(12) United States Patent
`Isozaki et al.
`
`USOO6926992B2
`US 6,926,992 B2
`Aug. 9, 2005
`
`(10) Patent No.:
`(45) Date of Patent:
`
`(54) NONAQUEOUSELECTROLYTE
`SECONDARY BATTERY
`
`(75) Inventors: Yoshiyuki Isozaki, Tokyo (JP); Yuji
`Satoh, Sagamihara (JP); Motoya
`Kanda, Yokohama (JP)
`(73) Assignee: Kabushiki Kaisha Toshiba, Tokyo (JP)
`(*) Notice:
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 251 days.
`
`(21) Appl. No.: 10/184,851
`(22) Filed:
`Jul. 1, 2002
`(65)
`Prior Publication Data
`US 2003/0031919 A1 Feb. 13, 2003
`Foreign Application Priority Data
`(30)
`Jun. 29, 2001
`(JP) ....................................... 2001-198327
`(51) Int. Cl. .......................... H01M 10/52; H01M 2/12
`(52) U.S. Cl. ............................. 429/59; 429/53; 429/56;
`429/82; 429/175
`(58) Field of Search .............................. 429/53, 54, 56,
`429/57, 59, 82, 175
`
`(56)
`
`References Cited
`U.S. PATENT DOCUMENTS
`5,741,606 A * 4/1998 Mayer et al. ................. 429/53
`6,037,071 A * 3/2000 Poirier et al. ...
`... 429/7
`6,210,824 B1
`4/2001 Sullivan et al. ............... 429/53
`
`8/2001 Wu ............................. 429/56
`6,270,918 B1
`6,531,242 B1 * 3/2003 Sugimoto et al. ............. 429/82
`6,620,544 B1
`9/2003 Shin et al. .................... 429/56
`6,723,465 B2 * 4/2004 Segawa et al. ............... 429/56
`6,805,991 B2 10/2004 Abe ............................ 429/56
`FOREIGN PATENT DOCUMENTS
`
`JP
`
`9-92335
`
`4/1997
`
`OTHER PUBLICATIONS
`Kinzoku (Metal) Date Book, Second Revision compiled by
`Nippon Metal Institute and published by Maruzen K. K. on
`Jan. 30, 1984, 9 pages, discussion in Specification only-p.
`12.
`* cited by examiner
`Primary Examiner Tracy Dove
`(74) Attorney, Agent, or Firm-Oblon, Spivak, McClelland,
`Maier & Neustadt, P.C.
`(57)
`ABSTRACT
`Disclosed is a nonaqueous electrolyte Secondary battery
`comprises a Sealing unit including a conductive Support
`plate, wherein the conductive Support plate contains at least
`one kind of a conductive material Selected from the group
`consisting of a metal, an alloy and a composite metallic
`material, each of the metal, the alloy and the composite
`metallic material has a modulus of elasticity (Young's
`modulus) at 25°C. that falls within a range from 1x10' Pa
`to 3.27x10' Pa, and the conductive support plate has an
`area resistance value RS at 20°C. falling within a range from
`0.032 (us2cm?) to 1.24 (uS2cm?).
`20 Claims, 3 Drawing Sheets
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`U.S. Patent
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`Aug. 9, 2005
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`Sheet 1 of 3
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`US 6,926,992 B2
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`F. G. 1
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`U.S. Patent
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`Aug. 9, 2005
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`Sheet 2 of 3
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`US 6,926,992 B2
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`U.S. Patent
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`Aug. 9, 2005
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`Sheet 3 of 3
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`US 6,926,992 B2
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`F. G. 8
`PRIOR ART
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`US 6,926,992 B2
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`1
`NONAQUEOUSELECTROLYTE
`SECONDARY BATTERY
`
`2
`internal pressure of the cell is increased to exceed a designed
`operation pressure to release the gas filling the inner Space
`of the battery container to the outside through the opened
`Safety vent, thereby preventing the explosion of the battery.
`However, in the high rate discharge type nonaqueous
`electrolyte Secondary battery, the operating pressure of the
`Safety vent is nonuniform, giving rise to the inconvenience
`that it is possible for the safety vent not to be operated even
`in the case where the internal preSSure of the cell is increased
`to reach a designed operation pressure by the occurrence of
`an abnormality Such as an overcharge.
