CN100492748C - Battery and center pin - Google Patents
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- CN100492748C CN100492748C CNB2005800400728A CN200580040072A CN100492748C CN 100492748 C CN100492748 C CN 100492748C CN B2005800400728 A CNB2005800400728 A CN B2005800400728A CN 200580040072 A CN200580040072 A CN 200580040072A CN 100492748 C CN100492748 C CN 100492748C
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- center pin
- battery
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- otch
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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
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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
- 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
Abstract
A battery increased in safety by securely short-circuiting electrodes when a center pin is collapsed by an external force. The center pin (30) is inserted into the center of a roll manufactured by laminating a positive pole and a negative pole on each other through a separator and spirally winding the laminated poles. The center pin (30) comprises a slit (31) in the longitudinal direction, and first cutout parts (32) crossing perpendicularly to the slit (31). When the center pin is collapsed by the external force, corner parts (33) at intersections between the slit (31) and the first cutout parts (32) are projected to securely produce a short-circuit. Also, second cutout parts (34) in a vertical direction to the slit (31) are desirably be formed at positions facing the slit (31) in the circumferential direction. The center pin (30) is desirably be formed in an elliptic or flat oval shape in cross section, and the slit (31) is desirably be formed at a position where the diameter of the elliptic or flat oval shape in cross section is largest.
Description
Technical field
The present invention relates to a kind of center and comprise the battery of center pin in the spirality winding electrode body that comprises bar shaped negative electrode, spacer and anode, and the center pin that is used for this battery.
Background technology
In recent years, introduced many portable electric appts and for example made up camera (video recording device), mobile phone and notebook personal computer, and the size of these equipment is reduced and weight saving.Promoted to improve battery energetically, especially as the research and development of the energy density of the secondary cell of key equipment as the compact power of this electronic equipment.Especially, rechargeable nonaqueous electrolytic battery (for example lithium rechargeable battery) is compared with the excide battery or the nickel-cadmium cell that contain the aqueous electrolyte solution secondary cell as routine, and higher energy density is provided.Therefore, in every field, considered its improvement.
Developed lithium rechargeable battery with different shape.As wherein a kind of, exist the stacked and spirality of negative electrode and anode twine and spacer therebetween, and center pin is inserted in the lithium rechargeable battery that spirality is twined the center of electrode body.For example as shown in Figure 34, existing center pin tubular body axially on have secant 131.When external force was applied to battery, main body 130 flattened.As a result, the edge of secant 131 is outwardly open, and open section penetrates spacer, makes negative electrode and anode in short circuit.Thereby, stop cell reaction, and deprive electricity generate function safely.
Have a kind of existing battery that a plurality of grooves for example are provided for center pin abreast with secant, perhaps the edge of secant is corrugated battery, make to produce between the electrode short circuit and no matter the direction (for example, referring to Patent Document 1) of applied force.In addition, propose, perhaps easily produce short circuit (for example, refer to Patent Document 2 and patent documentation 3) by forming helical spring center pin widely by recessed portion is provided to spirality on the surface of center pin.
Patent documentation 1: open 8-255631 number of Japanese uncensored patent application
Patent documentation 2: No. 3178586, Japan Patent
Patent documentation 3: open 8-273697 number of Japanese uncensored patent application
Summary of the invention
But, have in the battery of center pin of aforementioned existing structure in use, there is a problem, promptly the distortion of secant part is insufficient when flattening because of external force, so negative electrode and anode short circuit safely.Expect a kind of by between the electrode more safely short circuit guarantee the effective ways of fail safe.
Consider aforementionedly, the object of the present invention is to provide a kind of battery that improves fail safe that has, when flattening because of external force, this battery can more safely short circuit between electrode, and the center pin that is used for this battery.
First battery according to the present invention comprises: twine the therebetween spirality that obtains of negative electrode and anode and spacer by stacked and spirality and twine electrode body, negative electrode has the cathode active material bed of material on the surface of bar shaped cathode current collector, and anode has anode active material layers on the surface of bar shaped anode collector; And be arranged in spirality and twine the center of electrode body, have secant on vertically, and has tubular center's pin of first otch that crosses secant.
Second battery according to the present invention comprises: twine the therebetween spirality that obtains of negative electrode and anode and spacer by stacked and spirality and twine electrode body, negative electrode has the cathode active material bed of material on the surface of bar shaped cathode current collector, and anode has anode active material layers on the surface of bar shaped anode collector; And be arranged in tubular center's pin that spirality is twined the center of electrode body and provided bending crack.
Be respectively applied for first battery of the present invention and second battery according to first center pin of the present invention and second center pin.
" otch " or " breach " preferably penetrates the wall of center pin.But otch or breach can be in so-called recessed state, and promptly the thickness of center pin compares thin thickness on every side, and do not penetrate the wall of center pin.
At first battery according to the present invention or in according to first center pin of the present invention, when external force was applied to battery, center pin flattened, and center pin vertically on secant outwardly open.Because first otch crosses secant, along with secant is outwardly open, the sharp comer at place, the crosspoint of the secant and first otch is outwardly open and outstanding.When sharp comer penetrates spacer, the short circuit safely of negative electrode and anode.
Especially, when providing a end in cathode current collector, negative electrode on the central side that twines electrode body in spirality do not have the cathode active material bed of material to be provided at negative electrode exposed region on the two sides of cathode current collector, and when twining anode on the central side of electrode body in spirality and providing a end at anode collector and do not have anode active material layers to be provided at anode exposed region on the two sides of anode collector, have two exposed region direct short-circuits of low-resistance relatively cathode current collector and anode collector.Just, do not produce short circuit by having the high-resistance cathode active material bed of material.Therefore, prevent the temperature rising of the cathode active material bed of material.
At second battery according to the present invention with in according to second center pin of the present invention, when external force was applied to battery, center pin flattened, and breach is outwards outstanding.When the bend relief partial penetration spacer of breach, the short circuit safely of negative electrode and anode.
According to first battery of the present invention or first center pin of the present invention, provide first otch with the secant of cross center's pin on vertically.Therefore, when flattening because of external force or breaking, the short circuit safely of negative electrode and anode, and fail safe improves.
Especially, can insert and extract the electrode reaction thing and comprise metallic element and during at least a active material of positive electrode as element of nonmetalloid, the energy density of battery is big, and requires higher fail safe when anode comprises.Therefore, in this case, can obtain higher effect.
In addition, when providing second otch on the direction of secant is being crossed in the position of departing from secant in a circumferential direction, except the crosspoint of the secant and first otch, the marginal portion of second otch is outwardly open.Therefore, negative electrode and anode short circuit safely.In addition, the size by changing second otch, number etc. can be regulated the intensity of center pin.
In addition, when the center pin has avette or oval-shaped shape of cross section, and when providing secant in the position of avette or oval diameter maximum, even apply power from the direction identical with avette or oval-shaped maximum gauge direction, center pin is twined in the electrode body in spirality and is rotated, on avette or oval-shaped minimum diameter direction, flatten easily, thus distortion that can the direction center pin.As a result, no matter the direction of applied force, secant is not flatly to flatten but outwardly open, and produces short circuit safely.
According to second battery of the present invention or second center pin of the present invention, for center pin provides bending crack.Therefore, when flattening because of external force or breaking, thus the short circuit raising fail safe safely of negative electrode and anode.In addition, when otch is arranged on the whole center pin equably, no matter the direction of applied force, thus negative electrode and anode safely short circuit can improve fail safe.
