface The thickness of layer 21B.Its reason is that the easier stress that is applied in of inner surface anode active material layer 21C has crack (crack) and fracture (break) easily.The thickness of its outer surface anode active material layer 21B is expressed as T21B, the thickness of inner surface anode active material layer 21C is expressed as T21C, the gross thickness T21 of outer surface anode active material layer 21B and inner surface anode active material layer 21C is expressed as T21B+T21C, the thickness T 21B of outer surface anode active material layer 21B is preferably for example in the scope of 0.5 * T21＜T21B＜0.6 * T21, and the thickness T 21C of inner surface anode active material layer 21C is preferably for example in the scope of 0.4 * T21＜T21C＜0.5 * T21.In such scope, can improve capacity, can prevent crack and fracture simultaneously.
The porosity of outer surface anode active material layer 21B and inner surface anode active material layer 21C is preferably in 20% to 27% scope.In this scope, suppressed crack and fracture, and improved capacity.In addition, can under the situation of output high load currents, keep high power capacity.
Porosity (%) is the value that deducts filling rate (%) from 100.Filling rate is material (the anodal active material that forms outer surface anode active material layer 21B and inner surface anode active material layer 21C Deng) percentage by volume in their volume.For example, filling rate can be by outer surface anode active material layer 21B and the volume of inner surface anode active material layer 21C and these materials of per unit weight of per unit weight Volume (cumulative volumes of positive electrode active materials etc.) obtain.The anodal active material of outer surface The anodal active material of layer 21B and inner surface
Figure C200710107284D0010113037QIETU
The volume of layer 21C is represented by (Unit Weight) reciprocal.The volume of these materials calculates by the real density of this ratio and every kind of material.For example, at each material is under the situation of positive electrode active materials, electric conductor and bonding agent, when the ratio of positive electrode active materials, electric conductor and bonding agent and when being 1, volume is expressed as (real density of the ratio/positive electrode active materials of positive electrode active materials)+(real density of the ratio/electric conductor of electric conductor)+(real density of the ratio/bonding agent of bonding agent).
On anodal 21 screw winding central side, for example, be formed with two surperficial exposed region 21E, the anodal active material of outer surface is not set in this zone
Figure C200710107284D0011113046QIETU
Two surfaces of layer 21B and inner surface anode active material layer 21C and positive electrode collector 21A all expose, and go between and 25 be connected in this zone.In addition, on anodal 21 screw winding central side, the outer surface regions of active material 21F that only is provided with outer surface anode active material layer 21B is formed between two surperficial exposed region 21E and the two surface active materials zone 21D.The active material of outer surface
Figure C200710107284D0011113053QIETU
Zone 21F is formed on the active material of outer surface at least
Figure C200710107284D0011113053QIETU
In zone 21F and lead-in wire 25 positions of overlapping mutually.Thereby because of 25 end differences that produce (step) that go between are relaxed (relax) by outer surface anode active material layer 21B, thereby reduction is to the influence of inner surface anode active material layer 21C.
That is to say that as shown in Figure 3, two surface active materials zone 21D causes producing end difference 21G in this pair surface active material zone 21D and the lead-in wire 25 position bendings of overlapping mutually.Simultaneously, when outer surface regions of active material 21F is set, along with the increase of the thickness of the outer surface anode active material layer 21B of outer surface regions of active material 21F, from the screw winding center of spiral winding electrode 20 to two surface activity materials
Figure C200710107284D0011113053QIETU
The diameter of zone 21D increases.Thereby the angle of bend θ of end difference 21G increases, thereby stress is relaxed.
If necessary, wherein the two surperficial exposed region 21H that all exposes of two of positive electrode collector 21A surfaces also can be formed on anodal 21 the screw winding outer circumferential sides.Although do not illustrate, can form and only be provided with the anodal active material of inner surface
Figure C200710107284D0011113053QIETU
The inner surface regions of active material of layer 21C.
Positive electrode collector 21A is for example by making such as the metal forming of aluminium foil, Nie Be and Bu Xiu Gang Be.The anodal active material of outer surface anode active material layer 21B and inner surface
Figure C200710107284D0011113053QIETU
Layer 21C for example comprises (as the active material of positive pole
Figure C200710107284D0011113053QIETU
) can embed and deviate from one or more anodal materials as the lithium of electrode reaction thing
Figure C200710107284D0011113053QIETU
If necessary, the anodal active material of outer surface
Figure C200710107284D0011113053QIETU
Layer 21B and inner surface anode active material layer 21C can also comprise electric conductor, bonding agent etc.As the positive electrode that can embed and deviate from lithium, for example, can enumerate do not contain lithium metal chalcogenide (such as titanium sulfide (TiS 2), molybdenum sulfide (MoS 2), selenizing niobium (NbSe 2) and vanadium oxide (V 2O 5)) or comprise the lithium-containing compound of lithium.
Especially, preferably use some lithium-containing compounds, because can obtain high voltage and high-energy-density thus.As this lithium-containing compound, for example, can enumerate the composite oxides that comprise lithium and transition metal or comprise lithium and the phosphate compounds of transition metal.Particularly, preferably comprise at least a compound in cobalt (Co), nickel, manganese (Mn) and the iron, because can obtain higher capacity thus.Their chemical molecular formula is expressed as for example Li xMIO 2Or Li yMIIPO 4In molecular formula, MI and MII represent one or more transition metals.The value of x and y changes according to the charging and the discharge condition of battery, and usually in the scope of 0.05 ≦ x ≦ 1.10 and 0.05 ≦ y ≦ 1.10.