`BRIEF SUMMARY OF THE INVENTION
`An object of the present invention is to provide a non
`aqueous electrolyte Secondary battery, which permits Sup
`pressing the nonuniformity of the operating pressure of the
`safety vent so as to improve the reliability of the safety vent
`and, thus, to prevent the explosion of the battery.
`According to a first aspect of the present invention, there
`is provided a nonaqueous electrolyte Secondary battery,
`comprising:
`a CaSC,
`an electrode group provided in the case and including a
`positive electrode, a negative electrode and a nonaqueous
`electrolyte; and
`a Sealing unit arranged in an open portion of the case, the
`Sealing unit including a conductive Safety vent comprising a
`rupture portion that is ruptured by the increase in the internal
`preSSure of the case, a positive electrode terminal, and a
`conductive Support plate arranged between the conductive
`Safety vent and the positive electrode terminal,
`wherein the conductive Support plate contains at least one
`kind of a conductive material Selected from the group
`consisting of a metal having a modulus of elasticity
`(Young's modulus) at 25 C. falling within a range from
`1x10' Pa to 3.27x10' Pa, an alloy having a modulus of
`elasticity (Young's modulus) at 25 C. falling within a range
`from 1x10' Pa to 3.27x10' Pa, and a composite metallic
`material having a modulus of elasticity (Young's modulus)
`at 25°C. falling within a range from 1x10' Pa to 3.27x10'
`Pa, and the conductive Support plate having an area resis
`tance value RS at 20° C. falling within a range from 0.032
`(uS2cm) to 1.24 (uS2 cm).
`Further, according to a Second aspect of the present
`invention, there is provided a nonaqueous electrolyte Sec
`ondary battery, comprising:
`a CaSC,
`an electrode group provided in the case and including a
`positive electrode, a negative electrode and a nonaqueous
`electrolyte; and
`a Sealing unit arranged in an open portion of the case, the
`Sealing unit including a conductive Safety vent comprising a
`rupture portion that is ruptured by the increase in the internal
`preSSure of the case, a positive electrode terminal, and a
`conductive Support plate arranged between the Safety vent
`and the positive electrode terminal,
`the conductive Support plate contains at least one kind of
`a conductive material Selected from the group consisting of
`an alloy containing a metal element having a modulus of
`elasticity (Young's modulus) at 25 C. falling within a range
`from 1x10' Pa to 3.27x10' Pa, and a composite metallic
`material containing a metal element having a modulus of
`elasticity (Young's modulus) at 25 C. falling within a range
`from 1x10' Pa to 3.27x10' Pa, and the conductive support
`plate having an area resistance value RS at 20 C. falling
`within a range from 0.032 (uS2 cm) to 1.24 (uS2 cm).
`
`CROSS-REFERENCE TO RELATED
`APPLICATIONS
`This application is based upon and claims the benefit of
`priority from the prior Japanese Patent Application No.
`2001-198327, filed Jun. 29, 2001, the entire contents of
`which are incorporated herein by reference.
`
`BACKGROUND OF THE INVENTION
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`1. Field of the Invention
`The present invention relates to a nonaqueous electrolyte
`Secondary battery.
`2. Description of the Related Art
`In recent years, a nonaqueous electrolyte Secondary bat
`tery Such as a lithium-ion Secondary battery or a polymer
`lithium Secondary battery is widely used in an electronic
`appliance Such as a portable telephone. These Secondary
`batteries of this type have a lightweight, a high energy
`density, and provide a high operating Voltage near 4V
`compared with a nickel-cadmium battery or a nickel-metal
`25
`hydride secondary battery. The excellent performance of the
`Secondary battery of the type noted above attracts keen
`attentions in this technical field.
`In recent years, it is Studied to use the particular non
`aqueous electrolyte Secondary battery as a power Source for
`an electric vehicle, an electric tool, uninterruptible power
`Supply or a cordleSS cleaner. In Such a use, required is high
`power performance, compared with a nonaqueous electro
`lyte Secondary battery used in an electronic appliance Such
`as a portable telephone.
`In order to increase the high rate discharge capacity of the
`battery for obtaining a high power battery, it is necessary to
`decrease the internal resistance of the battery as much as
`possible. For decreasing the internal resistance of the
`battery, it is important to lower the resistance of the elec
`trode and the component parts to increase the current
`collecting efficiency. A measure for achieving the object is
`the development of a cylindrical lithium-ion Secondary
`battery or a prismatic lithium-ion Secondary battery com
`prising a plurality of current collecting leads connected to an
`45
`electrode, as proposed in, for example, Jpn. Pat. Appln.