Description of drawings
Fig. 1 is the cross section that shows according to the secondary battery construction of first embodiment of the invention;
Fig. 2 is presented at spirality to twine the cross section of the structure of negative electrode shown in Fig. 1 before;
Fig. 3 is presented at spirality to twine the cross section of the structure of anode shown in Fig. 1 before;
Fig. 4 is the perspective view of the example of display centre pin configuration;
Fig. 5 is the cross section that shows the structure that obtains along the line at the center of passing first otch of center pin shown in Fig. 4;
Fig. 6 is the view of explanation operation of center pin when secondary cell flattens shown in Fig. 1, and the cross section that obtains along the line VI-VI of Fig. 1;
Fig. 7 is the perspective view of another example of display centre pin configuration;
Fig. 8 is the perspective view of another example of display centre pin configuration;
Fig. 9 is the plane graph that shows the step of the method for using the center pin shown in Fig. 8 to make secondary cell;
Figure 10 is the plane graph of the modification of display centre pin;
Figure 11 is the plane graph that shows the structure of decomposing along the secant of center pin shown in Figure 10;
Figure 12 is the plane graph that the another kind of display centre pin is revised;
Figure 13 is the plane graph that shows the structure of decomposing along the secant of center pin shown in Figure 12;
Figure 14 is the plane graph of another modification of display centre pin;
Figure 15 is the cross section that shows according to the center pin structure of second embodiment of the invention;
Figure 16 A and 16B are the views of the operation of center pin shown in explanation Figure 15;
Figure 17 is the cross section of the modification of display centre pin;
Figure 18 is the plane graph that shows according to the center pin structure of third embodiment of the invention;
Figure 19 is the view that shows the example of breach arrangement on the circumferencial direction;
Figure 20 is the view that shows another example of breach arrangement;
Figure 21 is the view that shows another example of breach arrangement;
Figure 22 is the plane graph of the modification of display centre pin;
Figure 23 is the plane graph that the another kind of display centre pin is revised;
Figure 24 is the plane graph of another modification of display centre pin;
Figure 25 is the plane graph of another modification of display centre pin;
Figure 26 is the plane graph of another modification of display centre pin;
Figure 27 is the plane graph that shows according to the center pin structure of four embodiment of the invention;
Figure 28 is the plane graph of the modification of display centre pin;
Figure 29 is the plane graph of demonstration according to the amplification breach of the center pin of fifth embodiment of the invention;
Figure 30 A is the plane graph that shows according to the center pin structure of sixth embodiment of the invention, and Figure 30 B is its cross section;
Figure 31 is the cross section of the modification of display centre pin;
Figure 32 A and 32B are the cross sections of the modification of first otch shown in the displayed map 5 or second otch;
Figure 33 is the perspective view of the modification of display centre pin; And
Figure 34 is the perspective view that shows the example of existing center pin.
Embodiment
To be described in detail with reference to the attached drawings embodiment of the present invention hereinafter.For each unit among the figure, be appreciated that on the degree of the present invention schematically display shape, size and position relation, and shape, size and position relation are different from actual use those.
(first embodiment)
Fig. 1 shows the cross-sectional structure according to the secondary cell of first embodiment of the invention.Secondary cell is so-called cylindrical battery, and has spirality winding electrode body 20 in battery can 11 inside of approximate hollow cylinder shape.Battery can 11 is made by the iron (Fe) of for example nickel plating (Ni).The one end sealing of battery can 11, and the other end opens wide.In battery can 11 inside, vertically arrange a pair of insulation board 12 and 13 with the peripheral surface of spirality winding respectively, make spirality twine electrode body 20 and be clipped between insulation board 12 and 13.
At the open end of battery can 11, by balancing cell lid 14 via packing ring 17 joint fillings, and the safety valve that provides in battery cover 14 inside mechanism 15 and PTC0 (positive temperature coefficient) device 16.Therefore the inside gas-tight seal of battery can 11.Battery cover 14 is for example by making with battery can 11 materials similar.Safety valve mechanism 15 is electrically connected to battery cover 14 and PTC device 16 is therebetween.When the internal pressure of battery becomes certain rank because of internal short-circuit, external heat etc. or when higher, disc plate 15A upset is to cut off being electrically connected between battery cover 14 and the spirality winding electrode body 20.When temperature raise, PTC0 device 16 limited the abnormal heating of electric current to prevent to rise because of high-current leading by increasing resistance.Packing ring 17 is made by for example insulating material and its surface applied has pitch.
In spirality was twined electrode body 20, negative electrode 21 and anode 22 were stacked and spirality is twined and spacer 23 is therebetween, and center pin 30 is inserted its centers.The cathode leg of being made by aluminium (Al) etc. 24 is connected to the negative electrode 21 that spirality is twined electrode body 20.The anode tap of being made by nickel etc. 25 is connected to anode 22.Cathode leg 24 is electrically connected to battery cover 14 by being welded to safety valve mechanism 15.Anode tap 25 welding also are electrically connected to battery can 11.
Fig. 2 is presented at spirality and twines the cross-sectional structure of negative electrode 21 shown in Fig. 1 before.In negative electrode 21, on the two sides of bar shaped cathode current collector 21A, provide cathode active material bed of material 21B.More particularly, negative electrode 21 has cathode active material bed of material 21B and is present in the outer circumference face of cathode current collector 21A and the cathode-coated district 21C on the inside circumference face.In addition, in negative electrode 21, the end that spirality is twined the central side of electrode body is negative electrode exposed region 21D, and just, the two sides that cathode active material bed of material 21B and cathode current collector 21A be not provided on the two sides of cathode current collector 21A is area exposed all.
The for example about 5 μ m-50 μ m of cathode current collector 21A are thick, and for example aluminium foil, nickel foil and stainless steel foil are made by metal forming.
Cathode active material bed of material 21B comprises one or more cathode materials that for example can insert and extract as the lithium of electrode reaction thing as active material of cathode.If necessary, cathode active material bed of material 21B also can comprise for example material with carbon element and adhesive Kynoar for example of electric conducting material.As the cathode material that can insert and extract lithium, for example, can enumerate the metal sulfide titanium sulfide (TiS for example that does not comprise lithium
2), molybdenum sulfide (MoS
2), selenizing niobium (NbSe
2) and vanadium oxide (V
2O
5), metal selenide, metal oxide or comprise the lithium-containing compound of lithium.
Especially, lithium-containing compound is preferred, because some lithium-containing compounds can provide high voltage and high-energy-density.As this lithium-containing compound, for example, can enumerate the composite oxides that comprise lithium and transition metal, perhaps comprise the phosphate compounds of lithium and transition metal.Especially, it is preferred comprising in cobalt (Co), nickel and the manganese (Mn) at least a compound, because this compound can provide higher voltage.Its chemical formula can for example be expressed as Li
xMIO
2Or Li
yMIIPO
4In chemical 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 the value of x and y is 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 nickel composite oxide (Li
xNiO
2), lithium/nickel/cobalt composite oxide (Li
xNi
1-zCo
zO
2(z＜1)), have the complex Li-Mn-oxide (LiMn of spinel structure
2O
4) etc.Especially, the composite oxides that comprise nickel are preferred, because this composite oxides can provide high power capacity and superior cycle characteristics.As the instantiation of the phosphate compounds that comprises lithium and transition metal, for example, can enumerate lithium iron phosphate compound (LiFePO
4) or ithium iron manganese phosphate compounds (LiFe
1-vMn
vPO
4(v＜1)).
Fig. 3 shows the structure of anode 22.In anode 22, anode active material layers 22B is provided on the two sides of bar shaped anode collector 22A.More particularly, anode 22 has anode active material layers 22B and is present in the outer circumference face of anode collector 22A and the anode coating region 22C on the inside circumference face.In addition, in the end that spirality is twined the central side of electrode body, anode 22 has two sides exposed anode exposed region 22D all that anode active material layers 22B and anode collector 22A are not provided on the two sides of anode collector 22A.
For example make by Copper Foil, nickel foil and stainless steel foil by metal forming for example for anode collector 22A.The for example about 5 μ m-50 μ m of anode collector 22A are thick.
