CA2281136C - Lithium secondary cell - Google Patents
Lithium secondary cell Download PDFInfo
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- CA2281136C CA2281136C CA002281136A CA2281136A CA2281136C CA 2281136 C CA2281136 C CA 2281136C CA 002281136 A CA002281136 A CA 002281136A CA 2281136 A CA2281136 A CA 2281136A CA 2281136 C CA2281136 C CA 2281136C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/172—Arrangements of electric connectors penetrating the casing
- H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
- H01M50/179—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for cells having curved cross-section, e.g. round or elliptic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/547—Terminals characterised by the disposition of the terminals on the cells
- H01M50/548—Terminals characterised by the disposition of the terminals on the cells on opposite sides of the cell
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/552—Terminals characterised by their shape
- H01M50/559—Terminals adapted for cells having curved cross-section, e.g. round, elliptic or button cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/562—Terminals characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/571—Methods or arrangements for affording protection against corrosion; Selection of materials therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Connection Of Batteries Or Terminals (AREA)
- Secondary Cells (AREA)
Abstract
For use in lithium secondary cells, a positive electrode terminal 51 and a negative electrode terminal 81 are given an enhanced mechanical strength to improve the reliability of electrical connection between the cell and an external circuit, while the formation of oxide film on these terminals is inhibited to suppress the discharge voltage drop of the cell. To give these advantages to the lithium secondary cell embodying the invention, the positive electrode terminal 51 is formed from an aluminum alloy containing magnesium and silicon in a combined amount of at least 1.0 wt.% as additive elements, and the negative electrode terminal 81 is formed by plating a substrate of oxygen-free copper with nickel.
Description
TITLE OF THE INVENTION
LITHIUM SECONDARY CELL
FIELD OF THE INVENTION
The present invention relates to lithium secondary cells, i.e., to improvements in lithium secondary cells wherein the negative electrode is made chiefly from metallic lithium, lithium alloy and/or a carbon material or oxide material capable of absorbing and desorbing lithium, and the positive electrode is prepared mainly from a positive electrode material typical of which is a metallic oxide.
More particularly the invention relates to improvements in the positive electrode terminal and the negative electrode terminal for delivering current from an electrode unit serving as the electricity generating element to an external circuit.
BACKGROUND OF THE INVENTION
The negative electrode materials heretofore proposed for use in lithium secondary cells include graphite, coke and like carbon materials, metallic lithium, lithium alloys and tin oxides. Among these, carbon materials are already in use for negative electrodes to provide lithium secondary cells.
Graphite is one of the materials which are generally used for negative electrodes because graphite exhibits a discharge potential in close proximity to the potential of metallic lithium to afford lithium secondary cells of high energy density.
For example, JP-A No. 92335/1997 discloses one of lithium secondary cells wherein such materials are used for the negative electrode. The proposed cell has a negative electrode prepared from a carbon material and a negative electrode output terminal made from pure copper. Pure copper remains stable at the negative electrode potential during the charging and discharging of the lithium secondary cell and is therefore used for the negative electrode output terminal.
Besides pure copper, titanium, nickel, stainless steel, etc.
appear useful as potentially stable materials, whereas pure copper is thought suitable in view of ease of working.
However, pure copper is susceptible to oxidation and liable to form an oxide film at the portion of the cell exposed to the atmosphere, so that when used for the negative electrode terminal, pure copper has the problem of giving increased contact resistance at the connection to an external circuit, causing faulty contact to result in a discharge '2 voltage drop.
On the other hand, pure aluminum is used for the positive electrode terminal of such a lithium secondary cell (see, for example, JP-A No. 92335/1997) since pure aluminum is also stable at the positive electrode potential during the charging and discharging of the cell. Although titanium, stainless steel, etc. appear useful as potentially stable materials besides pure aluminum, pure aluminum is considered to be suitable from the viewpoint of easy of working, conductivity and material cost.
Pure aluminum is nevertheless prone to form an oxide film, so that when used for the positive electrode terminal, this metal has the problem of offering greater contact resistance at the connection to an external circuit, giving rise to faulty contact or causing a discharge voltage drop as in the case of the negative electrode terminal.
Moreover, the positive or negative electrode terminal is not always satisfactory in mechanical strength and is not always suitable to tighten up with sufficiently great torque when a lead is to be attached thereto for connection to an external power source. This entails the problem that the terminal mount portion will not be sealed off effectively.
;3 SUMMARY OF THE INVENTION
An object of the present invention, which is to overcome these problems, is to propose improved positive electrode terminal and negative electrode terminal, and an improved electrode terminal for a positive or negative electrode, for use in delivering the electric energy produced by an electricity generating element to an external device, and to further provide a lithium secondary cell having the positive electrode terminal and/or the negative electrode terminal.
Another object of the invention is to use the positive electrode terminal and/or the negative electrode terminal to assure the terminal or terminals of an enhanced mechanical strength in fabricating the cell and thereby improve the reliability of electrical connection of the cell to an external circuit and give an improved sealing effect to the terminal mount portion or portions. The formation of oxide film on the surfaces of the positive and negative electrode terminals is inhibited, enabling the terminals to retain high conductivity to suppress the discharge voltage drop of the cell.
To fulfill the above objects, the present invention provides a lithium secondary cell which comprises an battery can, a positive electrode terminal, a negative electrode terminal, an electrode unit and an insulating member, the battery can having the electrode unit housed therein, the electrode unit having a positive electrode and a negative electrode which are electrically connected to the positive electrode terminal and the negative electrode terminal, respectively, the electrode terminals being insulated from each other by the insulating member. The lithium secondary cell is characterized in that the positive electrode terminal is formed from an aluminum alloy containing at least 1.0 wt. % of a different metal as an additive element.
With the lithium secondary cell of the invention, the positive electrode terminal has a remarkably improved strength and can therefore be tightened up with sufficiently great torque.
Stated more specifically, the different metal in the aluminum alloy can be at least one element selected from the group consisting of Mg, Si, Fe, Cu, Mn, Zn, Cr and B.
When the aluminum alloy contains at least 0.30 wt. % to not greater than 0.85 wt. % of Mg, reduced electric resistance will result, giving the cell an increased power density.
Reduced electric resistance and an increased cell power density are available alternatively when the aluminum alloy contains at least 0.25 wt. % to not greater than 0.75 wt. % of Si.
Further stated more specifically, the aluminum alloy has the composition of A6101 prescribed in JIS, i.e., a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.%
of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. $ of B
and the balance Al.
The cell can be so constructed that the battery can and the positive electrode terminal are insulated from each other by the insulating member. Further the battery can and the negative electrode terminal can be insulated from each other by the insulating member. Additionally, the battery can and the positive electrode terminal, as well as the battery can and the negative electrode terminal, may be insulated from each other by the insulating member.