`KOKAI Publication No. 9-92335. The particular construc
`tion makes it possible to improve the current collecting
`efficiency, to lower the internal resistance of the cell, and to
`obtain a battery excellent in the high rate discharge charac
`teristics. Also, in a high rate discharge type lithium Second
`ary battery of this type, it is possible to charge the Secondary
`battery with a large current So as make it possible to achieve
`a rapid charging.
`In a nonaqueous electrolyte Secondary battery, it is
`Strongly required in general to ensure the Safety in the event
`of an abnormal increase in the internal pressure of the cell
`caused by the inappropriate handling Such as the situation
`that the Secondary battery is left to Stand under a high
`temperature atmosphere for a long time, an overcharge, or an
`external short-circuiting, not to mention the Safety of the
`Secondary battery during the normal use. In order to ensure
`the Safety, the nonaqueous electrolyte Secondary battery is
`provided with a safety vent that is operated by the internal
`preSSure of the cell battery, thereby preventing the explosion
`of the battery. In the nonaqueous electrolyte Secondary
`battery of this type, the Safety vent is opened when the
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`US 6,926,992 B2
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`3
`Further, according to a third aspect of the present
`invention, there is provided a nonaqueous electrolyte Sec
`ondary battery, comprising:
`a CaSC,
`an electrode group provided in the case and including a
`positive electrode, a negative electrode and a nonaqueous
`electrolyte; and
`a Sealing unit arranged in an open portion of the case, the
`Sealing unit including a conductive Safety vent comprising a
`rupture portion that is ruptured by the increase in the internal
`preSSure of the case, a positive electrode terminal, and a
`conductive Support plate arranged between the Safety vent
`and the positive electrode terminal,
`the conductive Support plate comprises a Supporting body
`and a Surface layer formed on at least a part of a Surface of
`the Supporting body, each of the Supporting body and the
`Surface layer contains a metal element having a modulus of
`elasticity (Young's modulus) at 25 C. that falls within a
`range from 1x10' Pa to 3.27x10' Pa.
`BRIEF DESCRIPTION OF THE SEVERAL
`VIEWS OF THE DRAWING
`FIG. 1 is a partial croSS Sectional view exemplifying the
`construction of a nonaqueous electrolyte Secondary battery
`of the present invention;
`FIG. 2 is a Schematic drawing for explaining the lead
`fixing member incorporated in the nonaqueous electrolyte
`secondary battery shown in FIG. 1;
`FIG. 3 is an oblique views showing the construction of the
`Safety Vent incorporated in the nonaqueous electrolyte Sec
`ondary battery shown in FIG. 1;
`FIG. 4 is a plan view showing the safety vent shown in
`FIG. 3 as viewed from the bottom side;
`FIG. 5 is a Schematic drawing for explaining the conduc
`tive Support plate incorporated in the nonaqueous electrolyte
`secondary battery shown in FIG. 1;
`FIG. 6 is a croSS Sectional view showing in a magnified
`fashion the Sealing unit and the positive electrode lead
`incorporated in the nonaqueous electrolyte Secondary bat
`tery shown in FIG. 1;
`FIG. 7 is a croSS Sectional view showing in a magnified
`fashion the operating State of the current breaking mecha
`nism included in the nonaqueous electrolyte Secondary
`battery shown in FIG. 1; and
`FIG. 8 is a cross sectional view showing the construction
`of the Safety vent used in the conventional nonaqueous
`electrolyte Secondary battery.
`
`DETAILED DESCRIPTION OF THE
`INVENTION
`The inconvenience of the safety vent is considered to be
`caused as follows. Specifically, FIG. 8 is a cross sectional
`View showing the construction of a conventional Safety vent.