Anode active material layers 22B comprises for example active material of positive electrode.If necessary, anode active material layers 22B can comprise other materials for example electric conductor and adhesive.As active material of positive electrode, for example, can enumerate and to insert and to extract as the lithium of electrode reaction thing and comprise metallic element and at least a anode material of nonmetalloid as element.Preferably use this anode material, because can obtain high-energy-density thus.As this anode material, can enumerate simple substance, alloy or the compound of metallic element or nonmetalloid, perhaps have the material of its one or more phases at least in part.In the present invention, except the alloy that comprises two or more metallic elements, alloy also comprises the alloy that comprises one or more metallic elements and one or more nonmetalloids.In addition, alloy can comprise nonmetalloid.Its structure can be the structure of two or more coexistences of solid solution, eutectic (eutectic mixture), interphase or aforementioned structure.
As this metallic element or this nonmetalloid of forming anode material, for example, can enumerate the metallic element or the nonmetalloid that can form alloy with lithium.More particularly, can enumerate magnesium (Mg), boron (B), aluminium (Al), gallium (Ga), indium (In), silicon, germanium (Ge), tin, lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), iridium (Y), palladium (Pd), platinum (Pt) etc.
Especially, as anode material, comprising in the long period periodic table metallic element of group 14 or nonmetalloid is preferred as the compound of element.At least a material as element that comprises tin and silicon is preferred especially.Tin and silicon have the high ability of inserting and extracting lithium and high-energy-density is provided.More particularly, can enumerate simple substance, alloy or the compound of silicon; The simple substance of tin, alloy or compound; The material that perhaps has its one or more phases at least in part.
Alloy as tin, for example, can enumerate and comprise at least a alloy that is selected from silicon, nickel, copper, iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr) as second element outside the detin.As the alloy of silicon, for example, can enumerate and comprise at least a alloy that is selected from tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium as second element outside the silica removal.
As the compound of tin or the compound of silicon, for example, can enumerate the compound that comprises oxygen (O) or carbon (C).Except tin or silicon, compound can comprise aforementioned second element.
Especially, as this anode material, comprising tin, cobalt and carbon is preferred as the CoSnC material that contains of element, and wherein carbon content is 9.9wt%-29.7wt%, and the ratio of the summation of cobalt and tin and cobalt is 30wt%-70wt%.In this compositing range, can obtain high-energy-density, and can obtain superior cycle characteristics.
If necessary, contain the CoSnC material and can further comprise other elements.As other elements, for example, silicon, iron, nickel, chromium, indium, niobium (Nb), germanium, titanium, molybdenum (Mo), aluminium (Al), phosphorus (P), gallium (Ga) or bismuth are preferred.Can comprise its two or more, because can further improve capacity or cycle characteristics thus.
Contain the CoSnC material and have the tin of comprising, cobalt and carbon mutually.This phase preferably has low-crystallinity structure or non crystalline structure.In addition, in containing the CoSnC material, the metallic element or the nonmetalloid that are attached to as another kind of element as at least a portion of the carbon of element are preferred.Its reason is as follows.May cause the cycle characteristics of reduction because of the cohesion of tin or crystallization etc.Can usually prevent this cohesion or crystallization by carbon being attached to other yuan.
As the method for measurement of checking the element bonding state, for example, can enumerate X ray photoelectric spectrum method (XPS).In XPS, in the situation of graphite, make and obtain to observe the peak value of the 1s track (C1s) of carbon at the 284.5eV place in the device of peak value of 4f track (Au4f) of gold atom carrying out energy correction at the 84.0eV place.Under the situation of surface contamination carbon, observe peak value at the 284.8eV place.Simultaneously, under the situation of the higher charge density of carbon, for example, when carbon is attached to metallic element or nonmetalloid, observe the peak value of C1s in the location that is lower than 284.5eV.Just, when when the location that is lower than 284.5eV is observed the composite wave peak value of the C1s that obtains for containing the CoSnC material, be included at least a portion that contains the carbon in the CoSnC material and be attached to metallic element or nonmetalloid as another kind of element.
In XPS measuring, for example, the peak value of C1s is used to proofread and correct the energy axes of spectrum.Because surface contamination carbon exists usually from the teeth outwards, the peak value of the C1s of surface contamination carbon is set to 284.8eV, and it is as the energy reference.In XPS measuring, the waveform of the peak value of C1s obtains with containing the shape of the peak value of carbon in the CoSnC material as the peak value that comprises surface contamination carbon.Therefore, by using analysis such as commercially available software, with the peak value and the peak separation that contains carbon in the CoSnC material of surface contamination carbon.In waveform analysis, the position that is present in the main peak on minimum binding energy one side is as energy reference (284.8eV).
As active material of positive electrode, but also can use material with carbon element for example native graphite, Delanium, can not graphitized carbon and graphitized carbon.Preferably use material with carbon element, because can obtain superior cycle characteristics.In addition, as active material of positive electrode, also can enumerate the lithium metal.As active material of positive electrode, can use aforesaid a kind ofly individually, perhaps can use its two or more by mixing them.
Spacer 23 shown in Fig. 1 by for example by the polyolefine material porous membrane made of polypropylene and polyethylene for example, perhaps by inorganic material for example the porous membrane made of ceramic fiber nonwoven fabric make.Spacer 23 can have two or more stacked structures of aforementioned porous membrane.
Electrolytic solution as liquid electrolyte injects spacer 23.Electrolytic solution comprises solvent for example and as the lithium salts of electrolyte salt.Solvent is used for dissolving and separate electrolyte salt.As solvent, for example, can enumerate propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxy-ethane, 1, the 2-diethoxyethane, Y-butyrolactone, oxolane, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl isophthalic acid, 3-dioxolane, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, propionitrile, methyl phenyl ethers anisole, acetic acid esters, butyrate, propionic ester etc.Can use solvent individually, perhaps can use its two or more by mixing.
As lithium salts, for example, can enumerate LiClO
4, LiAsF
6, LiPF
6, LiBF
4, LiB (C
6H
5)
4, CH
3SO
3Li, CF
3SO
3Li, LiCl, LiBr etc.As lithium salts, can use aforesaid a kind ofly individually, perhaps can use its two or more by mixing them.
The structure of center pin 30 shown in Fig. 4 displayed map 1.The cross-sectional structure of Fig. 5 display centre pin 30.Thin stripe board forms tubular form with center pin 30 by for example rolling.Center pin 30 is that for example diameter is the cylindrical of 3.0mm.The two ends of center pin 30 provide sloping portion 30A, thereby easily center pin 30 are inserted the center that said spiral shape is twined electrode body 20 in the aftermentioned manufacture process.
The secant 31 that center pin 30 passes through on having vertically.In addition, center pin 30 is formed with first otch 32 vertically to cross secant 31.At its crossing place, provide corner 33.Therefore, for example, as shown in Figure 6, when secondary cell flattened because of external force F, the corner at the crosspoint of the secant 31 and first otch 32 place 33 was outstanding with outwardly open and penetrate spacer 23.As a result, negative electrode 21 and anode 22 short circuit safely.
Especially, can insert and extract the electrode reaction thing and comprise metallic element and during at least a active material of positive electrode as element of nonmetalloid when anode 22 comprises, energy content of battery density is big and require higher fail safe.Therefore, in this case, can obtain higher effect.
Consider the material and the thickness of definite center pin 30 such as size, length of first otch 32.In the degree that usually keeps given intensity the material and the thickness of center pin 30 are set, but when battery flattens because of external force, center pin 30 flatten together and corner 33 outwardly open to penetrate spacer 23.More particularly, as the material of center pin 30, for example, can enumerate stainless steel.The thickness of center pin 30 preferably for example is 0.05mm-5mm.Be lower than under the situation of 0.05mm, intensity may reduce.Simultaneously, be higher than under the situation of 5mm, it is difficult that plate is rolled into tubular form.The length of center pin 30 changes according to the size of secondary cell, but 2.5cm-8.0cm for example preferably.
When in the aftermentioned manufacturing step, rolling into tubular form when forming center pin 30, provide secant 31 at interval by between the long relatively limit of center pin 30, forming by approaching stripe board.The width of secant 31 for example is 0.5mm.