The present invention provides another lithium secondary cell which comprises an battery can, a positive electrode terminal, a negative electrode terminal, an electrode unit and an insulating member, the battery can having the electrode unit housed therein, the electrode unit having a positive electrode and a negative electrode which are electrically connected to the positive electrode terminal and the negative electrode terminal, respectively, the electrode terminals being insulated from each other by the insulating member. The lithium secondary cell is characterized in that the negative electrode terminal is formed by plating a substrate of copper with nickel.
Most suitably, the substrate of the negative electrode terminal is made of oxygen-free copper.
The present invention provides another lithium secondary cell which comprises an battery can, an electrode terminal, an electrode unit and an insulating member, the battery can having the electrode unit housed therein, the electrode unit having two electrodes electrically connected to the electrode terminal and the battery can, respectively, the electrode terminal and the battery can being insulated from each other by the insulating member.
When serving as the positive electrode terminal, the electrode terminal is formed from an aluminum alloy containing at least 1.0 wt. % of a different metal as an additive element. Alternatively when serving as the negative electrode terminal, the electrode terminal is formed by plating a substrate of copper with nickel.
With the lithium secondary cell described of the invention, the electrode terminal has a remarkably improved strength and can therefore be tightened up with sufficiently great torque. Consequently, the terminal mount portion, i.e., the portion where the terminal is attached, is given an enhanced sealing effect.
Stated more specifically, the different metal in the aluminum alloy can be at least one element selected from the group consisting of Mg, Si, Fe, Cu, Mn, Zn, Cr and B.
When the aluminum alloy contains at least 0.30 wt. %
to not greater than 0.85 wt. % of Mg, reduced electric resistance will result, giving the cell an increased power density.
Reduced electric resistance and an increased cell power density are available alternatively when the aluminum alloy contains at least 0.25 wt. % to not greater than 0.75 wt. %
of Si.
Further stated more specifically, the aluminum alloy has the composition of A6101 prescribed in JIS, i.e., a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B and the balance Al.
Further it is most suitable that the substrate of copper be oxygen-free copper.
Examples of materials usable for the negative electrode of the cell of the invention are graphite, coke and like carbon materials, metallic lithium, lithium alloys and tin oxides.
Examples of materials usable for the positive electrode of the cell of the invention are a wide variety of those which have heretofore been used in nonaqueous-type cells, such as lithium containing composite oxides (e.g., LiCoO2).
Such a material is used as a kneaded mixture in combination with an electrically conductive agent, such as acetylene black or carbon black, and a binder, such as polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVdF).
Further examples o t solvents tiseful for forming the electrolyte are e:hvlene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ciiethyl carbonate, methylethyl carbonate, sulfolane, 3-methylsulfolane, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran and 1,3-dioxolane. These solvents are usable singly or in mixture. However, these ex<~mpl.es are not limitative.
Examples of preferr-=d electralytes are generally those containing flucrine, such as lithium hexafluorophosphate, because these electrolytes are stable and advantageous from the viewpoint cf discharge capaci;.y and c- harge-discharge cycle characteristics. specific examples of useful electrolytes are LiPF;,, L:L13F,, LiC'-',SO;, LiAsF",, LiN ( CF,SO, LiN ( CF,SO. )( C,F,SOz ), LiN r,, I'So ),,.:nd at Least (Dne of mixttlres of such compounds.
Examples of separators usab--e in t'ne lithium secondary cell embodving the invention are a wide variety of those having 'nigh ionic condut_.t;.vi'.-y an(d conventionally used in lithium secondary cells, si.ich as f_irlely p~)-Lous membranes of polyethylene or polyp.ro~;ylene.
li~
A further aspect, the present invention resides in a lithium secondary cell comprising a battery can having two ends and at least one lid at one end, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals attached as electrically insulated from each other to the battery can and lid, and the positive and negative electrode terminals extending through a hole in the lid of the can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals, respectively, the lithium secondary cell being characterized in that the positive electrode terminal is formed from an aluminum alloy containing additive elements selected from the group consisting of Mg, Si, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains at least magnesium and silicon as the additive elements and wherein the additive elements cumulatively total at least 1.0 wt. % of the aluminum alloy.
In another aspect, the present invention resides in a lithium secondary cell comprising a battery can having two ends and at least one lid at one end, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals attached as electrically insulated from each 10a other to the battery can and lid, and the positive and negative electrode terminals extending through a hole in the lid of the can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals, respectively, the lithium secondary cell being characterized in that the positive electrode terminal is formed from an aluminum alloy containing at least 1.0 wt. % in total of at least one element selected from the group consisting of Si, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains 0.30 wt. % to not greater than 0.85 wt. % of Mg.
In a further aspect, the present invention resides in a lithium secondary cell comprising a battery can having two ends and at least one lid at one end, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals attached as electrically insulated from each other to the battery can and lid, and the positive and negative electrode terminals extending through a hole in the lid of the can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals, respectively, the lithium secondary cell being characterized in that the positive electrode terminal is formed from an aluminum alloy containing at least 1.0 wt. % in total of at least one 10b element selected from the group consisting of Mg, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains 0.25 wt. % to not greater than 0.75 wt. % of Si.
In another aspect, the present invention resides in a lithium secondary cell comprising a battery can having two ends and at least one lid at one end, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals attached as electrically insulated from each other to the battery can and lid, and the positive and negative electrode terminals extending through a hole in the lid of the can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals, respectively, the lithium secondary cell being characterized in that the positive electrode terminal is formed from an aluminum alloy having a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. %
of B and the balance Al.
In a further aspect, the present invention resides in a positive electrode terminal for use in a lithium secondary cell, wherein the positive electrode terminal formed from an aluminum alloy containing at least 1.0 wt. % in total of at least one element selected from the group consisting of lOc Si, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains 0.30 wt. % to not greater than 0.85 wt. % of Mg;
and the secondary cell comprises a battery can, having two ends and a lid attached to one end, wherein the electrode terminal extends through a hole in the can, and the electrode terminal is attached to the lid.
In another aspect, the present invention resides in a positive electrode terminal for use in a lithium secondary cell, wherein the positive electrode terminal formed from an aluminum alloy containing at least 1.0 wt. % in total of at least one element selected from the group consisting of Mg, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains 0.25 wt. % to not greater than 0.75 wt. % of Si;
and the secondary cell comprises a battery can, having two ends and a lid attached to one end, wherein the electrode terminal extends through a hole in the can, and the electrode terminal is attached to the lid.
In a further aspect, the present invention resides in a positive electrode terminal for use with a lithium secondary cell, wherein the positive electrode terminal formed from an aluminum alloy having a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B and the balance Al; and the secondary cell comprises a battery can, 10d having two ends and a lid attached to one end, wherein the electrode terminal extends through a hole in the can, and the electrode terminal is attached to the lid.
In another aspect, the present invention resides in a lithium secondary cell comprising a battery can, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals which are attached as electrically insulated from each other to the battery can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals respectively, the lithium secondary cell being characterized in that the negative electrode terminal is formed by plating a substrate of oxygen-free copper with nickel, and the positive electrode terminal having an aluminum alloy having a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B, and the balance Al.