`AS shown in the drawing, a Safety vent 31 is electrically
`connected to a positive electrode lead 32 and exposed to the
`atmosphere within the cell, with the result that the safety
`vent 31 tends to be corroded by the nonaqueous electrolyte
`or to be Subjected to an electrochemical corrosion. In order
`to prevent the corrosion, it is desirable for the safety vent 31
`to be formed of aluminum. However, aluminum has a high
`ductility, i.e., has a low bending rigidity. Therefore, the
`safety vent 31 is pushed upward if the internal pressure of
`the cell begins to be increased, with the result that a
`peripheral portion 33 of the safety vent 31 is deformed, as
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`4
`shown in FIG.8. Further, an additional problem is generated
`that, even if the Safety vent 31 having a mechanical Strength
`as designed is prepared, a boundary between the peripheral
`portion 33 and a rupture portion is corroded by the non
`aqueous electrolyte, resulting in failure to obtain a mechani
`cal Strength as designed. Because of generation of the
`particular problem, if the peripheral portion 33 of the safety
`vent is much deformed, the rupture portion is not ruptured
`promptly in Some cases even if the internal pressure of the
`cell is increased to reach a designed operation pressure.
`AS a result of an extensive research conducted by the
`present inventors in an attempt to overcome the problems
`noted above, it has been found that a nonaqueous electrolyte
`Secondary battery Satisfying both the high rate discharge
`characteristics and the Safety can be obtained by arranging
`a conductive Support plate having a prescribed bending
`rigidity and a resistance value on the peripheral portion of
`the safety vent.
`To be more specific, the nonaqueous electrolyte Second
`ary battery according to the present invention comprises an
`electrode group including a positive electrode, a negative
`electrode, and a nonaqueous electrolyte arranged between
`the positive electrode and the negative electrode, a battery
`case electrically connected to the negative electrode, a
`conductive Safety vent that is arranged in the open portion of
`the battery case to Seal the battery case and is ruptured by the
`increase in the internal pressure of the cell, and a positive
`electrode terminal electrically connected to the positive
`electrode with the safety vent interposed therebetween. The
`nonaqueous electrolyte Secondary battery of the present
`invention is featured in that a conductive Support plate
`described below is arranged between the safety vent and the
`positive electrode terminal So as to fix the peripheral portion
`of the safety vent.
`The conductive Support plate used in the Secondary bat
`tery of the present invention contains at least one kind of a
`conductive material Selected from the group consisting of a
`first metal having a modulus of elasticity (Young's modulus)
`at 25°C. falling within a range from 1x10' Pa to 3.27x10'
`Pa, a first alloy having a modulus of elasticity (Young's
`modulus) at 25°C. falling within a range from 1x10' Pa to
`3.27x10' Pa, a first composite metallic material having a
`modulus of elasticity (Young's modulus) at 25 C. falling
`within a range from 1x10' Pa to 3.27x10' Pa, a second
`alloy containing a metal element having a modulus of
`elasticity (Young's modulus) at 25 C. falling within a range
`from 1x10' Pa to 3.27x10' Pa, and a second composite
`metallic material containing a metal element having a modu
`lus of elasticity (Young's modulus) at 25 C. falling within
`a range from 1x10' Pa to 3.27x10' Pa. It is possible for the
`modulus of elasticity (Young's modulus) at 25 C. of the
`conductive Support plate to be equal to or to differ from the
`modulus of elasticity (Young's modulus) at 25 C. of at least
`one kind of the conductive material noted above.
`Also, the conductive Support plate used in the present
`invention has an area resistance value RS at 20° C. falling
`within a range from 0.032 uS2 cm to 1.24 uS2 cm’.
`If the modulus of elasticity is smaller than 1x10' Pa, the
`ductility of the conductive Support plate is increased, with
`the result that the peripheral portion of the safety vent tends
`to be deformed when the internal pressure of the cell is
`increased So as to make it difficult to SuppreSS the nonuni
`formity in the operating pressure of the Safety vent. On the
`other hand, it is difficult to process easily a conductive
`material having a Young's modulus at 25 C. exceeding
`3.27x10' Pa and a conductive material containing a metal
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`S
`element having a Young's modulus at 25 C. exceeding
`3.27x10' Pa for forming a conductive support plate, with
`the result that the mass productivity of the Secondary battery
`tends to be impaired. It is desirable for the conductive
`Support plate to be formed of a material having the modulus
`of elasticity (Young's modulus) at 25 C. falling within a
`range from 1.36x10' Pa to 2.2x10' Pa. Where the modulus
`of elasticity (Young's modulus) falls within the range noted
`above, the effect of improving the Safety is increased.