Preferably 33 degree that can give prominence to safely are provided with the length of first otch 32 in the corner, just, and the size of first otch 32 on the circumferencial direction of center pin 30, for example, a semi-circumference of center pin 30.In addition, the width of first otch 32, just, the gravel size decision ground of vertical last first otch 32 of center pin 30 is 0.1mm-2.0mm.Thus, can obtain higher effect.
Be not specially limited the position of the number and first otch 32 of first otch 32.For example, as shown in Figure 4, can provide one first otch 32 at the center of secant 31.In addition, for example, as shown in Figure 7, except the heart therein, can near the two ends of secant 31, provide first otch 32.
In addition, except aforementioned first otch 32, for example, as shown in Figure 8, center pin 30 preferably has second otch 34 towards the position of secant 31 in a circumferential direction.The same with first otch 32, second otch 34 also is provided on the direction vertical with secant 31.Therefore, when external force applied, first otch 32 and second otch 34 were all outwardly open, penetrate spacer 23, and are pressed on negative electrode 21 and the anode 22.Thereby, can more safely produce short circuit.In addition, the size by changing second otch 34, number etc. can be regulated the intensity of center pin 30.
So that the length of second otch 34 can outwardly open degree at second otch 34 when flattening or break to be set.For example, the same with first otch 32, the length of second otch 34 is set to a semi-circumference of center pin 30.The same with first otch 32, the width of second otch 34 is 0.1mm-2.0mm for example preferably.Number and the position that can determine second otch 34 according to the number and the location-appropriate ground of first otch 32, and be not specially limited.
Can for example following manufacturing secondary cell.The description of the example under the situation of for example making the secondary cell with center pin shown in Fig. 8 30 will be given in.
At first, for example, mix active material of cathode, electric conductor and adhesive with the preparation cathode mix, its be dispersed in solvent for example in the N-N-methyl-2-2-pyrrolidone N-to form pulpous state cathode mix mud.Subsequently, make cathode current collector 21A be coated with cathode mix mud equably by using scraper, metering bar coater etc., its by roll squeezer dry and pressing mold forming cathode active material bed of material 21B, thereby formation negative electrode 21.
Next, for example, multilayer anode active material and adhesive be with the preparation anode mixture, its be dispersed in solvent for example in the N-N-methyl-2-2-pyrrolidone N-to form pulpous state anode mixture mud.Subsequently, make anode collector 22A be coated with anode mixture mud equably by using scraper, metering bar coater etc., its by roll squeezer dry and pressing mold forming anode active material layers 22B, thereby formation anode 22.Can use roll squeezer to heat simultaneously.In addition, pressing mold can be carried out repeatedly up to the physical values that obtains expection.In addition, can use press except roll squeezer.
Subsequently, cathode leg 25 waits by welding and is connected to cathode current collector 21A, and anode tap 26 is connected to anode collector 22A by welding etc.After this, negative electrode 21 and anode 22 are stacked and spacer 23 is therebetween, and spirality is twined several times and twined electrode body 20 to form spirality on the spirality winding direction shown in Fig. 2 and Fig. 3.
Simultaneously, as shown in Figure 9, the thin stripe board 41 that preparation is made by for example stainless steel.By steel wire septum 41, form first otch 32 and second otch 34.Subsequently, as shown in Figure 8, plate 41 is rolled into cylindrical shape, two ends are tapered so that sloping portion 30A to be provided.Thereby, form center pin 30.
After forming center pin 30, center pin 30 is inserted the center that spirality is twined electrode body 20.Subsequently, spirality is twined electrode body 20 and is clipped in this between insulation board 12 and 13, and anode tap 25 is welded to battery can 11, and cathode leg 24 is welded to safety valve mechanism 15, and spirality winding electrode body 20 is included in battery can 11 inside.After this, electrolytic solution is injected battery can 11, and pour in the spacer 23.After this, at the open end of battery can 11, by fix battery cover 14, safety valve mechanism 15 and PTC device 16 via packing ring 17 joint fillings.Thereby finish the secondary cell shown in Fig. 1.
In secondary cell, when charging, for example, lithium ion extracts from negative electrode 21, and inserts anode 22 via the electrolytic solution that injects spacer 23.When discharge, for example, lithium ion extracts from anode 22, and inserts negative electrode 21 via the electrolytic solution that injects spacer 23.In secondary cell, center pin 30 provides secant 31 in the vertical, and provides first otch 32 vertically to cross secant 31.Therefore, when external force applied, center pin 30 flattened or breaks, and secant 31 is outwardly open.Therefore, spacer 23 is given prominence to and penetrated in the corner 33 at place, the crosspoint of the secant 31 and first otch 32.As a result, negative electrode 21 and anode 22 short circuit safely.
In addition, in secondary cell, twining to provide on the central side in the spirality of negative electrode 21 does not have cathode active material bed of material 21B to be provided at negative electrode exposed region 21D on the two sides.In addition, twine to provide on the central side in the spirality of anode 22 and do not have anode active material layers 22B to be provided at anode exposed region 22D on the two sides.Therefore, when corner 33 penetrates spacer 23, has direct short-circuit between low-resistance relatively cathode current collector 21A and the anode collector 22A.Just, in this embodiment, the anode exposed region 22D of the negative electrode exposed region 21D of negative electrode 21 and anode 22 is by corner 33 short circuits of center pin 30, and do not produce short circuit by having high-resistance cathode active material bed of material 21B.Therefore, prevent the temperature rising of cathode active material bed of material 21B.
As above, in this embodiment, provide the secant 31 of first otch 32 with vertical cross center pin 30.Therefore, when external force applied, sharp comer 33 was outwards outstanding with short circuit negative electrode 21 and anode 22 safely.In addition, on spirality is twined the central side of electrode body 20, provide especially and do not have cathode active material bed of material 21B to be provided at negative electrode exposed region 21D on the two sides.In addition, on spirality is twined the central side of electrode body 20, provide especially and do not have anode active material layers 22B to be provided at anode exposed region 22D on the two sides.Therefore, when corner 33 penetrates spacer 23, has low-resistance relatively cathode current collector 21A and anode collector 22A direct short-circuit.Therefore, raise though prevent the temperature of cathode active material bed of material 21B, thus negative electrode 21 and anode 22 short circuit raising fail safe safely.
Especially, can insert and extract the electrode reaction thing and comprise metallic element and during at least a active material of positive electrode as element of nonmetalloid when anode 22 comprises, energy content of battery density is big and require higher fail safe.Therefore, in this case, can obtain higher effect.
In addition, in this embodiment, by providing second otch 34 first otch 32 except providing for center pin 30, when external force applied, second otch 34 was also outwardly open and be pressed on negative electrode 21 and the anode 22, was possible thereby be easy to generate short circuit.In addition, the size by changing second otch 34, number etc. can be regulated the intensity of center pin 30.
(modification of first embodiment)
Figure 10 shows the modification of aforementioned center pin 30.The structure that Figure 11 display centre pin 30 decomposes along secant 31.As shown in FIG., first otch, 32 diagonal cross secant 31, and cross at diagonal that to provide second otch 34 on the direction of secant 31 be possible.Second otch 34 not necessarily provides.
The another kind of Figure 12 display centre pin 30 is revised.The structure that Figure 13 display centre pin 30 decomposes along secant 31.As shown in FIG., when flattening or break first otch 32 and the distortion of second otch 34 to make corner 33 outstanding be enough.Its shape be not limited to first embodiment in the same linear, and may be V-arrangement.Second otch 34 not necessarily provides.
Another modification of Figure 14 display centre pin 30.As shown in FIG., second otch 34 departs from secant 31 in a circumferential direction, and not necessarily the position towards secant 31 is enough on the circumferencial direction as being positioned in first embodiment.In addition, not necessarily all second otch 34 all are positioned at position identical on the circumferencial direction, and second otch 34 may be positioned at the position of departing from each other.