As the instantiation of the composite oxides that comprise lithium and transition metal, can enumerate lithium-cobalt composite oxide (Li xCoO 2), lithium-ni compound oxide (Li xNiO 2), lithium-nickel-cobalt composite oxide (Li xNi 1-zCo zO 2(z＜1)), lithium-manganese composite oxide (LiMn with acicular texture 2O 4) etc.As comprising the instantiation that lithium and transition belong to the phosphate compounds of element entirely, for example, can enumerate lithium-iron phosphate compounds (LiFePO 4) or lithium-iron-manganese phosphate compound (LiFe 1-vMn vPO 4(v＜1)).
Negative pole 22 for example has: negative electrode collector 22A has a pair of apparent surface; Outer surface anode active material layer 22B is arranged on the screw winding outer surface side of negative electrode collector 22A; And inner surface anode active material layer 22C, be arranged on the screw winding inner surface side of negative electrode collector 22A.With as identical mode in anodal 21, in negative pole 22, form and be provided with outer surface anode active material layer 22B and inner surface negative electrode active material
Figure C200710107284D0011113053QIETU
Two surface active materials zone 22D of layer 22C.Arrange, thereby make outer surface anode active material layer 22B at least in part, and inner surface anode active material layer 22C is towards outer surface anode active material layer 21B towards inner surface anode active material layer 21C.The thickness of outer surface anode active material layer 22B can be identical with the thickness of inner surface anode active material layer 22C, but preferably less than the inner surface negative electrode active material
Figure C200710107284D0011113053QIETU
The thickness of layer 22C.Because outer surface anode active material layer 22B is towards inner surface anode active material layer 21C, so the capacity of the per unit area of outer surface anode active material layer 22B can be less than the capacity of the per unit area of inner surface anode active material layer 22C.Therefore, the thickness of outer surface anode active material layer 22B can exactly reduce so much.As a result, the nonuseable part of volume can be eliminated, and capacity can be improved more.
If necessary, on the screw winding central side of negative pole 22, can be formed with two surperficial exposed region 22E, two surfaces that outer surface anode active material layer 22B and inner surface anode active material layer 22C and negative electrode collector 22A are not set in this zone all expose.In addition, on the screw winding central side of negative pole 22, the sided area 22F that only is provided with outer surface anode active material layer 22B or inner surface anode active material layer 22C is formed between two surperficial exposed region 22E and the two surface active materials zone 22D.
For example, wherein the two surperficial exposed region 22G that all exposes of two of negative electrode collector 22A surfaces is formed on the screw winding outer circumferential sides of negative pole 22, and lead-in wire 26 is connected on this zone.Although do not illustrate, the inner surface regions of active material that only is provided with inner surface anode active material layer 22C can be formed on the screw winding outer circumferential sides of negative pole 22.
Negative electrode collector 22A is for example by making such as the metal forming of copper (Cu) paper tinsel, nickel foil and stainless steel foil.Outer surface anode active material layer 22B and inner surface anode active material layer 22C comprise: as positive electrode active materials, for example, at least a or multiple negative material can be embedded and deviate from, and electric conductor, bonding agent etc. can be comprised if necessary as the lithium of electrode reaction thing.As the negative material that can embed and deviate from lithium, for example, can enumerate material with carbon element (but such as native graphite, Delanium, can not graphitized carbon and graphitized carbon) or comprise and to form at least a metallic element of alloy and metalloid element material with lithium as element.
Especially, the preferred use comprises metallic element or the metalloid element negative material as element, because can improve capacity thus.As this negative material, can enumerate simple substance, alloy or the compound of metallic element or metalloid element or the material that has one or more their phases at least in part
Figure C200710107284D0011113053QIETU
In the present invention, except the alloy that comprises two or more metallic elements, alloy also comprises the alloy that comprises one or more metallic elements and one or more metalloid elements.In addition, alloy can comprise nonmetalloid.Its tissue (texture) can be the tissue of two or more coexistences in solid solution, eutectic (eutectic mixture), intermetallic compound or the wherein aforementioned tissue.
As this metallic element or this metalloid element that constitute negative material, can enumerate magnesium (Mg), boron (B), aluminium, gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn), plumbous (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd), platinum (Pt) etc.Especially, preferred silicon or tin.
Especially, as this negative material, preferably comprise tin, cobalt and carbon (C) and contain the CoSnC material as element
Figure C200710107284D0014113244QIETU
, or comprise tin, iron and carbon and contain the FeSnC material as element
Figure C200710107284D0014113244QIETU
Therefore, can obtain high-energy-density, and obtain excellent cycle characteristics.The carbon content that contains in the CoSnC material is preferably 16.8wt% to 24.8wt%, and the ratio of cobalt and tin and cobalt total amount is preferably 30wt% to 45wt%.The carbon content that contains in the FeSnC material is preferably 11.9wt% to 29.7wt%, and the ratio that iron accounts for tin and iron total amount is preferably 26.4wt% to 48.5wt%.In this scope, can obtain higher characteristic.
If necessary, contain the CoSnC material
Figure C200710107284D0014113244QIETU
With contain the FeSnC material and can further comprise other element.As being used to contain the CoSnC material
Figure C200710107284D0014113244QIETU
Other element, for example, preferred silicon, iron, nickel, chromium (Cr), indium, niobium (Nb), germanium, titanium (Ti), molybdenum (Mo), aluminium, phosphorus (P), gallium or bismuth, and can comprise they two or more.As other element that is used to contain the FeSnC material, for example, be preferably selected from least a in the group of forming by aluminium, titanium, vanadium (V), chromium, niobium and tantalum (Ta) and be selected from least a in the group of forming by cobalt, nickel, copper, zinc, gallium and indium.In addition, also preferred silver.