`The metal having a modulus of elasticity (Young's
`modulus) at 25°C. falling within a range from 1x10' Pa to
`3.27x10' Pa includes, for example Co (from 2.1x10' Pa to
`2.2x10' Pa), Cr (2.53x10' Pa), Cu (1.36x10' Pa), Fe
`(1.90x10 Pa), Mo (3.27x10' Pa), Ni (2.05x10' Pa), Ta
`(1.811x10 Pa) and V (1.326x10' Pa). Particularly, it is
`desirable to use Ni, Cu or both of Ni and Cu as the metal
`having the modulus of elasticity noted above.
`The modulus of elasticity (Young's modulus) at 25 C. of
`each of the metal elements is based on “International Tables
`of Selected Constants, 16, Metals, Thermal and Mechanical
`Data” given in Tables 1 and 231 on page 35 of “Kinzoku
`(Metal) Data Book, Second Revision” compiled by Nippon
`Metal Institute and published by Maruzen K. K. on Jan. 30,
`1984. The modulus of elasticity (Young's modulus) is
`denoted by the unit “dyn/cm” in the Table given above, and
`the unit is converted into “Pa” in this specification.
`It is desirable for the first alloy having the modulus of
`elasticity (Young's modulus) at 25 C. falling within a range
`from 1x10' Pa to 3.27x10' Pa to have a composition
`containing at least one element Selected from the group
`consisting of Ni and Cu. Particularly, it is desirable for the
`first alloy to have a composition containing Ni and Fe. In the
`case of using the particular alloy, it is possible to further
`improve the Safety of the Secondary battery.
`The first composite metallic material used in the present
`invention for forming the conductive Support plate includes,
`for example, a metal plate having a metal layer or an alloy
`layer formed on at least a part of the Surface by, for example,
`the plating, an alloy plate having a metal layer or an alloy
`layer formed on at least a part of the Surface by, for example,
`the plating, a clad material, a metal mesh Supporting a
`material containing a metal or an alloy, or a mixture con
`taining at least one of a metal and an alloy, and a binder.
`It is desirable for the first composite metallic material
`having a modulus of elasticity (Young's modulus) at 25 C.
`falling within a range from 1x10' Pa to 3.27x10' Pa to
`have a composition containing at least one kind of an
`element Selected from the group consisting of Ni and Cu.
`Particularly, it is desirable for the first composite metallic
`material to have a composition containing both Ni and Cu.
`In the case of using the particular composite metallic
`material, it is possible to further improve both the high rate
`discharge characteristics and the Safety of the Secondary
`battery.
`The second alloy used in the present invention for form
`ing the conductive Support plate, the Second alloy containing
`a metal element having a modulus of elasticity (Young's
`modulus) at 25°C. falling within a range from 1x10' Pa to
`3.27x10' Pa, includes, for example, alloys containing at
`least one kind of a metal element Selected from the group
`consisting of Co, Cr, Cu, Fe, Mo, Ni, Ta and V. Among the
`alloys noted above, it is desirable to use an alloy containing
`at least one metal element Selected from the group consisting
`of Ni and Cu. Particularly, it is desirable to use the Ni-Fe
`alloy because the alloy permits further improving the Safety
`of the Secondary battery.
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`US 6,926,992 B2
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`6
`The Second conductive Support plate containing a com
`posite metallic material, which is used in the present
`invention, Said Second composite metallic material contain
`ing a metal element having a modulus of elasticity (Young's
`modulus) at 25°C. falling within a range from 1x10' Pa to
`3.27x10' Pa, includes, for example, a structure comprising
`a Support body and a Surface layer formed in at least a part
`of the Surface of Said Support body, a clad material contain
`ing Said metal element, a metal mesh Supporting a conduc
`tive powder, and a mixture containing a metal powder and
`a binder. At least one of the Support body and the Surface
`layer noted above is formed of a metal element having a
`modulus of elasticity (Young's modulus) at 25 C. falling
`within a range from 1x10' Pa to 3.27x10' Pa or an alloy
`containing the metal element noted above. Also, at least one
`of the metal mesh and the conductive powder contains a
`metal element having a modulus of elasticity (Young's
`modulus) at 25°C. falling within a range from 1x10' Pa to
`3.27x10' Pa.
`Particularly, it is desirable to use a conductive Support
`plate comprising a conductive Support body containing the
`metal element noted above and a Surface layer formed in at
`least a part of the Surface of the Support body and containing
`the metal element. In the case of using the particular
`conductive Support plate, it is possible to further improve
`both the high rate discharge characteristics and the Safety of
`the Secondary battery.