In a further aspect, the present invention resides in a positive electrode terminal for use in lithium secondary cells which is formed from an aluminum alloy, the positive electrode terminal for use in lithium secondary cells being characterized in that the aluminum alloy has a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of 10e Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B and the balance Al.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view showing the appearance of l Of a cylindrical lithium secondary cell as a first embodiment of the invention;
FIG. 2 is an exploded perspective view of the lithium secondary cell;
FIG. 3 is a fragmentary view in section of the lithium secondary cell;
FIG. 4 is a perspective view showing the appearance of another cylindrical lithium secondary cell as a second embodiment of the invention; and FIG. 5 is a graph showing the relationship between the aluminum content and the incidence of leak.
DETAILED DESCRIPTION OF EMBODIMENTS
The present invention will be described in greater detail with reference to the following embodiments, whereas the invention is in no way limited to these embodiments and can be practiced as suitably modified within the scope of the essential feature thereof.
Embodim n 1 Embodiment 1 will be described which is a cylindrical lithium secondary cell having a relatively large capacity and equipped with a positive electrode terminal and a negative electrode terminal. FIG. 1 is an overall perspective view of the cell of the invention, FIG. 2 is an exploded perspective view of the cell, and FIG. 3 is a view partly in section of the cell.
As shown in FIGS. 1 and 2, the cell of the invention comprises a cylindrical battery can 3 having an aluminum cylinder 1 and lids 2, 2 welded to the respective ends thereof, and a rolled-up electrode unit 4 encased in the can 3. A pair of positive and negative electrode terminal assemblies 5, 5 are attached respectively to the lids 2, 2 which are made of aluminum. The rolled-up electrode unit 4 is connected to the terminal assemblies 5, 5 by a plurality of electrode tabs 6, whereby the electric power generated by the electrode unit 4 can be delivered to an external device from the pair of terminal assemblies 5, 5. Each lid 2 is provided with a gas vent plug 7.
With reference to FIG. 3, the rolled-up electrode unit 4 comprises a positive electrode 41 containing a lithium composite oxide, a separator 42 impregnated with a nonaqueous electrolyte, and a negative electrode 43 containing a carbon material which are lapped over one another and rolled up into a cylinder. A plurality of electrode tabs 6 outwardly extend from each of the positive electrode 41 and the negative electrode 43, and the outer ends 61 of the electrode tabs 6 of the same polarity are joined to one electrode terminal assembly 5. For convenience' sake, only some of these tabs 6 are shown as being joined at their outer ends to the terminal assembly 5 in FIG. 3, while the connection of the ends of the other tabs to the assembly 5 is omitted from the illustration.
The positive electrode terminal assembly 5 has a positive electrode terminal 51 comprising a screw member which extends through a hole in the lid 2 of the battery can 3 and is attached to the lid. The terminal 51 has a flange 52 at its base end. An insulating member 53 of polypropylene is fitted in the hole of the lid 2 to provide electrical insulation and serve as a seal. The positive electrode terminal 51 has a washer 54 fitted therearound from outside the battery can 3, and a first nut 55 and a second nut 56 screwed thereon similarly. The first nut 55 is tightened up to clamp the insulating member 53 between the flange 52 of the terminal 51 and the washer 54 and thereby seal off the hole more effectively. The second nut 56 is utilized for connection to an external circuit.
The electrode tabs 6 extending from the positive electrode of the rolled-up electrode unit 4 are prepared from 1:3 aluminum foil having a thickness of about 0.1 mm. The outer ends 61 of the tabs 6 are secured to the flange 52 of the terminal 51 by spot welding. Alternatively, the tab ends 61 can be secured by ultrasonic welding.
The negative electrode terminal assembly 5 also has the same construction as described above and comprises a negative electrode terminal 81, which extends through, and is attached to, the lid 2 of the battery can 3. The electrode tabs 6 extending from the negative electrode of the rolled-up electrode unit 4 are prepared from nickel foil having a thickness of about 0.1 mm. The outer ends 61 of the tabs 6 are secured to the flange of the negative electrode terminal 81 by spot welding.
With the lithium secondary cell of the present invention, the positive electrode terminal 51 is made from an aluminum alloy. The aluminum alloy is, for example, an Al-Mg-Si alloy comprising aluminum (Al), magnesium (Mg) and silicon (Si). Typical of such alloys is A6101 prescribed in Japanese Industrial Standards (JIS).
The aluminum alloy, A6101 according to JIS, has a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B and the balance Al.
On the other hand, the negative electrode terminal 81 is made from a material prepared by plating a substrate of copper with nickel. Most suitably, the copper is oxygen-free copper.
The cylindrical lithium secondary cell is fabricated by attaching an electrode terminal assembly 5 to each of lids 2 for forming an battery can 3, welding the outer ends 61 of electrode tabs 6 extending from the positive electrode and the negative electrode of a rolled-up electrode unit 4 to the respective flanges 52 of a positive electrode terminal 51 and a negative electrode terminal 81 in corresponding relation, with the electrode unit 4 placed in a cylinder 1, and finally securing the lids 2 to the cylinder 1 by welding, with the respective open ends of the cylinder fitted with the lids.
Embodiment 2 Embodiment 2 will be described wherein an battery can serves also as a positive electrode terminal for delivering electricity to an external circuit.
This embodiment differs from Embodiment 1 described in the following feature. An electrode terminal 511 serving as the negative electrode terminal is attached to one lid 2 for forming an battery can 3 with an insulating member 53 provided between the lid and the terminal. A plurality of electrode tabs extending from the positive electrode of a rolled-up electrode unit 4 are joined directly to the inner surface of the battery can 3, while a plurality of electrode tabs extending from the negative electrode of the unit 4 are connected to the electrode terminal 511. Embodiment 2 is the same as Embodiment 1 with respect to the other components such as a gas vent plug 7.
The electrode terminal 511 is made from a material prepared by plating a substrate of copper with nickel. Most suitably, the copper is oxygen-free copper.
In the case where a cell is to be fabricated according to Embodiment 2 with the positive electrode and the negative electrode replaced by each other, the electrode terminal 511 serving the function of the positive terminal is made from an aluminum alloy. The aluminum alloy is, for example, an Al-Mg-Si alloy comprising aluminum (Al), magnesium (Mg) and silicon (Si). Typical of such alloys is A6101 prescribed in Japanese Industrial Standards (JIS). Instead of aluminum, stainless steel or the like is used as the material for the battery can 3.
Experiment 1_ In this experiment, lithium secondary cells having the construction of Embodiment 1 described were tested for comparison between two cases, i.e., use of pure aluminum for making the positive electrode terminal 51, and use of the aluminum alloy, A6101 according to JIS, for the terminal 51.