Contain the CoSnC material
Figure C200710107284D0014113244QIETU
Preferably has the tin of comprising, cobalt and carbon mutually.This phase preferably has the structure or the impalpable structure of low-crystallinity.Similarly, contain the FeSnC material and preferably have the tin of comprising, iron and carbon mutually.This phase preferably has the structure or the impalpable structure of low-crystallinity.In addition, preferably, containing the CoSnC material
Figure C200710107284D0014113244QIETU
With contain in the FeSnC material, connected (bond) to metallic element or metalloid element as at least a portion of the carbon of element by key as other element.Its reason is as follows.Cohesion of tin etc. (cohesion) or crystallization can cause cycle characteristics lower.Can prevent this cohesion or crystallization by carbon bond being connected to other element.
Spacer 23 separates positive pole 21 and negative pole 22, prevents the short circuit current that the contact owing to two electrodes produces, and lithium ion is passed through.Spacer 23 is made by for example perforated membrane, and this perforated membrane is by making such as polytetrafluoroethylene, polypropylene and poly synthetic resin or by ceramic porous membrane.Spacer 23 can have the structure that wherein is laminated with two or more aforementioned perforated membranes.
For example, electrolytic solution is submerged in the spacer 23.This electrolytic solution comprises for example solvent and electrolytic salt.As solvent, can enumerate nonaqueous solvents, such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1, the 2-dimethoxy-ethane, 1, the 2--diethoxyethane, gamma-butyrolacton, gamma-valerolactone, oxolane, the 2-methyltetrahydrofuran, 1, the 3-dioxolanes, the 4-methyl isophthalic acid, the 3-dioxolanes, 1,3-dioxole-2-ketone, 4-vinyl-1,3-dioxy ring penta-2-ketone, 4-fluoro-1,3-dioxy ring penta-2-ketone, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, propionitrile, anisole, acetic acid esters (esteracetate), butyrate (ester butyrate), propionic ester (ester propionate), fluorobenzene, and cured ethylene.As electrolytic salt, for example, can enumerate such as LiPF 6, LiBF 4, LiClO 4, LiAsF 6, LiN (CF 3SO 2) 2, LiN (C 2F 5SO 2) 2, LiC (CF 3SO 2) 3, LiB (C 6H 5) 4, LiB (C 2O 4) 2, LiCF 3SO 3, LiCH 3SO 3, LiCl and LiBr lithium salts.As solvent and electrolytic salt, can use a kind of in above-mentioned separately, perhaps wherein two or more can be used by mixing.
For example, can make this secondary cell as follows.
At first, with the anodal active material of outer surface
Figure C200710107284D0014113244QIETU
Layer 21B and inner surface anode active material layer 21C are formed on the positive electrode collector 21A, to form anodal 21.For example be formed as follows the anodal active material of outer surface anode active material layer 21B and inner surface
Figure C200710107284D0014113244QIETU
Layer 21C.With the active material of positive pole
Figure C200710107284D0014113244QIETU
, electric conductor and bonding agent mix.This mixture is dispersed in a kind of decentralized medium.With producing thing positive electrode collector 21A is applied, be dried then and compression molded, to form anodal 21.With with anodal 21 identical modes, by on negative electrode collector 22A, forming the outer surface negative electrode active material
Figure C200710107284D0014113244QIETU
Layer 22B and inner surface negative electrode active material
Figure C200710107284D0014113244QIETU
Layer 22C and form negative pole 22.Then, outer surface anode active material layer 21B as indicated above, inner surface anode active material layer 21C, outer surface anode active material layer 21B and inner surface anode active material layer 21C thickness and position relation adjust.Then, wait go between by welding 25 to be connected to positive electrode collector 21A, and 26 be connected to negative electrode collector 22A by welding etc. to go between.
Next, with anodal 21 and negative pole 22 reel spirally in the mode of between the two spacer 23.Centrepin 24 is inserted in the center of spiral winding electrode.Then, according to this embodiment, the anodal active material of inner surface
Figure C200710107284D0014113244QIETU
The thickness of layer 21C is less than the thickness of outer surface anode active material layer 21B.In addition, will only be provided with the anodal active material of outer surface
Figure C200710107284D0014113244QIETU
The active material of the outer surface of layer 21B
Figure C200710107284D0014113244QIETU
Zone 21F is arranged to and goes between 25 overlap, to relax the end difference of lead-in wire 25.Therefore, crack and fracture have been prevented from inner surface anode active material layer 21C, to produce.Afterwards, lead-in wire 25 end is welded in relief valve device 15, the end of lead-in wire 26 is welded in battery case 11.The positive pole 21 of screw winding and the negative pole 22 of screw winding are clipped between a pair of insulation board 12 and 13, and are contained in the battery case 11.Then, electrolytic solution is injected in the battery case 11, and is impregnated in the spacer 23.Afterwards, by battery cover 14, relief valve mechanism 15 and PTC device 16 being fixed on the open end of battery case 11 with packing ring 17 caulkeds.Thereby finished the secondary cell shown in Fig. 1 and 2.
As mentioned above, according to this embodiment, the thickness of inner surface anode active material layer 21C is less than the thickness of outer surface anode active material layer 21B.In addition, on the screw winding central side, 25 overlappings that the outer surface regions of active material 21F that only is provided with outer surface anode active material layer 21B is arranged to and goes between are to relax because of 25 end differences that produced that go between.Therefore, even when the thickness of positive pole 21 increases, also can prevent to produce crack and fracture.Thereby, can improve capacity.