(second embodiment)
Figure 15 shows the cross-sectional structure according to the center pin 30 of the secondary cell of second embodiment of the invention.This secondary cell has structure, operation and the effect similar with first embodiment, except the shape of cross section of center pin 30 is avette and secant 31 is positioned on the avette long diameter.Can with the same second battery of making in first embodiment.Therefore, will provide description by this way, promptly use identical symbol mark with those identical unit of first embodiment.
In secondary cell, the shape of cross section of center pin 30 is avette and secant 31 is positioned on the avette long diameter.Therefore, for example, as shown in Figure 16 A, when external force F when the direction identical with avette long diametric(al) applies, center pin 30 is twined electrode body 20 inner rotations in spirality on the direction of for example arrow R.As a result, the attitude of center pin 30 becomes as shown in Figure 16 B, and center pin 30 flattens on avette short diametric(al) as shown in Figure 16 C.Therefore, secant 31 is not flatly to flatten but outwardly open, and the corner 33 at the place, crosspoint of the secant 31 and first otch 32 is outstanding, and negative electrode 21 and anode 22 short circuit safely.
As above, in this embodiment, the shape of cross section of center pin 30 is avette and secant 31 is positioned on the avette long diameter.Therefore, center pin 30 flattens on avette short diametric(al) easily, thereby can provide deformation direction for center pin 30.As a result, no matter the direction of applied force, secant 31 is not flatly to flatten but outwardly open, and can produce short circuit safely.
In this embodiment, the shape of cross section that has provided center pin 30 is the description of avette situation.But as shown in Figure 17, the shape of cross section of center pin 30 can be oval, and secant 31 is positioned at the position of oval-shaped diameter maximum.
In addition, as the secondary cell according to aforementioned modifications, first otch, 32 diagonal cross secant 31 and cross at diagonal that to provide second otch 34 (referring to Figure 10 and Figure 11) on the direction of secant 31 be possible.In addition, when flattening or break first otch 32 and the distortion of second otch 34 to make corner 33 to give prominence to be enough.Its shape be not limited to first embodiment in the same linear, and may be V-arrangement (with reference to Figure 12 and Figure 13).In addition, it is enough that second otch 34 departs from (referring to Figure 14) with secant 31 in a circumferential direction, and second otch 34 is not necessarily as the position that is positioned in first embodiment on the circumferencial direction towards secant 31.In addition, not necessarily all second otch 34 all are positioned at position identical on the circumferencial direction, and second otch 34 may be positioned at the position of departing from each other.
(the 3rd embodiment)
Figure 18 shows the structure according to the center pin 30 of the secondary cell of third embodiment of the invention.This secondary cell has the structure with the similar of first embodiment, except providing the bending crack 35 for center pin 30.Therefore, will provide description by this way, promptly use identical symbol mark with those identical unit of first embodiment.
The degree that can give prominence to safely with breach 35 is provided with the length of the 35A of first and the length of second portion 35B, just, and the size on the bearing of trend, for example, a semi-circumference of about center pin 30.The width of the width of the 35A of first and second portion 35B, just, the gravel size decision ground of breach 35 for example is 0.1mm-2.0mm on the direction vertical with bearing of trend.Thereby, can obtain higher effect.The length of the length of the 35A of first and second portion 35B is not necessarily identical.
Preferably, the 35A of first be parallel to center pin 30 vertically, and second portion 35B and the 35A of first are vertically from the end extension of the 35A of first.Thereby, can boost productivity.
Distance D between each breach 35 preferably for example is 0.1mm or more.Thereby, can boost productivity.
In addition, preferably, on the circumferencial direction of center pin 30, arrange odd number otch 35 discretely.Thereby otch 35 can be arranged on the whole center pin 30 equably.The meaning that aforementioned literal " is arranged odd number otch 35 " discretely is that the interval between each breach 35 on the circumferencial direction (the center C angulation of immediate each other two otch 35 and center pin 30 on the circumferencial direction) is the angle that 360 degree obtain divided by this odd number.Each interval on the circumferencial direction between each breach 35 is not necessarily identical from one another, but may almost be equal to each other.In addition, breach 35 not necessarily on identical circumference, and may center pin 30 vertically on provide with departing from a little each other.
More particularly, as shown in Figure 19, can arrange three otch 35 in a circumferential direction discretely.In addition, as shown in Figure 20, can arrange five otch 35 in a circumferential direction discretely.In addition, as shown in Figure 21, can arrange seven otch 35 in a circumferential direction discretely.Especially, it is preferred arranging seven otch 35 discretely.Thus, proofread and correct the alignment deviations of otch 35, thus the short circuit and no matter the direction of applied force safely of negative electrode 21 and anode 22.Simultaneously, when arranging eight or more otch 35 discretely, the size of breach 35 should reduce.As a result, existence can not obtain the possibility of abundant effect.
Can with the same secondary cell of making in first embodiment, except by provide breach 35 plate 41 that rolls then to form the center pin 30 for plate 41.
In secondary cell, when external force was applied to secondary cell, center pin 30 flattened, and breach 35 is outwards outstanding.The bossing 35C of breach 35 penetrates spacer 23, thus negative electrode 21 and anode 22 short circuit safely.
As above, in this embodiment, for center pin 30 provides breach 35.Therefore, when flattening because of external force or breaking, thus negative electrode 21 and anode 22 short circuit raising fail safe safely.
Especially, when on the circumferencial direction of center pin 30, arranging odd number otch 35 discretely, especially, when on the circumferencial direction of center pin 30, arranging seven otch 35 discretely, otch 35 can be evenly arranged on the whole center pin 30, the short circuit and no matter the direction of applied force safely of negative electrode and anode, and fail safe can further improve.
(modification of the 3rd embodiment)
In this embodiment, provided description with the situation of arranged at regular intervals otch 35.But, can arrange otch 35 by irregular spacing.In addition, in this embodiment, provided the 35A of first and be parallel to the vertical of center pin 30, and second portion 35B is perpendicular to the description of the situation of first.But as shown in Figure 22, the 35A of first and second portion 35B can become diagonal to arrange with the vertical of center pin 30.
In addition, in this embodiment, the description of the situation that the direction that has provided second portion 35B and the 35A of first is vertically extended from the end of the 35A of first.But as shown in Figure 23, second portion 35B can acutangulate from the end of the 35A of first with the 35A of first and extend.In addition, second portion 35B and the 35A of first acutangulate from the end of the 35A of first and extend, simultaneously the 35A of first and second portion 35B and center pin 30 vertical to become the diagonal arrangement be possible.
In addition, the breach 35 linear second portion 35B that can have the linear 35A of first and cross the 35A of first.In this case, second portion 35B can or cross the 35A of first with T shape as shown in Figure 25 as shown in Figure 24 with cross.In addition, the crossing angle of 35A of first and second portion 35B is the right angle not necessarily, and may be acute angle or obtuse angle.
In addition, breach 35 does not always have linear, and may have circular bend shape as shown in Figure 26.
(the 4th embodiment)
Figure 27 shows the structure according to the center pin 30 of the secondary cell of four embodiment of the invention.This secondary cell has structure, operation and the effect similar with the 3rd embodiment, except breach 35 not only being provided but also providing the secant 31 of first otch, 32 similar otch 32 with cross center's pin 30 with first embodiment.Can be as making secondary cell in the 3rd embodiment.
With the same construction incision 32 in first embodiment, except only on a side of secant 31, providing the otch 32.
In this embodiment, provide breach 35 and otch 32 for center pin 30.Therefore, when tired external force flattens or breaks, thus negative electrode 21 and anode 22 short circuit raising fail safe safely.
In this embodiment, be given the description that center pin 30 provides the situation of breach shown in Figure 18 35.But, can be provided in the breach 35 of other shapes of describing in the modification of the 3rd embodiment.For example, as shown in Figure 28, can provide X-fracture shown in Figure 24 35.