Prepared for the experiment were comparative cells each having a positive electrode terminal 51 in the form of a pure aluminum bolt of M8 (diameter, 8 mm) and pure aluminum nuts 55, 56, and cells of the invention each having a positive electrode terminal 51 in the form of an aluminum alloy bolt and aluminum alloy nuts 55, 56. The cells were then checked for sealing effect and changes in appearance after tightening up the first nut 55 with varying torques. The sealing effect was evaluated immediately after the completion of tightening or after subjecting the cell to 100 heat cycles of -20 C -80 C, by filling the cell with nitrogen gas to a pressure of kgf/cm2 and visually checking the cell for a leak of nitrogen gas using an aqueous solution of soap.
Table 1 shows the results.
Table 1 TIGHTENING INITIAL SEALING CHANGE IN EvAL
TORQUE SEALING FFECT AFTE APPEARANCE UATIoN
(kgf = cm) EFFECT EAT CYCLES
C I 40 NO LEAK LEAK NO CHANGE ~
EN
I
N
L M 60 NO LEAK LEAK DEFOkM ED x L P THREADS
70 \OT NOT BREAK IN x MEASURABLE MEASURABL SCREW
80 iVOT NOT BREAK IN X
iMFASURABLEIMEASURABLEI SCREW
The results indicate that when the tightening torque was not greater than 50 kgf=cm, both the cell of the invention and the comparative cell failed to exhibit a sealing effect after the heat cycles owing to insufficient tightening torque. The failure is irrelevant to the terminal material and attributable to the sealing structure. When the tightening torque was 60 kgf=cm, the cell of the invention was free of deformation and satisfactory in sealing effect, whereas a sealing failure occurred in the comparative cell due to deformed threads leading to insufficient tightening.
When the tightening torque was not smaller than 70 kgf=cm, the screw broke in the comparative cell, failing to serve the intended function, whereas the cell of the invention retained a satisfactory sealing effect. These findings reveal that the aluminum alloy A6101 prescribed in JIS is advantageous to use as the material for the positive electrode terminal.
F.xpe i m nt 2 In this experiment, lithium secondary cells having the construction of Embodiment 1 described were tested for comparison using pure nickel, pure copper or oxygen-free copper plated with nickel for making the negative electrode terminal 81.
Prepared for the experiment were Comparative Cell 1 having a negative electrode terminal 81 in the form of a pure nickel bolt of M8 and pure nickel nuts 55, 56, Comparative Cell 2 having a negative electrode terminal 81 in the form of a pure copper bolt and pure copper nuts 55, 56, and cells of the invention each having a negative electrode terminal 81 in the form of a bolt made of oxygen-free copper and plated with nickel and nuts 55, 56 made of oxygen-free copper and plated with nickel. The term "oxygen-free copper" refers to copper which has a high purity, contains no oxygen and is prepared by reduction in a reducing gas or melting in a vacuum for use as a material for vacuum tubes, etc.
First, Comparative Cell 1 and one of the cells of the invention were checked for sealing effect and changes in appearance after tightening up the first nut 55 with a torque of 70 kgf=cm. The cells were tested for sealing effect by filling the cell with nitrogen gas to a pressure of 5 kgf/cm' and visually checking the cell for a leak of nitrogen gas using an aqueous solution of soap.
Table 2 shows the results.
Table 2 MATERIAL OF
INCIDENCE
NEGATIVE PEARANCE
ELECTRODE OF LEAK
TERMINAL
CELL Cu + Ni WITH NO
PLATING FAULTS
COMP. IIARD
CELL 1 PURE Ni 32/100 MCAR~~ IAL, DISTORTION
The results reveal the superiority of the cell of the invention wherein the bolt providing the negative electrode terminal 81 and the nuts 55, 56 were made of oxygen-free copper and plated with nickel, over Comparative Cell 1 wherein the bolt of pure nickel and the nuts 55, 56 of pure nickel were used, hence the advantage of the material of the invention for the negative electrode terminal. Incidentally, the nickel plating layer is about 100 pm in thickness.
Next, Comparative Cell 2 and the cell of the invention were checked for the electric conductivity of the negative electrode terminal after tightening up the first nut 55 with a torque of 70 kgf=cm. The lithium secondary cells used for the evaluation of the conductivity were of 50 Wh class and 40 mm in diameter and 190 mm in height. Each cell was discharged at a definite current value for a specified period of time, and the voltage drop was measured from the open-circuit voltage to calculate the cell resistance from the measurement. Stated more specifically, the positive terminal and the negative terminal of an external measuring instrument were connected to the positive electrode terminal and the negative electrode terminal, each as clamped between the two nuts 55, 56, and the voltage drop was measured with the IR
drop of the positive and negative electrode terminals involved. The measurement was made twice, i.e., immediately after the fabrication of the cell and after preservation at 60 C for 20 days. The cell was discharged at a current value of 10 A, 30 A, 60 A and 90 A, for 10 seconds at each value, and the resulting voltage drop was measured each time. The cell resistance was calculated form the measurements obtained.
Table 3 shows the results.
Table 3 NEGATIVE CELL RESISTANCE CELL RESISTANCE
ELECTRODE IMMEDIATELY AFTER PRESERVATION
AFTER AT 60,C FOR 20 DAYS
TERMINAL FABRICATION
INVENTION OXYGEN - FREE
CELL Cu + Ni 5.23~-5.47m 9 5.42-5.73m Q
PLATING
COMP. PURE Ni 5.30---5.51m Q 6.23-7.34m 0 The results reveal the superiority of the cell of the invention wherein the bolt providing the negative electrode terminal 81 and the nuts 55, 56 were made of oxygen-free copper and plated with nickel, over Comparative Cell 2 wherein the bolt of pure copper and the nuts 55, 56 of pure copper were used, hence the advantage of the material of the invention for the negative electrode terminal. The reason is that with Comparative Cell 2, an oxide film is formed on the surface of the negative electrode terminal, giving increased contact resistance to the connection to the external circuit.
Further studies were made on the composition of aluminum alloys for forming the positive electrode terminal 51 for use in the cylindrical lithium secondary cell according to Embodiment 1 shown in FIGS. 1 to 3. The negative electrode terminal 81 was prepared from a substrate of copper plated with nickel.
Tnvention Cells 1-8 Positive electrode terminals 51 each comprising a bolt of M8, and nuts 55, 56 were prepared from eight kinds of aluminum alloys different in composition and containing Si, Mg, Fe or Cu as an additive element as listed in Tables 4 to 7, and Invention Cells 1 to 8 were fabricated.
The cells were then checked for sealing effect after tightening up the first nut 55 with a torque of 70 kgf=cm.
The sealing effect was evaluated after subjecting the cell to 100 heat cycles of -20 C - 80 C, by filling the cell with nitrogen gas to a pressure of 5 kgf/cm2 and visually checking the cell for a leak of nitrogen gas using an aqueous solution of soap.
The cells were also checked for electric conductivity by discharging the cell at a definite current value for a specified period of time, measuring the voltage drop from the open-circuit voltage and calculating the cell resistance from the measurement.