Second embodiment
Fig. 4 shows the structure according to the secondary cell of second embodiment of the invention.This secondary cell is so-called lamination membranous type secondary cell.In this secondary cell, spiral winding electrode 30 is contained in the film packaging part (film package member) 40, and lead-in wire 31 and 32 is connected to this spiral winding electrode.
Lead-in wire 31 and 32 is guided to the outside from the inside of packaging part 40, and for example, derives along equidirectional.For example, lead-in wire 31 and 32 is respectively for example by such as aluminium, copper, nickel and stainless metal material
Figure C200710107284D0014113244QIETU
Make, and be the shape of thin plate or net.
Packaging part 40 is made by the aluminium lamination press mold of rectangle, and wherein, for example, nylon membrane, aluminium foil and polyethylene film are bonded together in proper order with this.Packaging part 40 is arranged to, and for example, makes polyethylene film side and spiral winding electrode 30 face mutually, and corresponding outer rim is in contact with one another by fusion welding or adhesive.In order to prevent that extraneous air from entering, adhesive film 41 is inserted between packaging part 40 and the lead-in wire 31 and 32.Adhesive film 41 is by making 31 and 32 materials with contact performance that go between, for example, and by making such as the vistanex of polyethylene, polypropylene, modified poly ethylene and modified polypropene.
Packaging part 40 can be by the laminated film with other structure, make such as polyacrylic polymeric membrane or metal film, rather than is made by aforesaid aluminium lamination press mold.
Fig. 5 shows along the cross section structure of the line V-V intercepting of spiral winding electrode shown in Figure 4 30.In spiral winding electrode 30, anodal 33 and negative pole 34 stacked and in the mode that has spacer 35 and dielectric substrate 36 between the two by screw winding.Its outermost layer week cause boundary belt 37 protections.In addition, spiral winding electrode 30 has flat pattern, comprises a pair of relative bend 30A and the par 30B between this a pair of relative bend 30A.
Anodal 33 have such structure, and promptly its outer surface anode active material layer 33B is arranged on the screw winding outer surface side of positive electrode collector 33A, and inner surface anode active material layer 33C is arranged on the screw winding inner surface side of positive electrode collector 33A.The structure of positive electrode collector 33A, outer surface anode active material layer 33B and inner surface anode active material layer 33C and the positive electrode collector 21A in first embodiment, the anodal active material of outer surface
Figure C200710107284D0014113244QIETU
The anodal active material of layer 21B and inner surface
Figure C200710107284D0014113244QIETU
21C is similar for layer.
That is to say that in anodal 33, be formed with two surface active materials zone 33D, this zone is provided with outer surface anode active material layer 33B and the anodal active material of inner surface
Figure C200710107284D0014113244QIETU
Layer 33C.The thickness of inner surface anode active material layer 33C is less than the thickness of outer surface anode active material layer 33B.The anodal active material of outer surface
Figure C200710107284D0014113244QIETU
The thickness of layer 33B and the thickness of inner surface anode active material layer 33C are similar to the thickness of the outer surface anode active material layer 21B among first embodiment and the thickness of inner surface anode active material layer 21C.In addition, the anodal active material of outer surface
Figure C200710107284D0014113244QIETU
The anodal active material of layer 33B and inner surface
Figure C200710107284D0014113244QIETU
The porosity of layer 33C is similar to outer surface anode active material layer 21B and the anodal active material of inner surface
Figure C200710107284D0014113244QIETU
The porosity of layer 21C.
On anodal 33 screw winding central side, be formed with two-sided exposed region 33E, two surfaces that outer surface anode active material layer 33B and inner surface anode active material layer 33C and positive electrode collector 33A are not set in this zone all expose, and go between and 31 be connected in this zone.In addition, on anodal 33 screw winding central side, the outer surface regions of active material 33F that only is provided with outer surface anode active material layer 33B is formed between two surperficial exposed region 33E and the two surface active materials zone 33D.
Outer surface regions of active material 33F is formed among the bend 30A at least.Therefore, the bending among the bend 30A is relaxed by outer surface anode active material layer 33B, and has reduced the influence to inner surface anode active material layer 33C.
In other words, as shown in Figure 6, two surface active materials zone 33D is crooked at bend 30A place.At this moment, when outer surface regions of active material 33F was set, along with the increase of the thickness of the outer surface anode active material layer 33B of outer surface regions of active material 33F, the diameter from the screw winding center of bend 30A to two surface active materials zone 33D increased.Thereby the angle of bend θ of bend 30A increases, thereby stress is relaxed.
Negative pole 34 has such structure, and promptly its outer surface anode active material layer 34B is arranged on the screw winding outer surface side of negative electrode collector 34A, and inner surface anode active material layer 34C is arranged on the screw winding inner surface side of negative electrode collector 34A.With with anodal 33 in identical mode, in negative pole 34, be formed with two surface active materials zone 34D, this zone is provided with outer surface anode active material layer 34B and inner surface anode active material layer 34C.Negative electrode collector 34A, outer surface anode active material layer 34B and inner surface anode active material layer 34C are in the mode identical with negative electrode collector 22A, outer surface anode active material layer 22B in first embodiment and inner surface anode active material layer 22C and be configured.
If necessary, wherein the two surperficial exposed region 34E that all exposes of two of negative electrode collector 34A surfaces can be formed on the screw winding outer circumferential sides of negative pole 34.The inner surface negative active core-shell material zone 34F that only is provided with inner surface anode active material layer 34C is arranged on the screw winding outer circumferential sides of negative pole 34.