`Each of the first composite metal material containing both
`Ni and Cu and the Second composite metal material con
`taining both Ni and Cu includes, for example, a
`Cu-containing plate having both main Surfaces plated with
`Ni. It is desirable for the Sum of the thickness of the first
`plated Ni-containing layer on one main Surface of the
`Cu-containing plate and the thickness of the Second plated
`Ni-containing layer on the other main Surface of the
`Cu-containing plate to fall within a range from 2 um to 10
`tim. If the total thickness of the first and Second plated
`Ni-containing layerS is Smaller than 2 um, the resistance to
`corrosion of the conductive Support plate caused by the
`nonaqueous electrolyte is lowered, with the result that the
`high rate discharge characteristics or the Safety of the
`secondary battery tend to be impaired. On the other hand, if
`the total thickness of the first and Second plated
`Ni-containing layers exceeds 10 tim, it is possible for the
`manufacturing cost to be increased. It is more desirable for
`the total thickness of the first and Second plated
`Ni-containing layers to fall within a range from 4 um to 6
`plm.
`In the first composite metal material and the Second
`composite metal material, it is desirable for the clad material
`containing both Ni and Cu to comprise a Cu-containing
`layer and nickel-containing layerS laminated on both Sur
`faces of the Cu-containing layer. The term “clad material”
`noted above represents a composite metal material prepared
`by making integral at least two different kinds of metal
`bodies such that the interfaces of the different kinds of metal
`bodies are fused to each other by the diffusion joining. The
`clad material can be commercially manufactured by, for
`example, the Sintering or diffusion annealing method in
`which the raw material is Subjected to a hot rolling or cold
`rolling, followed by heating the rolled raw material in, for
`example, an electric furnace. Also, where the thickness of
`the Cu-containing layer is Set at 1, it is desirable for the total
`thickness of the Ni-containing layerS plated on both Surfaces
`of the Cu-containing layer to fall within a range of between
`0.1 and 1. If the total thickness of the Ni-containing layers
`is Smaller than 0.1 relative to the thickness of the
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`7
`Cu-containing layer that is Set at 1, the bonding Strength at
`the interface between the Cu-containing layer and the
`Ni-containing layers tends to be lowered, with the result that
`a clearance tends to be generated in the bonding interface
`and that the Ni-containing layers tend to be peeled off the
`Cu-containing layer. On the other hand, if the total thickneSS
`of the Ni-containing layerS exceeds 1 relative to the thick
`neSS of the Cu-containing layer that is Set at 1, the area
`resistance value at 20 C. of the conductive Support plate
`tends to be increased. It is more desirable for the total
`thickness of the Ni-containing layerS relative to the thick
`neSS of the Cu-containing layer that is Set at 1 to fall within
`a range from 0.25 to 0.5.
`It is possible for each of the first alloy, the second alloy,
`the first composite metal material and the Second composite
`metal material to contain additional elements Such as Ti.
`In the nonaqueous electrolyte Secondary battery of the
`present invention, it is desirable for the conductive material
`noted above to be formed of a metal Selected from the group
`consisting of nickel, copper, and a metallic material con
`taining nickel or copper as a main component.
`It is desirable for the conductive Support plate to contain
`the material or the metal element in amount falling within a
`range from 80 to 100% by weight. Incidentally, the material
`is at least one kind of the conductive material Selected from
`the group consisting the first metal, the first alloy and the
`first composite metallic material. Also, the metal element
`has a modulus of elasticity (Young's modulus) at 25 C. that
`falls within a range from 1x10' Pa to 3.27x10' Pa.
`If either the amount of said at least one kind of the
`conductive material or the amount of Said metal element
`contained in the conductive Support plate is Smaller than
`80% by weight, it is difficult to suppress sufficiently the
`deformation in the peripheral portion of the Safety vent when
`the internal preSSure of the cell is increased, with the result
`that the nonuniformity in the operating pressure of the Safety
`vent tends to be increased. It is more desirable for the
`amount of the at least one kind of the conductive material
`noted above to fall within a range from 90 to 100% by
`weight, most desirably from 95 to 100% by weight. On the
`other hand, it is more desirable for the amount of the metal
`element noted above to fall within a range from 90 to 100%
`by weight, most desirably from 95 to 100% by weight.