Table 4 Al sl (wt 'o) (wt%) INVENTION CELL 1 99.00 1.00 INVENTION CELL2 98.50 1.50 Table 5 Al Mg (wt a) (wt o) INVENTION CELL 3 99.00 1.00 INVENTION CELL 4 98,50 1.50 Table 6 Al Fe (wt o) (vvt 'o) INVENTION CELL 5 99.00 1.00 INVENTION CELL 6 98.50 1.50 Table 7 Al Cu (wt%) (wt%) INVENTION CELL 7 99.00 1.00 INVENTION CELL 8 98.50 1.50 Znvention Cells 9-12 Positive electrode terminals each comprising a bolt of M8, and nuts were prepared from four kinds of aluminum alloys different in the ratio of components and containing Mg, Si, Fe, Cu, Mn, Cr, Zn and B as additive elements as listed in Table 8, and Invention Cells 9 to 12 were fabricated.
Invention Cells 13-19 Positive electrode terminals each comprising a bolt of M8, and nuts were prepared from seven kinds of aluminum alloys different in the ratio of components and containing Mg, Si, Fe, Cu, Mn, Cr, Zn and B as additive elements as listed in Table 9, and Invention Cells 13 to 19 were fabricated.
Invention Cells 20-26 Positive electrode terminals each comprising a bolt of M8, and nuts were prepared from seven kinds of aluminum alloys different in the ratio of components and containing Mg, Si, Fe, Cu, Mn, Cr, Zn and B as additive elements as listed in Table 10, and Invention Cells 20 to 26 were fabricated.
=nvention Cells 27. 28 Positive electrode terminals each comprising a bolt of M8, and nuts were prepared from two kinds of aluminum alloys different in the ratio of components and containing Mg, Si, Fe, Cu, Mn, Cr, Zn and B as additive elements as listed in Table 11, and Invention Cells 27 and 28 were fabricated.
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Comparative Cells 3-10 Positive electrode terminals each comprising a bolt of M8, and nuts were prepared from eight kinds of aluminum alloys different in composition and containing Si, Mg, Fe or Cu as an additive element as listed in Tables 12 to 15, and Comparative Cells 3 to 10 were fabricated.
Comnarative Cells 11. 12 Positive electrode terminals each comprising a bolt of M8, and nuts were prepared from two kinds of aluminum alloys containing Mg, Si, Fe, Cu, Mn, Cr, Zn and B as additive elements as listed in Table 16, and Invention Cells 11 and 12 were fabricated.
Table 12 Al SI
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Tables 17 to 20 show that the incidence of leak can be reduced by preparing the positive electrode terminal from an aluminum alloy containing any one of the additive elements Si, Mg, Fe and Cu in an amount of at least 1.0 wt. %. This is attributable to an increased alloy strength due to the presence of the different metal and resulting in suppressed deformation of the positive electrode terminal at the tightening torque of 70 kgf=cm.
Table 21 reveals that the use of the aluminum alloy containing Mg, Si, Fe, Cu, Mn, Cr, Zn and B as additive elements in a combined amount of at least 1.0 wt. % results in reduced cell resistance, increased power density and decreased incidence of leak.
FIG. 5 is a graph showing the relationship between the aluminum content and the incidence of leak established for Comparative Cells 11 and 12 and Invention Cells 9 to 12. The graph reveals that the incidence of leak decreases markedly when the aluminum content is lower than 99 wt. % which is a boundary value. Accordingly the combined content of additive elements other than aluminum which should be at least 1.0 wt. % has a critical significance.
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This result substantiates the superiority of the Si content of aluminum alloys which should be in the range of at least 0.25 wt. % to not higher than 0.75 wt. %.
:35 Table 17 Al Si INCIDENCE OF
(Wt%) (Wt%) LEAK
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(Wt%) (Wt%) LEAK
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(wt%) (~o~1 LEAK
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tti While the embodiments described above are cylindrical lithium secondary cells to which the present invention is applied, the cells of the invention are not limited specifically in shape, but the present invention is applicable to lithium secondary cells of various shapes such as those of square or rectangular cross section.
As described above in detail, the use of the positive electrode terminal and/or the negative electrode terminal of the invention in lithium secondary cells ensures more reliable electrical connection between the cell and an external circuit and gives an improved sealing effect to the portions where the terminals are attached because of the enhanced mechanical strength of the terminals. Further because the formation of oxide film is inhibited over the surfaces of the positive and negative electrode terminals, these terminals are capable of retaining high conductivity to suppress the discharge voltage drop of the cell. Thus the invention is of immense industrial value.
LITHIUM SECONDARY CELL
FIELD OF THE INVENTION
The present invention relates to lithium secondary cells, i.e., to improvements in lithium secondary cells wherein the negative electrode is made chiefly from metallic lithium, lithium alloy and/or a carbon material or oxide material capable of absorbing and desorbing lithium, and the positive electrode is prepared mainly from a positive electrode material typical of which is a metallic oxide.
More particularly the invention relates to improvements in the positive electrode terminal and the negative electrode terminal for delivering current from an electrode unit serving as the electricity generating element to an external circuit.
BACKGROUND OF THE INVENTION
The negative electrode materials heretofore proposed for use in lithium secondary cells include graphite, coke and like carbon materials, metallic lithium, lithium alloys and tin oxides. Among these, carbon materials are already in use for negative electrodes to provide lithium secondary cells.
Graphite is one of the materials which are generally used for negative electrodes because graphite exhibits a discharge potential in close proximity to the potential of metallic lithium to afford lithium secondary cells of high energy density.
For example, JP-A No. 92335/1997 discloses one of lithium secondary cells wherein such materials are used for the negative electrode. The proposed cell has a negative electrode prepared from a carbon material and a negative electrode output terminal made from pure copper. Pure copper remains stable at the negative electrode potential during the charging and discharging of the lithium secondary cell and is therefore used for the negative electrode output terminal.
Besides pure copper, titanium, nickel, stainless steel, etc.
appear useful as potentially stable materials, whereas pure copper is thought suitable in view of ease of working.
However, pure copper is susceptible to oxidation and liable to form an oxide film at the portion of the cell exposed to the atmosphere, so that when used for the negative electrode terminal, pure copper has the problem of giving increased contact resistance at the connection to an external circuit, causing faulty contact to result in a discharge '2 voltage drop.
On the other hand, pure aluminum is used for the positive electrode terminal of such a lithium secondary cell (see, for example, JP-A No. 92335/1997) since pure aluminum is also stable at the positive electrode potential during the charging and discharging of the cell. Although titanium, stainless steel, etc. appear useful as potentially stable materials besides pure aluminum, pure aluminum is considered to be suitable from the viewpoint of easy of working, conductivity and material cost.
Pure aluminum is nevertheless prone to form an oxide film, so that when used for the positive electrode terminal, this metal has the problem of offering greater contact resistance at the connection to an external circuit, giving rise to faulty contact or causing a discharge voltage drop as in the case of the negative electrode terminal.
Moreover, the positive or negative electrode terminal is not always satisfactory in mechanical strength and is not always suitable to tighten up with sufficiently great torque when a lead is to be attached thereto for connection to an external power source. This entails the problem that the terminal mount portion will not be sealed off effectively.