On the screw winding central side of negative pole 34, for example, be formed with two-sided exposed region 34G, two surfaces that outer surface anode active material layer 34B and inner surface anode active material layer 34C and negative electrode collector 34A are not set in this zone all expose, and go between and 32 be connected in this zone.In addition, on the screw winding central side of negative pole 34, though not shown, the sided area that only is provided with outer surface anode active material layer 34B or inner surface anode active material layer 34C can be formed between two-sided exposed region 34G and the two surface active materials zone 34D.
Spacer 35 is in the mode identical with spacer 23 among first embodiment and be configured.
Dielectric substrate 36 is so-called gelatinous, comprise electrolytic solution and polymer compound with become hold electrolytic solution hold body (holding body).Preferred gel electrolyte because can obtain high ionic conductivity thus, thereby and can prevent the leakage of battery.The similar of electrolytic solution is in the electrolytic solution of first embodiment.As polymer compound, for example, can enumerate such as poly(ethylene oxide) and comprise the ether polymer compound of the crosslinked body of poly(ethylene oxide), such as the ester polymer compound of polymethacrylates or acrylate polymer compound or such as the polymer of the vinylidene fluoride of polyvinylidene fluoride and the copolymer of vinylidene fluoride and hexafluoro-propylene.Can use separately wherein a kind of, perhaps by mix using wherein two or more.Especially, consider oxidation-reduction stability, the polymer compound of fluoridizing is used in expectation, such as the polymer of vinylidene fluoride.
For example, can make this secondary cell as follows.
At first, with the identical mode of aforementioned first embodiment, form anodal 33 and negative pole 34 form, and it is applied respectively with the precursor solution that comprises electrolytic solution, polymer compound and mixed solvent.This mixed solvent is evaporated to form dielectric substrate 36.Then, will go between 31 is connected to positive electrode collector 33A, and will go between and 32 be connected to negative electrode collector 34A.Then, the positive pole 33 and the negative pole 34 that will be formed with dielectric substrate 36 are stacked by spacer 35 between the two, to obtain lamination.Afterwards,, boundary belt 37 is bonded to its outermost layer periphery, to form spiral winding electrode 30 with this lamination screw winding longitudinally.Afterwards, for example, spiral winding electrode 30 is clipped between the packaging part 40, and the outward flange of packaging part 40 is contacted by methods such as sweat solderings, with sealing spiral winding electrode 30.At this moment, adhesive film 41 is inserted into the lead-in wire 31 and 32 and packaging part 40 between.Thereby finished the secondary cell shown in the Figure 4 and 5.
In addition, can make this secondary cell as follows.At first, with aforementioned first embodiment in identical mode form anodal 33 and negative pole 34, and will go between and 31 and 32 be connected to positive pole 33 and negative pole 34 respectively.Afterwards, with anodal 33 and the spacer 35 of negative pole 34 by between the two carry out stacked and carry out screw winding.Boundary belt 37 is bonded to its outermost layer periphery, forms the precursor of spiral winding electrode 30.Then, this precursor is clipped between the packaging part 40, those outermost layer periphery sweat solderings that will be except a side to be obtaining a bag shape (pouched state), and this precursor is contained in packaging part 40.Then, the preparation electrolyte composition, it comprises electrolytic solution, as being used for other material of raw-material monomer, (if necessary) such as polymerization initiator and the polymerization inhibitor of polymer compound, and said composition is injected in the packaging part 40.Afterwards, with the opening sweat soldering of packaging part 40 and sealing hermetically.Afterwards, will produce the thing heating so that monomer carries out polymerization, so that obtain polymer compound.Thereby, formed gel electrolyte layer 36, and finished the secondary cell shown in Figure 4 and 5.
This secondary cell with carry out work according to the identical mode of the secondary cell of first embodiment, and provide similar effect.
Example
In addition, will be described in detail instantiation of the present invention.
As an example 1 to 5, made column secondary battery as illustrated in fig. 1 and 2.At first, will be as the cobalt acid lithium (LiCoO of positive electrode active materials 2), mix with the preparation mixture as the graphite of electric conductor and as the polyvinylidene fluoride of bonding agent.Then, this mixture is dispersed in the decentralized medium.Two surfaces that will be made by aluminium foil and that have a positive electrode collector 21A of 15 μ m thickness all evenly apply with this generation thing, are dried then.Afterwards, should produce thing carry out compression molded forming outer surface anode active material layer 21B and inner surface anode active material layer 21C, thereby form anodal 21.At this moment, the thickness of outer surface anode active material layer 21B and inner surface anode active material layer 21C is changed according to example as shown in table 11 to 5, and its porosity is set at 22%.Then, on the screw winding central side, form the outer surface regions of active material 21F that only has outer surface anode active material layer 21B.Then, lead-in wire made of aluminum 25 is connected to the screw winding central side of positive electrode collector 21A.Outer surface regions of active material 21F and lead-in wire 25 position adjustments are overlapping each other as shown in Figure 2.
In addition, will contain the CoSnC material as negative active core-shell material.Will containing CoSnC material, Delanium and carbon black, mix as electric conductor and negative active core-shell material as the polyvinylidene fluoride of bonding agent.Its mixture is dispersed in the decentralized medium.Two surfaces of the negative electrode collector 22A that will be made by Copper Foil all apply with this generation thing, are dried and compression molded to form outer surface anode active material layer 22B and inner surface anode active material layer 22C.Thereby formed negative pole 22.At this moment, change according to the thickness of 1 to the 5 outer surface anode active material layer 22B of the example shown in the table 1 and the thickness of inner surface anode active material layer 22C.Then, will be connected to the screw winding outer circumferential sides of negative electrode collector 22A by the lead-in wire 26 that nickel is made.