In addition, in this embodiment, having provided provides breach 35 and otch 32 with towards each other and the description of the therebetween situation of secant 31.But breach 35 and otch 32 not necessarily are positioned at towards position each other.In this case, otch 32 can be as the both sides of describing in first embodiment that are provided at secant 31.In addition, otch 32 can be other shapes of describing in the modification of first embodiment.
(the 5th embodiment)
Figure 29 is the zoomed-in view according to the breach 35 of the center pin 30 of the secondary cell of fifth embodiment of the invention.In secondary cell, provide stepwise step 35D in a side of the breach 35 of center pin 30.Thus, bossing 35C protrudes into spacer 23 easily, perhaps deeper protrudes into spacer 23, thus negative electrode 21 and more safely short circuit of anode 22.Except this aspect, the similar of the structure of the 5th embodiment and the 3rd embodiment.Therefore, will provide description by this way, promptly use identical symbol mark with those identical unit of the 3rd embodiment.
At least it is enough providing step 35D in the side of bossing 35C, but can provide step 35D in the whole side of breach 35.The shape of step 35D, angle etc. are restriction especially not, may for example be zigzag.In addition, step 35D can be straight line or curve.In fact, it is difficult the corner of step 35D being formed complete straight line.Therefore, the corner may cavetto.Step 35D preferably with the surface of center pin 30 on par, perhaps from the surface of center pin 30 towards interior.When step 35D is outwards outstanding from the surface of center pin 30, there is when in manufacturing step, center pin 30 being inserted the center of spiralitys winding electrode body 20 possibility that spacer 23 is damaged by step 35D.
As above, in this embodiment, provide step 35D in the side of the breach 35 of center pin 30.Therefore, bossing 35C protrudes into spacer 23 easily, perhaps deeper protrudes into spacer 23.As a result, negative electrode 21 and more safely short circuit of anode 22, thus fail safe further improves.
(the 6th embodiment)
Figure 30 shows the structure according to the center pin 30 of the secondary cell of sixth embodiment of the invention.In secondary cell, the shape of cross section of center pin 30 is triangles.Thus, when external force applied, the vertex of a triangle of center pin 30 was invaded spacer 23, thus negative electrode 21 and anode 22 short circuits.Except this aspect, those of the structure of the 6th embodiment, operation and effect and the 3rd embodiment are similar, and can with the same secondary cell of making the 6th embodiment in the 3rd embodiment.Therefore, will provide description by this way, promptly use identical symbol mark with those identical unit of the 3rd embodiment.
The position of secant 31 is restriction especially, but preferably in the vertex of a triangle of center pin 30.Thereby when external force applied, secant 31 can be outwardly open with intrusion spacer 23, thus negative electrode 21 and more safely short circuit of anode 22.
As above, in this embodiment, the shape of cross section of center pin 30 is triangles.Therefore, when external force applies, can produce short circuit safely.
In this embodiment, the shape of cross section that has provided center pin 30 is the description of leg-of-mutton situation.But the shape of cross section of center pin 30 can be other polygons, for example the rectangle shown in Figure 31 and have the polygon on 5 or more summits.In addition, secant 31 not necessarily is provided at the summit, and may be provided at flat as shown in Figure 31.
Example
In addition, will describe instantiation of the present invention in detail.
(example 1-1 to 1-4)
Make secondary cell and the modification thereof described in first embodiment.
At first, with Li
2CO
3: CoCO
3Mixed lithium carbonate (the Li of=0.5:1 (mol ratio)
2CO
3) and cobalt carbonate (CoCO
3).In air, fire mixture under 900 degrees centigrade and reach 5 hours, to obtain lithium cobalt composite oxide (LiCoO as active material of cathode
2).Next, mix the lithium cobalt composite oxide of 91 weight portions, the graphite as conductive agent of 6 weight portions, and 3 weight portions as the Kynoar of adhesive with the preparation cathode mix.Subsequently, cathode mix be dispersed in as in the N-N-methyl-2-2-pyrrolidone N-of solvent to form cathode mix mud.The two sides of the cathode current collector 21A that is made by the thick aluminium foil of 20 μ m all is coated with cathode mix mud equably, and is dry then.By roll squeezer pressing mold product forming cathode active material bed of material 21B, thereby form negative electrode 21.Subsequently, cathode leg 25 made of aluminum is connected to the end of cathode current collector 21A.
In addition, formation contains the CoSnC material as active material of positive electrode.At first, as raw material, be ready to cobalt dust, tin powder and carbon dust.Fusion cobalt dust and tin powder are to form the cobalt tin alloy powder, and carbon dust adds to wherein and does and mix.Subsequently, by using mechanico-chemical reaction synthetic mixture in planetary-type grinding machine to contain the CoSnC material with acquisition.
Analyze the composition that contains the CoSnC material that obtains.As a result, cobalt content is 29.3wt%, and tin content is 49.9wt%, and carbon content is 19.8wt%.Use the analysis of carbon and sulfur device to measure carbon content.Use ICP (inductively coupled plasma) emission spectroscopy to measure cobalt content and tin content.In addition, contain the CoSnC material, carry out X-ray diffraction about what obtain.As a result, observing bandwidth and the angle of diffraction 2 θ with a half-breadth in the scope of the angle of diffraction 2 θ=20-50 degree is 1.0 degree or more diffraction maximum.In addition, when when containing the CoSnC material and carry out XPS, in being lower than the zone of 284.5eV, obtain to contain the C1s peak value of CoSnC material.Just, confirm that the carbon that contains in the CoSnC material is attached to other elements.
Next, that mixes 60 weight portions contains the CoSnC material, the Delanium as conductive agent and active material of positive electrode of 28 weight portions, and 10 weight portions as the Kynoar of adhesive with the preparation anode mixture.Subsequently, anode mixture be dispersed in as in the N-N-methyl-2-2-pyrrolidone N-of solvent to obtain anode mixture mud.The two sides of the anode collector 22A that is made by the thick Copper Foil of 15 μ m all is coated with anode mixture mud, and is dry then.By roll squeezer pressing mold product to form anode active material layers 22B.After this, the anode tap of being made by nickel 26 is connected to the end of anode collector 22A.
Subsequently, prepare the spacer of making by the thick microporous polypropylene film of 25 μ m 23.Then, negative electrode 21, spacer 23, anode 22 and spacer 23 are stacked to form lamination with this order.After this, the lamination spirality is twined several times to form spirality winding electrode body 20.The maximum gauge that spirality is twined electrode body 20 is 13.5mm.
After forming spirality winding electrode body 20, the thin stripe board 41 that preparation is made by stainless steel.By steel wire septum 41, form first otch 32 and second otch 34.In example 1-1, as shown in Figure 4, provide one first otch 32 vertically crossing secant 31, and second otch 34 is not provided.In example 1-2, as shown in Figure 7, provide three first otch 32 vertically crossing secant 31, and second otch 34 is not provided.In example 1-3, as shown in Figure 8, provide five first otch 32 vertically crossing secant 31, and on the direction vertical with secant 31 in a circumferential direction the position towards secant 31 four second otch 34 are provided.In example 1-4, as shown in Figure 10 and Figure 11, provide three first otch 32 to cross secant 31, and cross at diagonal on the direction of secant 31 three second otch 34 are provided with diagonal.
After this, rolling plate 41 also forms cylindrical shape, and provide sloping portion 30A at its two ends.Thus, form center pin 30, and center pin 30 is inserted the center that spirality is twined electrode body 20.
After this, spirality is twined electrode body 20 and is clipped in this between insulation board 12 and 13, and anode tap 25 is welded to battery can 11, and cathode leg 24 is welded to safety valve mechanism 15, and spirality winding electrode body 20 is included in the battery can 11 that internal diameter is 14.0mm.After this, electrolytic solution injects battery can 11.As electrolytic solution, use and pass through 1mol/dm
3The LiPF as electrolyte salt
6Be dissolved in the mixed solvent of diethyl carbonate of the ethylene carbonate of 50 volume % and 50 volume % and the solution that obtains.