;3 SUMMARY OF THE INVENTION
An object of the present invention, which is to overcome these problems, is to propose improved positive electrode terminal and negative electrode terminal, and an improved electrode terminal for a positive or negative electrode, for use in delivering the electric energy produced by an electricity generating element to an external device, and to further provide a lithium secondary cell having the positive electrode terminal and/or the negative electrode terminal.
Another object of the invention is to use the positive electrode terminal and/or the negative electrode terminal to assure the terminal or terminals of an enhanced mechanical strength in fabricating the cell and thereby improve the reliability of electrical connection of the cell to an external circuit and give an improved sealing effect to the terminal mount portion or portions. The formation of oxide film on the surfaces of the positive and negative electrode terminals is inhibited, enabling the terminals to retain high conductivity to suppress the discharge voltage drop of the cell.
To fulfill the above objects, the present invention provides a lithium secondary cell which comprises an battery can, a positive electrode terminal, a negative electrode terminal, an electrode unit and an insulating member, the battery can having the electrode unit housed therein, the electrode unit having a positive electrode and a negative electrode which are electrically connected to the positive electrode terminal and the negative electrode terminal, respectively, the electrode terminals being insulated from each other by the insulating member. The lithium secondary cell is characterized in that the positive electrode terminal is formed from an aluminum alloy containing at least 1.0 wt. % of a different metal as an additive element.
With the lithium secondary cell of the invention, the positive electrode terminal has a remarkably improved strength and can therefore be tightened up with sufficiently great torque.
Stated more specifically, the different metal in the aluminum alloy can be at least one element selected from the group consisting of Mg, Si, Fe, Cu, Mn, Zn, Cr and B.
When the aluminum alloy contains at least 0.30 wt. % to not greater than 0.85 wt. % of Mg, reduced electric resistance will result, giving the cell an increased power density.
Reduced electric resistance and an increased cell power density are available alternatively when the aluminum alloy contains at least 0.25 wt. % to not greater than 0.75 wt. % of Si.
Further stated more specifically, the aluminum alloy has the composition of A6101 prescribed in JIS, i.e., a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.%
of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. $ of B
and the balance Al.
The cell can be so constructed that the battery can and the positive electrode terminal are insulated from each other by the insulating member. Further the battery can and the negative electrode terminal can be insulated from each other by the insulating member. Additionally, the battery can and the positive electrode terminal, as well as the battery can and the negative electrode terminal, may be insulated from each other by the insulating member.
The present invention provides another lithium secondary cell which comprises an battery can, a positive electrode terminal, a negative electrode terminal, an electrode unit and an insulating member, the battery can having the electrode unit housed therein, the electrode unit having a positive electrode and a negative electrode which are electrically connected to the positive electrode terminal and the negative electrode terminal, respectively, the electrode terminals being insulated from each other by the insulating member. The lithium secondary cell is characterized in that the negative electrode terminal is formed by plating a substrate of copper with nickel.
Most suitably, the substrate of the negative electrode terminal is made of oxygen-free copper.
The present invention provides another lithium secondary cell which comprises an battery can, an electrode terminal, an electrode unit and an insulating member, the battery can having the electrode unit housed therein, the electrode unit having two electrodes electrically connected to the electrode terminal and the battery can, respectively, the electrode terminal and the battery can being insulated from each other by the insulating member.
When serving as the positive electrode terminal, the electrode terminal is formed from an aluminum alloy containing at least 1.0 wt. % of a different metal as an additive element. Alternatively when serving as the negative electrode terminal, the electrode terminal is formed by plating a substrate of copper with nickel.
With the lithium secondary cell described of the invention, the electrode terminal has a remarkably improved strength and can therefore be tightened up with sufficiently great torque. Consequently, the terminal mount portion, i.e., the portion where the terminal is attached, is given an enhanced sealing effect.
Stated more specifically, the different metal in the aluminum alloy can be at least one element selected from the group consisting of Mg, Si, Fe, Cu, Mn, Zn, Cr and B.
When the aluminum alloy contains at least 0.30 wt. %
to not greater than 0.85 wt. % of Mg, reduced electric resistance will result, giving the cell an increased power density.
Reduced electric resistance and an increased cell power density are available alternatively when the aluminum alloy contains at least 0.25 wt. % to not greater than 0.75 wt. %
of Si.
Further stated more specifically, the aluminum alloy has the composition of A6101 prescribed in JIS, i.e., a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B and the balance Al.
Further it is most suitable that the substrate of copper be oxygen-free copper.
Examples of materials usable for the negative electrode of the cell of the invention are graphite, coke and like carbon materials, metallic lithium, lithium alloys and tin oxides.
Examples of materials usable for the positive electrode of the cell of the invention are a wide variety of those which have heretofore been used in nonaqueous-type cells, such as lithium containing composite oxides (e.g., LiCoO2).
Such a material is used as a kneaded mixture in combination with an electrically conductive agent, such as acetylene black or carbon black, and a binder, such as polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVdF).
Further examples o t solvents tiseful for forming the electrolyte are e:hvlene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ciiethyl carbonate, methylethyl carbonate, sulfolane, 3-methylsulfolane, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran and 1,3-dioxolane. These solvents are usable singly or in mixture. However, these ex<~mpl.es are not limitative.
Examples of preferr-=d electralytes are generally those containing flucrine, such as lithium hexafluorophosphate, because these electrolytes are stable and advantageous from the viewpoint cf discharge capaci;.y and c- harge-discharge cycle characteristics. specific examples of useful electrolytes are LiPF;,, L:L13F,, LiC'-',SO;, LiAsF",, LiN ( CF,SO, LiN ( CF,SO. )( C,F,SOz ), LiN r,, I'So ),,.:nd at Least (Dne of mixttlres of such compounds.
Examples of separators usab--e in t'ne lithium secondary cell embodving the invention are a wide variety of those having 'nigh ionic condut_.t;.vi'.-y an(d conventionally used in lithium secondary cells, si.ich as f_irlely p~)-Lous membranes of polyethylene or polyp.ro~;ylene.
li~
A further aspect, the present invention resides in a lithium secondary cell comprising a battery can having two ends and at least one lid at one end, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals attached as electrically insulated from each other to the battery can and lid, and the positive and negative electrode terminals extending through a hole in the lid of the can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals, respectively, the lithium secondary cell being characterized in that the positive electrode terminal is formed from an aluminum alloy containing additive elements selected from the group consisting of Mg, Si, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains at least magnesium and silicon as the additive elements and wherein the additive elements cumulatively total at least 1.0 wt. % of the aluminum alloy.
In another aspect, the present invention resides in a lithium secondary cell comprising a battery can having two ends and at least one lid at one end, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals attached as electrically insulated from each 10a other to the battery can and lid, and the positive and negative electrode terminals extending through a hole in the lid of the can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals, respectively, the lithium secondary cell being characterized in that the positive electrode terminal is formed from an aluminum alloy containing at least 1.0 wt. % in total of at least one element selected from the group consisting of Si, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains 0.30 wt. % to not greater than 0.85 wt. % of Mg.