By with tin-cobalt alloy powder with carbon dust mixes and contain the CoSnC material by adopting mechanico-chemical reaction to synthesize.The component that contains the CoSnC material of being synthesized is analyzed.As a result, cobalt content is 29.3wt%, and tin content is 49.9wt%, and carbon content is 19.8wt%.Carbon content is measured by carbon and sulfur analytical instrument.Cobalt content and tin content are measured by ICP (inductively coupled plasma) optical emission spectroscopy method.In addition, contained the CoSnC material, carry out X-ray diffraction for what obtain.In the result, the angle of diffraction 2 θ in the scope of the angle of diffraction 2 θ=20 to 50 degree, have been obtained to have and are the diffraction maximum of 1.0 degree or bigger half-breadth bandwidth (wide half bandwidth).In addition, when when containing the CoSnC material and carry out XPS (x-ray photoelectron spectroscopy), in being lower than the scope of 284.5eV, obtained to contain the Cls peak in the CoSnC material.That is to say that the carbon bond of having confirmed to contain in the CoSnC material is connected in other element.
Then, prepare the spacer of making by the micro-porous polypropylene film 23.Then, carry out positive pole 21, spacer 23, negative pole 22 and spacer 23 stacked in proper order by this to form lamination.Afterwards, this laminated spiral is reeled for several times, and centrepin 24 is inserted into the center.Afterwards, will go between 25 is connected to relief valve mechanism 15, and will go between and 26 be connected to battery case 11.The positive pole 21 of screw winding and the negative pole 22 of screw winding are clipped between a pair of insulation board 12 and 13, and are contained in the battery case 11.Then, electrolytic solution is injected in the battery case 11.As electrolytic solution, adopted by will be as the 1mol/dm of electrolytic salt 3LiPF 6Be dissolved in the mixed solvent of diethyl carbonate of ethylene carbonate and 50% (volume) of 50% (volume) and the solution that obtains.Then, by relief valve mechanism 15, PTC device 16 and battery cover 14 being fixed on the open end of battery case 11 with packing ring 17 caulkeds.Thereby obtained the secondary cell of example 1 to 5.
Made three secondary cells respectively for example 1 to 5, and observed during the screw winding step in anodal 21 the production of crack or fracture.As a result, in all secondary cells, all do not find crack or fracture.Size because of 25 end differences that produce that go between in example 1 to 5 is about 100 μ m.
Example 1 and 2 as a comparison, make secondary cell in the mode identical with example 1 to 5, only the thickness with outer surface anode active material layer, inner surface anode active material layer, outer surface anode active material layer and inner surface anode active material layer changes as shown in table 1ly, and the thickness of outer surface anode active material layer is identical with the thickness of inner surface anode active material layer, and the thickness of outer surface anode active material layer is identical with the thickness of inner surface anode active material layer.In addition, example 3 as a comparison, make secondary cell in the mode identical with example 1 to 5, only as illustrated in fig. 7 with the end part aligning on the screw winding central side of end on the screw winding central side of outer surface anode active material layer 121B and inner surface anode active material layer 121C and do not form the outer surface regions of active material, and outer surface anode active material layer 121B, inner surface anode active material layer 121C, outer surface anode active material layer 122B, and the thickness of inner surface anode active material layer 122C and example 2 as shown in table 1 is identical.
Also make three secondary cells respectively for comparative example 1 to 4, and observed during the screw winding step production of crack in the positive pole or fracture.As a result, in comparative example 1 to 4, all do not find crack or fracture.Simultaneously, crack or fracture have all been produced in all secondary cells in comparative example 2.In comparative example 3, in two secondary cells, crack or fracture have been produced.
For the secondary cell of example 1 to 5 and comparative example 1,3 and 4 manufacturings, after the discharge capacity of measuring circulation for the first time and the 100th circulation time by the following method, obtained discharge capacitance.At first, carry out the charging of constant current and constant voltage at upper voltage limit 4.2V with under electric current 0.7C up to reaching 3 hours, and under electric current 0.2C and final voltage 2.5V, carry out constant current discharge to obtain the discharge capacity of the circulation time first time from the total charging time that begins to charge.Then, charging under identical charging and discharging condition and discharging reaches 100 circulations up to the global cycle number, to obtain the discharge capacity at the 100th circulation time.At last, calculate discharge capacitance (%), discharge capacitance=(discharge capacity of the discharge capacity of the 100th circulation time/first time circulation time) * 100.The current value when 0.7C to be battery capacity discharge in (1/0.7) hour fully, and the current value that 0.2C is a battery capacity when discharging fully in 5 hours.What obtained the results are shown in the table 1.Discharge capacity shown in the table 1, be the mean value of three secondary cells at the discharge capacity and the discharge capacitance of the 100th circulation time at the circulation time first time.Except as otherwise noted, otherwise following (example) uses identical condition.For comparative example 2, owing in positive pole, produced crack and fracture, so fail to obtain discharge capacitance.For comparative example 3, obtained wherein not produce the discharge capacitance of 1 secondary cell of crack and fracture.
Table 1:
Negative active core-shell material: contain the CoSnC material
As shown in table 1, according to example 1 to 5, even when the thickness of positive pole 21 increases, do not have crack or fracture to produce yet, and can improve discharge capacity at the circulation time first time.In addition, in example 1 to 5, discharge capacity can be improved greatly, and the discharge capacitance (85% or higher) that equates with comparative example 1,3 and 4 can be obtained at the 100th circulation time.Simultaneously, in the comparative example 1 that Zheng Ji thickness reduces, although do not have crack and fracture to produce, the discharge capacity of circulation time is lower for the first time therein.Therein the thickness of the thickness of outer surface anode active material layer and inner surface anode active material layer increase in the same manner and the outer surface regions of active material is arranged to and the comparative example 2 that overlaps that goes between in, and the thickness of inner surface anode active material layer 122C is reduced and is not provided with in the comparative example 3 of outer surface regions of active material therein, does not all have crack and fracture to produce.