After electrolytic solution injects battery can 11, by covering 14 via packing ring 17 joint filling self-contained batteries.As a result, obtaining external diameter is the column secondary battery of 14mm and high 43mm.
(example 2)
Make the secondary cell of describing in second embodiment.Just, as shown in Figure 15, with the same secondary cell of making among the example 1-3, except the shape of cross section of center pin 30 is avette and secant 31 is positioned on the avette long diameter.
As comparative example 1,, only have secant 131 as shown in Figure 34 and do not have the existing center pin of first otch and second otch except using with the same secondary cell of making among the example 1-1 to 1-4 with respect to example 1-1 to 1-4 and example 2.
Respectively for example 1-1 to 1-4, five secondary cells (battery 1 is to battery 5) that example 2 and comparative example manufacturing as above obtain.These batteries are carried out the appearance that crushing test is lighted and exploded with inspection.The result who obtains shows in form 1.
[form 1]
Confirm as form 1,, do not have blast according to example 1-1 to 1-4 with first otch 32 that crosses secant 31 and example 2.Simultaneously, in the comparative example that first otch is not provided, whole five secondary cells all explode.Just, find when center pin 30 provides first otch 32 that crosses secant 31 that even battery flattens or breaks and cause short circuit, fail safe can improve.
(example 3)
Make the secondary cell of describing in the 3rd embodiment.Just, with the same secondary cell of making among the example 1-1 to 1-4, except providing the L shaped bending crack 35 for center pin 30 as shown in Figure 18.
(example 4-1 to 4-2)
Make the secondary cell of describing in the 4th embodiment.Just, with the same secondary cell of making among the example 1-1 to 1-4, except providing breach 35 and the otch 32 for center pin 30.In example 4-1, the L shaped breach 35 shown in Figure 27 is provided, and in example 4-2, provides the X-fracture 35 shown in Figure 28.
(example 5)
Make the secondary cell of describing in the 5th embodiment.Just, with the same secondary cell of making among the example 1-1 to 1-4, except the side at the breach 35 of center pin 30 as shown in Figure 29 provides the stepwise step 35D.
(example 6)
Make the secondary cell of describing in the 6th embodiment.Just, with the same secondary cell of making among the example 1-1 to 1-4, except providing the L shaped bending crack 35 for center pin 30 with triangular cross section.
Respectively for example 3,4-1 to 4-2,5 and 6 make five secondary cells (battery 1 is to battery 5) that as above obtain.These batteries are carried out the appearance that crushing test is lighted and exploded with inspection.In addition, for example 3 and 5, check the duration of short-circuit (up to the time of short circuit).Duration by measuring in five batteries each also obtains its mean value and obtains the duration of short-circuit.The result who obtains shows in form 2.Comparative example 2 is identical with comparative example 1.
[form 2]
As confirming by form 2, according to example 3 with breach 35,4-1,4-2,5 and 6, there is not blast.Simultaneously, in the comparative example that breach 35 is not provided, whole five secondary cells all explode.Just, find when center pin 30 provides bending crack 35 that even battery flattens or breaks and cause short circuit, fail safe can improve.
In addition, when comparative example 3 and example 5, provide the example 5 of step 35D than the example 3 shorter ground short circuits that step 35D is not provided in a side of breach 35.Just, find when the side at breach 35 provides step 35D, negative electrode 21 and anode 22 short circuit more quickly, and fail safe can improve more.
(example 7-1 to 7-4)
The same secondary cell of describing in the 3rd embodiment made from example 1-1 to 1-4, except in example 7-1, arranging two otch 35 in a circumferential direction discretely, in example 7-2, arrange three otch 35 in a circumferential direction discretely, in example 7-3, arrange five otch 35 in a circumferential direction discretely, and in example 7-4, arrange discretely in a circumferential direction outside seven otch 35.
Make five secondary cells (battery 1 is to battery 5) that as above obtain for example 7-1 to 7-4 respectively.These batteries are carried out the appearance that crushing test is lighted and exploded with inspection.The result who obtains shows in form 3.Comparative example 3 is identical with comparative example 1.
[example 3]
As confirming, in all example 7-1 to 7-4, compare with comparative example 3 and can suppress blast by form 3.When being compared to each other example 7-1 to 7-4, the arranging density of breach 35 is high more, and the blast ratio is low more.Especially, in arranging the example 7-4 of seven otch 35 discretely, there is not blast.Just, find when on the circumferencial direction of center pin 30, arranging seven otch 35 discretely, can obtain higher effect.
Reference implementation scheme and case description the present invention.But the present invention is not limited to embodiment and example, and can carry out various modifications.For example, in previous embodiments and previous examples, first otch 32 and second otch 34 have been provided and are the description of the situation in the hole that on thickness direction, penetrates center pin 30.But as shown in Figure 32, first otch 32 and second otch 34 can be the thin grooves that the thickness by the part that reduces center pin 30 on thickness direction obtains.Go for breach 35 equally.
In addition, for example, the shape of first otch 32 is that first otch 32 is connected with secant 31 and corner 33 is enough in the shape that its place, crosspoint forms.Therefore, it is linear that the shape of first otch 32 is not limited to describe in previous embodiments and the previous examples, for example, as shown in Figure 33, can be by being centrosymmetric two butterflies that triangle is formed with secant 31.
In addition, in previous embodiments and previous examples, provided for solvent and used the description of electrolytic solution as the situation of liquid electrolyte.But, can use other electrolyte to replace electrolytic solution.As other electrolyte, for example, can enumerate the mixture that electrolytic solution is contained in the gelated electrolyte in the polymer, the solid electrolyte with ionic conductivity, solid electrolyte and electrolytic solution, perhaps the mixture of solid electrolyte and gelated electrolyte.
For gelated electrolyte, can use various polymer, as long as polymer can absorb and the gelling electrolytic solution.As polymer, can enumerate for example copolymer of Kynoar and vinylidene and hexafluoropropylene of fluorinated polymer, ether polymer is polyethylene glycol oxide and the crosslinked body that comprises polyethylene glycol oxide, polyacrylonitrile etc. for example.Especially, aspect reduction-oxidation stability, fluorinated polymer is expected.
As solid electrolyte, for example, can use electrolyte salt to be dispersed in organic solid electrolyte based in the polymer with ionic conductivity, the perhaps inorganic solid electrolyte that forms by ionic conduction glass, ionic crystals etc.As polymer, for example, can be individually, by mixing, perhaps use ether polymer for example polyethylene glycol oxide and the crosslinked body that comprises polyethylene glycol oxide by copolymerization in molecule, ester polymer is polymethacrylates for example, perhaps acrylate polymer.As inorganic solid electrolyte, can use lithium nitride, lithium iodide etc.
In addition, in previous embodiments and previous examples, provided the description of column secondary battery with spirality winding arrangement.But the present invention goes for having the secondary cell of Any shape, as long as secondary cell has the spirality winding arrangement.In addition, the present invention also goes for primary cell.
In addition, in previous embodiments and previous examples, provided and used the description of lithium as the situation of electrode reaction thing.But the present invention goes for also using that other organize 1 element for example sodium (Na) and potassium (K) in the long period periodic table; Group 2 elements in the long period periodic table are magnesium and calcium (Ca) for example; Other light metals are aluminium for example, the perhaps situation of the alloy of lithium and aforementioned elements, and can obtain similar effects.At that time, for the active material of positive electrode that can insert and extract the electrode reaction thing, can select active material of cathode, solvent etc. according to the electrode reaction thing.
Claims (44)
1. battery comprises:
Spirality is twined electrode body, twine negative electrode and anode and spacer is therebetween obtains by stacked and spirality, negative electrode has the cathode active material bed of material on the surface of bar shaped cathode current collector, and anode has anode active material layers on the surface of bar shaped anode collector; And
Tubular center's pin is arranged in the center that spirality is twined electrode body, has secant on vertically, and has first otch that crosses secant.
2. according to the battery of claim 1, wherein first otch of center pin vertically crosses secant.