In a further aspect, the present invention resides in a lithium secondary cell comprising a battery can having two ends and at least one lid at one end, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals attached as electrically insulated from each other to the battery can and lid, and the positive and negative electrode terminals extending through a hole in the lid of the can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals, respectively, the lithium secondary cell being characterized in that the positive electrode terminal is formed from an aluminum alloy containing at least 1.0 wt. % in total of at least one 10b element selected from the group consisting of Mg, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains 0.25 wt. % to not greater than 0.75 wt. % of Si.
In another aspect, the present invention resides in a lithium secondary cell comprising a battery can having two ends and at least one lid at one end, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals attached as electrically insulated from each other to the battery can and lid, and the positive and negative electrode terminals extending through a hole in the lid of the can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals, respectively, the lithium secondary cell being characterized in that the positive electrode terminal is formed from an aluminum alloy having a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. %
of B and the balance Al.
In a further aspect, the present invention resides in a positive electrode terminal for use in a lithium secondary cell, wherein the positive electrode terminal formed from an aluminum alloy containing at least 1.0 wt. % in total of at least one element selected from the group consisting of lOc Si, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains 0.30 wt. % to not greater than 0.85 wt. % of Mg;
and the secondary cell comprises a battery can, having two ends and a lid attached to one end, wherein the electrode terminal extends through a hole in the can, and the electrode terminal is attached to the lid.
In another aspect, the present invention resides in a positive electrode terminal for use in a lithium secondary cell, wherein the positive electrode terminal formed from an aluminum alloy containing at least 1.0 wt. % in total of at least one element selected from the group consisting of Mg, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains 0.25 wt. % to not greater than 0.75 wt. % of Si;
and the secondary cell comprises a battery can, having two ends and a lid attached to one end, wherein the electrode terminal extends through a hole in the can, and the electrode terminal is attached to the lid.
In a further aspect, the present invention resides in a positive electrode terminal for use with a lithium secondary cell, wherein the positive electrode terminal formed from an aluminum alloy having a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B and the balance Al; and the secondary cell comprises a battery can, 10d having two ends and a lid attached to one end, wherein the electrode terminal extends through a hole in the can, and the electrode terminal is attached to the lid.
In another aspect, the present invention resides in a lithium secondary cell comprising a battery can, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals which are attached as electrically insulated from each other to the battery can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals respectively, the lithium secondary cell being characterized in that the negative electrode terminal is formed by plating a substrate of oxygen-free copper with nickel, and the positive electrode terminal having an aluminum alloy having a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B, and the balance Al.
In a further aspect, the present invention resides in a positive electrode terminal for use in lithium secondary cells which is formed from an aluminum alloy, the positive electrode terminal for use in lithium secondary cells being characterized in that the aluminum alloy has a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of 10e Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B and the balance Al.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view showing the appearance of l Of a cylindrical lithium secondary cell as a first embodiment of the invention;
FIG. 2 is an exploded perspective view of the lithium secondary cell;
FIG. 3 is a fragmentary view in section of the lithium secondary cell;
FIG. 4 is a perspective view showing the appearance of another cylindrical lithium secondary cell as a second embodiment of the invention; and FIG. 5 is a graph showing the relationship between the aluminum content and the incidence of leak.
DETAILED DESCRIPTION OF EMBODIMENTS
The present invention will be described in greater detail with reference to the following embodiments, whereas the invention is in no way limited to these embodiments and can be practiced as suitably modified within the scope of the essential feature thereof.
Embodim n 1 Embodiment 1 will be described which is a cylindrical lithium secondary cell having a relatively large capacity and equipped with a positive electrode terminal and a negative electrode terminal. FIG. 1 is an overall perspective view of the cell of the invention, FIG. 2 is an exploded perspective view of the cell, and FIG. 3 is a view partly in section of the cell.
As shown in FIGS. 1 and 2, the cell of the invention comprises a cylindrical battery can 3 having an aluminum cylinder 1 and lids 2, 2 welded to the respective ends thereof, and a rolled-up electrode unit 4 encased in the can 3. A pair of positive and negative electrode terminal assemblies 5, 5 are attached respectively to the lids 2, 2 which are made of aluminum. The rolled-up electrode unit 4 is connected to the terminal assemblies 5, 5 by a plurality of electrode tabs 6, whereby the electric power generated by the electrode unit 4 can be delivered to an external device from the pair of terminal assemblies 5, 5. Each lid 2 is provided with a gas vent plug 7.
With reference to FIG. 3, the rolled-up electrode unit 4 comprises a positive electrode 41 containing a lithium composite oxide, a separator 42 impregnated with a nonaqueous electrolyte, and a negative electrode 43 containing a carbon material which are lapped over one another and rolled up into a cylinder. A plurality of electrode tabs 6 outwardly extend from each of the positive electrode 41 and the negative electrode 43, and the outer ends 61 of the electrode tabs 6 of the same polarity are joined to one electrode terminal assembly 5. For convenience' sake, only some of these tabs 6 are shown as being joined at their outer ends to the terminal assembly 5 in FIG. 3, while the connection of the ends of the other tabs to the assembly 5 is omitted from the illustration.
The positive electrode terminal assembly 5 has a positive electrode terminal 51 comprising a screw member which extends through a hole in the lid 2 of the battery can 3 and is attached to the lid. The terminal 51 has a flange 52 at its base end. An insulating member 53 of polypropylene is fitted in the hole of the lid 2 to provide electrical insulation and serve as a seal. The positive electrode terminal 51 has a washer 54 fitted therearound from outside the battery can 3, and a first nut 55 and a second nut 56 screwed thereon similarly. The first nut 55 is tightened up to clamp the insulating member 53 between the flange 52 of the terminal 51 and the washer 54 and thereby seal off the hole more effectively. The second nut 56 is utilized for connection to an external circuit.
The electrode tabs 6 extending from the positive electrode of the rolled-up electrode unit 4 are prepared from 1:3 aluminum foil having a thickness of about 0.1 mm. The outer ends 61 of the tabs 6 are secured to the flange 52 of the terminal 51 by spot welding. Alternatively, the tab ends 61 can be secured by ultrasonic welding.
The negative electrode terminal assembly 5 also has the same construction as described above and comprises a negative electrode terminal 81, which extends through, and is attached to, the lid 2 of the battery can 3. The electrode tabs 6 extending from the negative electrode of the rolled-up electrode unit 4 are prepared from nickel foil having a thickness of about 0.1 mm. The outer ends 61 of the tabs 6 are secured to the flange of the negative electrode terminal 81 by spot welding.
With the lithium secondary cell of the present invention, the positive electrode terminal 51 is made from an aluminum alloy. The aluminum alloy is, for example, an Al-Mg-Si alloy comprising aluminum (Al), magnesium (Mg) and silicon (Si). Typical of such alloys is A6101 prescribed in Japanese Industrial Standards (JIS).
The aluminum alloy, A6101 according to JIS, has a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B and the balance Al.