That is to say, find when the thickness of inner surface anode active material layer 21C less than the thickness of outer surface anode active material layer 21B and the outer surface regions of active material 21F that only is provided with outer surface anode active material layer 21B is configured on the screw winding central side and lead-in wire 25 overlappings the time, under the situation of at least a negative active core-shell material as element in comprising tin and silicon, even the thickness when anodal 21 also can suppress the generation of crack and fracture when increasing, thereby and can improve capacity.
In addition, as certified by example 2 and example 4 are compared, in example 2, can obtain circulation time for the first time than high discharge capacity.That is to say, find to improve capacity more as outer surface anode active material layer 22B during less than the thickness of inner surface anode active material layer 22C.
As an example 6 to 10, make secondary cell in the mode identical with example 1, only the thickness of the porosity of outer surface anode active material layer 21B and inner surface anode active material layer 21C and outer surface anode active material layer 22B and inner surface anode active material layer 22C changes as shown in table 2ly.At this moment, porosity is changed in 18% to 29% scope.
For secondary cell according to example 6 to 10 manufacturings, in order to detect the capacity under high load condition (high capacity discharge capacity), at upper voltage limit 4.2V with carrying out the charging of constant current and constant voltage under the electric current 0.7C, under electric current 2C and final voltage 2.5V, carry out constant current discharge to obtain the high capacity discharge capacity of the circulation time first time up to after the total charging time that begins to charge reaches 3 hours.2C is the current value of battery capacity when discharging fully in 5 hours.The result who is obtained is shown among table 2 and Fig. 8 with the result of example 1.
Table 2:
Negative active core-shell material: contain the CoSnC material
Figure C200710107284D00291
As table 2 and shown in Figure 8, according to example 1 and 6 to 10, along with the increase of porosity, the high capacity discharge capacity increases and becomes almost constant, reduces then.In this case, be lower than 20% or greater than 27% the time, the high capacity discharge capacity significantly reduces when porosity.That is to say, when finding that porosity as outer surface anode active material layer 21B and inner surface anode active material layer 21C is in 20% to 27% scope, suppressed the generation of crack and fracture and improved capacity, in addition, under situation, kept high power capacity with high load currents output.
As an example 11, make secondary cell in the mode identical with example 1 to 5, only adopt Delanium as negative active core-shell material double as electric conducting material, and the thickness of outer surface anode active material layer 21B, inner surface anode active material layer 21C, outer surface anode active material layer 22B and inner surface anode active material layer 22C change as shown in table 3ly.For example 11, made three secondary cells, and observed during the screw winding step production of crack in anodal 21 or fracture.As a result, in all secondary cells, all do not find crack and fracture.Size because of 25 end differences that produce that go between in the example 11 is identical with example 1.
Example 5 and 6 as a comparison, make secondary cell in the mode identical with example 11, only the thickness of outer surface anode active material layer, inner surface anode active material layer, outer surface anode active material layer and inner surface anode active material layer changes as shown in table 3ly, the thickness of outer surface anode active material layer is identical with the thickness of inner surface anode active material layer, and the thickness of outer surface anode active material layer is identical with the thickness of inner surface anode active material layer.Example 7 as a comparison, make secondary cell in the mode identical with comparative example 6, only the porosity of outer surface anode active material layer and inner surface anode active material layer is changed into 25%, and the thickness of outer surface anode active material layer and inner surface anode active material layer is changed into 80 μ m.
For comparative example 5 to 7, made three secondary cells, and observed during the screw winding step production of crack in the positive pole or fracture.As a result, comparative example 5 and all secondary cells of 7 are not all observed crack or fracture.Simultaneously, in 1 secondary cell of comparative example 6, observe crack or fracture.
For the secondary cell of example 11 and comparative example 5 to 7 manufacturings,, measured the discharge capacity of circulation for the first time and the 100th circulation time, to obtain discharge capacitance as under the situation of example 1 to 5.What obtained the results are shown in the table 3.For comparative example 6, obtained wherein not produce the discharge capacitance of two secondary cells of crack and fracture.
Table 3:
Negative active core-shell material: graphite
Figure C200710107284D00311
As shown in table 3, according to example 11,, and can improve the discharge capacity of the first time and the 100th circulation time greatly even when the thickness of positive pole 21 increases, also do not produce crack or fracture.In addition, in example 11, can obtain to be equal to or greater than the discharge capacitance of comparative example 5 to 7.Simultaneously, in the comparative example 5 that only anodal therein thickness reduces, although do not have crack and fracture to produce, the discharge capacity of circulation time is lower for the first time.In addition, the anodal active material of the thickness of outer surface anode active material layer and inner surface therein
Figure C200710107284D0014113244QIETU
In the identical comparative example 6 of thickness of layer, crack and fracture have been produced.In addition, in the comparative example 7 that porosity increases, do not have crack and fracture to produce, but the discharge capacity of circulation time is lower for the first time therein.
That is to say, find when the thickness of inner surface anode active material layer 21C is configured on the screw winding central side less than the thickness of outer surface anode active material layer 21B and the outer surface regions of active material 21F that only is provided with outer surface anode active material layer 21B and goes between 25 overlappings, under the situation that comprises the cathode of carbon material active material, even the thickness when anodal 21 also can suppress the generation of crack and fracture when increasing, thereby can improve capacity.