3. according to the battery of claim 1, wherein first otch of center pin crosses secant sideling.
4. according to the battery of claim 1, comprise in a circumferential direction position that the secant with center pin departs from the side of crossing secant upwardly extending second otch.
5. according to the battery of claim 4, wherein second otch of center pin is located on the circumferencial direction position towards secant.
6. according to the battery of claim 1, wherein center pin has avette or oval-shaped shape of cross section, and secant is provided at the position of avette or oval-shaped diameter maximum.
7. according to the battery of claim 1, wherein the thickness of center pin is 0.05mm-5mm.
8. according to the battery of claim 1, wherein
Twine negative electrode on the central side of electrode body in spirality and have a end in cathode current collector and do not have the cathode active material bed of material to be provided at negative electrode exposed region on the two sides of cathode current collector, and
Having a end at anode collector at the central side Shangyang that spirality is twined electrode body does not have anode active material layers to be provided at anode exposed region on the two sides of anode collector.
9. according to the battery of claim 1, wherein anode comprises and can insert and extract the electrode reaction thing and comprise metallic element and at least a active material of positive electrode as element of nonmetalloid.
10. according to the battery of claim 9, wherein anode comprises that at least a material as element that comprises tin (Sn) and silicon (Si) is as active material of positive electrode.
11. battery according to claim 9, wherein anode comprises and comprises tin, cobalt (Co) and carbon (C) as element, and the carbon content with 9.9wt%-29.7wt%, and the material of the ratio of the summation of the cobalt of 30wt%-70wt% and tin and cobalt is as active material of positive electrode.
12. a battery comprises:
Spirality is twined electrode body, twine negative electrode and anode and spacer is therebetween obtains by stacked and spirality, negative electrode has the cathode active material bed of material on the surface of bar shaped cathode current collector, and anode has anode active material layers on the surface of bar shaped anode collector; And
Tubular center's pin is arranged in spirality and twines the center of electrode body and provide bending crack,
Secant on wherein center pin has vertically and the otch that crosses secant.
13. according to the battery of claim 12, the breach linear second portion that has linear first and on the direction different, extend wherein from an end of first with the direction of first.
14. according to the battery of claim 12, wherein breach has linear first and the linear second portion that crosses first.
15. according to the battery of claim 12, wherein breach has the circular bend shape.
16. according to the battery of claim 12, wherein the otch of center pin vertically crosses secant.
17. according to the battery of claim 12, wherein the side at breach provides stepwise or zigzag step.
18. according to the battery of claim 17, wherein the bend relief side partly at breach provides step.
19. according to the battery of claim 12, wherein provide a plurality of breaches, and arrange the odd number breach discretely.
20. according to the battery of claim 12, wherein provide a plurality of breaches, and the distance between each of a plurality of breaches is 0.1mm or bigger.
21. according to the battery of claim 12, wherein the thickness of center pin is 0.05mm-5mm.
22. according to the battery of claim 12, wherein center pin has polygonal shape of cross section.
23. according to the battery of claim 12, wherein
Twine negative electrode on the central side of electrode body in spirality and have a end in cathode current collector and do not have the cathode active material bed of material to be provided at negative electrode exposed region on the two sides of cathode current collector, and
Having a end at anode collector at the central side Shangyang that spirality is twined electrode body does not have anode active material layers to be provided at anode exposed region on the two sides of anode collector.
24. according to the battery of claim 12, wherein anode comprises and can insert and extract the electrode reaction thing and comprise metallic element and at least a active material of positive electrode as element of nonmetalloid.
25. according to the battery of claim 24, wherein anode comprises that at least a material as element that comprises tin (Sn) and silicon (Si) is as active material of positive electrode.
26. battery according to claim 24, wherein anode comprises and comprises tin, cobalt (Co) and carbon (C) as element, and the carbon content with 9.9wt%-29.7wt%, and the material of the ratio of the summation of the cobalt of 30wt%-70wt% and tin and cobalt is as active material of positive electrode.
27. a center pin, the spirality that has tubular form and be provided at the battery with spirality winding arrangement is twined the electrode body center, comprising:
Secant vertically; And
Cross first otch of secant.
28. according to the center pin of claim 27, wherein first otch vertically crosses secant.
29. according to the center pin of claim 27, wherein first otch crosses secant sideling.
30. according to the center pin of claim 27, comprise in a circumferential direction the position of departing from, upwardly extending second otch in the side of crossing secant with secant.
31. according to the center pin of claim 30, wherein second otch is located on the circumferencial direction position towards secant.
32. according to the center pin of claim 27, have avette or oval-shaped shape of cross section, wherein secant is provided at the position of avette or oval-shaped diameter maximum.
33., have the thickness of 0.05mm-5mm according to the center pin of claim 27.
34. a center pin, the spirality that has tubular form and be provided at the battery with spirality winding arrangement is twined the electrode body center, it is characterized in that providing bending crack; Secant vertically; And the otch that crosses secant.
35. according to the center pin of claim 34, the breach linear second portion that has linear first and on the direction different, extend wherein from an end of first with the direction of first.
36. according to the center pin of claim 34, wherein breach has linear first and the linear second portion that crosses first.
37. according to the center pin of claim 34, wherein breach has the circular bend shape.
38. according to the center pin of claim 34, wherein otch vertically crosses secant.
39. according to the center pin of claim 34, wherein the side at breach provides stepwise or zigzag step.
40. according to the center pin of claim 39, wherein the bend relief side partly at breach provides step.
41. according to the center pin of claim 34, wherein provide a plurality of breaches, and arrange the odd number breach discretely.
42. according to the center pin of claim 34, wherein provide a plurality of breaches, and the distance between each of a plurality of otch is 0.1mm or bigger.
43., have the thickness of 0.05mm-5mm according to the center pin of claim 34.
44., have polygonal shape of cross section according to the center pin of claim 34.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP323996/2004 | 2004-11-08 | ||
| JP2004323996 | 2004-11-08 | ||
| JP080445/2005 | 2005-03-18 |
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| Publication Number | Publication Date |
|---|---|
| CN101065875A CN101065875A (en) | 2007-10-31 |
| CN100492748C true CN100492748C (en) | 2009-05-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800400728A Active CN100492748C (en) | 2004-11-08 | 2005-11-01 | Battery and center pin |
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|---|---|
| CN (1) | CN100492748C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100216014A1 (en) * | 2009-02-24 | 2010-08-26 | Eveready Battery Company, Inc. | Closure Assembly for Electrochemical Cells |
| CN113386080A (en) * | 2020-03-12 | 2021-09-14 | Oppo（重庆）智能科技有限公司 | Electronic equipment disassembling device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5882815A (en) * | 1996-04-01 | 1999-03-16 | Tagawa; Kazuo | Spiral rolled electrode assembly having a serrated center pin |
| CN1423361A (en) * | 2001-11-28 | 2003-06-11 | 三洋电机株式会社 | Enclosed cell |
| US20040131938A1 (en) * | 2002-09-17 | 2004-07-08 | Takatomo Nishino | Anode material and battery using the same |
-
2005
- 2005-11-01 CN CNB2005800400728A patent/CN100492748C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5882815A (en) * | 1996-04-01 | 1999-03-16 | Tagawa; Kazuo | Spiral rolled electrode assembly having a serrated center pin |
| CN1423361A (en) * | 2001-11-28 | 2003-06-11 | 三洋电机株式会社 | Enclosed cell |
| US20040131938A1 (en) * | 2002-09-17 | 2004-07-08 | Takatomo Nishino | Anode material and battery using the same |
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| Publication number | Publication date |
|---|---|
| CN101065875A (en) | 2007-10-31 |
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Effective date of registration: 20180410 Address after: Kyoto Japan Patentee after: Murata Manufacturing Co.,Ltd. Address before: Fukushima Patentee before: Murata, Northeast China Effective date of registration: 20180410 Address after: Fukushima Patentee after: Murata, Northeast China Address before: Tokyo, Japan Patentee before: Sony Corp. |