`The area resistance value RS at 20° C. of the conductive
`Support plate is calculated by formula (1) given below:
`(1)
`RS=RXS
`where R represents the resistance value (u2) at 20° C. of
`the conductive Support plate, and S represents the area (cm)
`of the main surface of the conductive support plate. Where
`the conductive Support plate is shaped, for example, annular
`as shown in the plan view of FIG. 5, the region of half-tone
`dot meshing in FIG. 5 denotes the main surface of the
`conductive Support plate.
`The resistance value (uS2) at 20° C. of the conductive
`Support plate can be measured by, for example, a four-probes
`method.
`The four-probes method is a method in which the current
`and the Voltage are measured by different circuits.
`Specifically, a current up to 1A is allowed to flow through
`two optional points of the conductive Support plate for the
`time not exceeding 5 Seconds So as to measure the Voltage
`at the measuring point. The resistance value is calculated by
`the Ohm’s law from the relationship between the flowing
`current and the measured Voltage. It is necessary for the
`measurement to be performed under the condition that a
`
`1O
`
`15
`
`25
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`US 6,926,992 B2
`
`8
`Sufficiently uniform temperature is maintained in the envi
`ronment in which the conductive Support plate is positioned
`and that it needs for the measurement to prevent from being
`affected by both of the heat radiation and the compulsory
`flow of the air. Also, the allowable deviation in the tem
`perature at which the resistance value is measured should be
`20° C.2° C.
`If the surface resistance value RS at 20° C. of the
`conductive Support plate exceeds 1.24 uS2 cm, the high rate
`discharge characteristics of the nonaqueous electrolyte Sec
`ondary battery are lowered. On the other hand, the high rate
`discharge characteristics of the Secondary battery are
`improved with decrease in the area resistance value RS.
`However, a large current tends to flow easily through the
`Secondary battery in the event of the abnormality Such as an
`overcharge. Therefore, if the area resistance value RS at 20
`C. of the conductive support plate is smaller than 0.032
`AuS2 cm, a rapid temperature elevation or a gas generation
`tend to take place in the event of an abnormality Such as an
`overcharge So as to increase the probability of bringing
`about the explosion or ignition. It is desirable for the area
`resistance value RS at 20° C. of the conductive Support plate
`to fall within a range from 0.05 uS2 cm to 0.35 uS2 cm’. If
`the area Surface resistance value RS falls within the range
`noted above, the high rate discharge characteristics of the
`Secondary battery can be markedly improved. It is more
`desirable for the area resistance value RS at 20° C. of the
`conductive support plate to fall within a range from 0.05
`tuS2 cm to 0.21 uS2 cm.
`In the nonaqueous electrolyte Secondary battery of the
`present invention, the peripheral portion of the Safety vent is
`firmly supported by the conductive support plate. Therefore,
`the peripheral portion of the Safety vent is not deformed even
`if the internal pressure of the cell is increased by the
`occurrence of an abnormality Such as an overcharge. It
`follows that the rupture portion is promptly ruputured in the
`case where the internal preSSure of the cell is increased to
`exceed a designed operation preSSure. As a result, the gas
`filling the inner Space of the battery case is released to the
`outside So as to prevent the explosion of the battery. AS a
`result, it is possible to realize a nonaqueous electrolyte
`Secondary battery excellent in both of the high rate discharge
`characteristics and Safety.
`The thickness of the conductive Support plate can be set
`at an optional value as far as the area resistance value RS at
`20° C. falls within the range specified in the present inven
`tion. However, it is desirable for the thickness of the
`conductive Support plate to fall within a range from 0.2 mm
`to 0.5 mm. If the thickness of the conductive support plate
`exceeds 0.5 mm, an inconvenience tends to take place in the
`caulking process So as to bring about leakage of the elec
`trolyte. On the other hand, if the thickness of the conductive
`Support plate is Smaller than 0.2 mm, it is difficult to obtain
`a Sufficient effect of improving the Safety. It is more desir
`able for the thickness of the conductive support plate to fall
`within a range from 0.25 mm to 0.35 mm.
`The positive electrode, the negative electrode and the
`nonaqueous electrolyte included in the nonaqueous electro
`lyte secondary battery of the present invention will now be
`described.
`a) Positive E