As from table 1 to shown in 3 the result proved, find, do not consider the material of negative active core-shell material, when the thickness of inner surface anode active material layer 21C less than the anodal active material of outer surface
Figure C200710107284D0014113244QIETU
The thickness of layer 21B and the outer surface regions of active material 21F that only is provided with outer surface anode active material layer 21B are configured on the screw winding central lateral plane and go between 25 when overlapping, even the thickness when anodal 21 also can suppress the generation of crack and fracture when increasing, thereby and can improve capacity.Especially, at least a negative electrode active material in comprising tin and silicon (it has the advantage of raising capacity) as a kind of element
Figure C200710107284D0014113244QIETU
Situation under, can obtain better effect.Under the situation of the screw winding body 30 that comprises the flat pattern that has shown in Figure 4 and 5, when the thickness of inner surface anode active material layer 33C is set among the bend 30A less than the thickness of outer surface anode active material layer 33B and outer surface regions of active material 33F, can obtain the effect identical with spiral winding electrode 20 on the screw winding central side.
Invention has been described with reference to embodiment and example.Yet, the invention is not restricted to these embodiment and example, and can make various modification.For example, in aforementioned second embodiment, describe content and specifically provided and comprise a pair of relative bend 30A and be accommodated in situation in the packaging part of making by the aluminium lamination press mold 40 in this flat spiral winding electrode 30 to the par 30B between the bend 30A.Yet the present invention can also be applied to so-called rectangular cell, and wherein spiral winding electrode 30 is accommodated in the shell of being made by the iron (Fe) that is coated with nickel (Ni) etc.In this case, gel electrolyte layer 36 is not set, and is injected into electrolytic solution in the shell and is impregnated in the spacer in the identical mode of first embodiment.
In addition, in previous embodiment and previous examples, the description content has specifically provided the material of positive pole 21, negative pole 22, electrolytic solution etc.Yet, in the present invention, can use other material, as long as adopt the said spiral winding-structure.In addition, the present invention not only can be used for secondary cell, and can be used for other battery such as primary cell similarly.
It will be understood by those skilled in the art that according to design requirement and other factors and can carry out various modifications, combination, sub-portfolio and change, as long as they are in the scope of claims or its equivalent.

Claims (8)

1. battery, it comprises spiral winding electrode, in described spiral winding electrode anodal and negative pole in the mode that has spacer between the two stacked and screw winding,
Wherein, described spiral winding electrode is connected with at least one lead-in wire on the screw winding central side,
Described just have: positive electrode collector has a pair of apparent surface; The outer surface anode active material layer is arranged on the screw winding outer surface side of described positive electrode collector; And the inner surface anode active material layer, be arranged on the screw winding inner surface side of described positive electrode collector,
The thickness of described inner surface anode active material layer is less than the thickness of described outer surface anode active material layer, and
On the screw winding central side of described positive pole, only be provided with the anodal active material of described outer surface
Figure C200710107284C0002133949QIETU
The outer surface regions of active material of layer forms with described lead-in wire and overlaps.
2. battery according to claim 1,
Wherein, described negative pole has: negative electrode collector has a pair of apparent surface; The outer surface negative electrode active material
Figure C200710107284C0002133949QIETU
Layer is arranged on the screw winding outer surface side of described negative electrode collector; And the inner surface anode active material layer, be arranged on the screw winding inner surface side of described negative electrode collector, and
The thickness of described outer surface anode active material layer is identical with the thickness of described inner surface anode active material layer, perhaps less than the thickness of described inner surface anode active material layer.
3. battery according to claim 1, wherein, described negative pole comprises negative active core-shell material, and described negative active core-shell material comprises at least a formation element in tin (Sn) and the silicon (Si).
4. battery according to claim 1, wherein, the anodal active material of described outer surface
Figure C200710107284C0002133949QIETU
The porosity of layer and described inner surface anode active material layer is in 20% to 27% scope.
5. battery, it comprises spiral winding electrode, anodal and negative pole carries out stacked and screw winding in the mode that has spacer between the two in described spiral winding electrode,
Wherein, described spiral winding electrode is flat pattern, and this flat pattern comprises a pair of relative bend and be arranged on par between the described a pair of relative bend,
Described just have: positive electrode collector has a pair of apparent surface; The anodal active material of outer surface
Figure C200710107284C0002133949QIETU
Layer is arranged on the screw winding outer surface side of described positive electrode collector; And the anodal active material of inner surface
Figure C200710107284C0002133949QIETU
Layer is arranged on the screw winding inner surface side of described positive electrode collector,
The thickness of described inner surface anode active material layer is less than the thickness of described outer surface anode active material layer, and
On the screw winding central side of described positive pole, the outer surface regions of active material that only is provided with described outer surface anode active material layer is formed in the described bend.
6. battery according to claim 5, wherein, described negative pole has: negative electrode collector has a pair of apparent surface; The outer surface anode active material layer is arranged on the screw winding outer surface side of described negative electrode collector; And the inner surface anode active material layer, be arranged on the screw winding inner surface side of described negative electrode collector, and
The thickness of described outer surface anode active material layer is identical with the thickness of described inner surface anode active material layer, perhaps less than described inner surface negative electrode active material
Figure C200710107284C0002133949QIETU
The thickness of layer.
7. battery according to claim 5, wherein, described negative pole comprises negative active core-shell material, described negative electrode active material
Figure C200710107284C0002133949QIETU
Comprise at least a formation element in tin (Sn) and the silicon (Si).
8. battery according to claim 5, wherein, the porosity of described outer surface anode active material layer and described inner surface anode active material layer is in 20% to 27% scope.
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