On the other hand, the negative electrode terminal 81 is made from a material prepared by plating a substrate of copper with nickel. Most suitably, the copper is oxygen-free copper.
The cylindrical lithium secondary cell is fabricated by attaching an electrode terminal assembly 5 to each of lids 2 for forming an battery can 3, welding the outer ends 61 of electrode tabs 6 extending from the positive electrode and the negative electrode of a rolled-up electrode unit 4 to the respective flanges 52 of a positive electrode terminal 51 and a negative electrode terminal 81 in corresponding relation, with the electrode unit 4 placed in a cylinder 1, and finally securing the lids 2 to the cylinder 1 by welding, with the respective open ends of the cylinder fitted with the lids.
Embodiment 2 Embodiment 2 will be described wherein an battery can serves also as a positive electrode terminal for delivering electricity to an external circuit.
This embodiment differs from Embodiment 1 described in the following feature. An electrode terminal 511 serving as the negative electrode terminal is attached to one lid 2 for forming an battery can 3 with an insulating member 53 provided between the lid and the terminal. A plurality of electrode tabs extending from the positive electrode of a rolled-up electrode unit 4 are joined directly to the inner surface of the battery can 3, while a plurality of electrode tabs extending from the negative electrode of the unit 4 are connected to the electrode terminal 511. Embodiment 2 is the same as Embodiment 1 with respect to the other components such as a gas vent plug 7.
The electrode terminal 511 is made from a material prepared by plating a substrate of copper with nickel. Most suitably, the copper is oxygen-free copper.
In the case where a cell is to be fabricated according to Embodiment 2 with the positive electrode and the negative electrode replaced by each other, the electrode terminal 511 serving the function of the positive terminal is made from an aluminum alloy. The aluminum alloy is, for example, an Al-Mg-Si alloy comprising aluminum (Al), magnesium (Mg) and silicon (Si). Typical of such alloys is A6101 prescribed in Japanese Industrial Standards (JIS). Instead of aluminum, stainless steel or the like is used as the material for the battery can 3.
Experiment 1_ In this experiment, lithium secondary cells having the construction of Embodiment 1 described were tested for comparison between two cases, i.e., use of pure aluminum for making the positive electrode terminal 51, and use of the aluminum alloy, A6101 according to JIS, for the terminal 51.
Prepared for the experiment were comparative cells each having a positive electrode terminal 51 in the form of a pure aluminum bolt of M8 (diameter, 8 mm) and pure aluminum nuts 55, 56, and cells of the invention each having a positive electrode terminal 51 in the form of an aluminum alloy bolt and aluminum alloy nuts 55, 56. The cells were then checked for sealing effect and changes in appearance after tightening up the first nut 55 with varying torques. The sealing effect was evaluated immediately after the completion of tightening or after subjecting the cell to 100 heat cycles of -20 C -80 C, by filling the cell with nitrogen gas to a pressure of kgf/cm2 and visually checking the cell for a leak of nitrogen gas using an aqueous solution of soap.
Table 1 shows the results.
Table 1 TIGHTENING INITIAL SEALING CHANGE IN EvAL
TORQUE SEALING FFECT AFTE APPEARANCE UATIoN
(kgf = cm) EFFECT EAT CYCLES
C I 40 NO LEAK LEAK NO CHANGE ~
EN
I
N
L M 60 NO LEAK LEAK DEFOkM ED x L P THREADS
70 \OT NOT BREAK IN x MEASURABLE MEASURABL SCREW
80 iVOT NOT BREAK IN X
iMFASURABLEIMEASURABLEI SCREW
The results indicate that when the tightening torque was not greater than 50 kgf=cm, both the cell of the invention and the comparative cell failed to exhibit a sealing effect after the heat cycles owing to insufficient tightening torque. The failure is irrelevant to the terminal material and attributable to the sealing structure. When the tightening torque was 60 kgf=cm, the cell of the invention was free of deformation and satisfactory in sealing effect, whereas a sealing failure occurred in the comparative cell due to deformed threads leading to insufficient tightening.
When the tightening torque was not smaller than 70 kgf=cm, the screw broke in the comparative cell, failing to serve the intended function, whereas the cell of the invention retained a satisfactory sealing effect. These findings reveal that the aluminum alloy A6101 prescribed in JIS is advantageous to use as the material for the positive electrode terminal.
F.xpe i m nt 2 In this experiment, lithium secondary cells having the construction of Embodiment 1 described were tested for comparison using pure nickel, pure copper or oxygen-free copper plated with nickel for making the negative electrode terminal 81.
Prepared for the experiment were Comparative Cell 1 having a negative electrode terminal 81 in the form of a pure nickel bolt of M8 and pure nickel nuts 55, 56, Comparative Cell 2 having a negative electrode terminal 81 in the form of a pure copper bolt and pure copper nuts 55, 56, and cells of the invention each having a negative electrode terminal 81 in the form of a bolt made of oxygen-free copper and plated with nickel and nuts 55, 56 made of oxygen-free copper and plated with nickel. The term "oxygen-free copper" refers to copper which has a high purity, contains no oxygen and is prepared by reduction in a reducing gas or melting in a vacuum for use as a material for vacuum tubes, etc.
First, Comparative Cell 1 and one of the cells of the invention were checked for sealing effect and changes in appearance after tightening up the first nut 55 with a torque of 70 kgf=cm. The cells were tested for sealing effect by filling the cell with nitrogen gas to a pressure of 5 kgf/cm' and visually checking the cell for a leak of nitrogen gas using an aqueous solution of soap.
Table 2 shows the results.
Table 2 MATERIAL OF
INCIDENCE
NEGATIVE PEARANCE
ELECTRODE OF LEAK
TERMINAL
CELL Cu + Ni WITH NO
PLATING FAULTS
COMP. IIARD
CELL 1 PURE Ni 32/100 MCAR~~ IAL, DISTORTION
The results reveal the superiority of the cell of the invention wherein the bolt providing the negative electrode terminal 81 and the nuts 55, 56 were made of oxygen-free copper and plated with nickel, over Comparative Cell 1 wherein the bolt of pure nickel and the nuts 55, 56 of pure nickel were used, hence the advantage of the material of the invention for the negative electrode terminal. Incidentally, the nickel plating layer is about 100 pm in thickness.
Next, Comparative Cell 2 and the cell of the invention were checked for the electric conductivity of the negative electrode terminal after tightening up the first nut 55 with a torque of 70 kgf=cm. The lithium secondary cells used for the evaluation of the conductivity were of 50 Wh class and 40 mm in diameter and 190 mm in height. Each cell was discharged at a definite current value for a specified period of time, and the voltage drop was measured from the open-circuit voltage to calculate the cell resistance from the measurement. Stated more specifically, the positive terminal and the negative terminal of an external measuring instrument were connected to the positive electrode terminal and the negative electrode terminal, each as clamped between the two nuts 55, 56, and the voltage drop was measured with the IR
drop of the positive and negative electrode terminals involved. The measurement was made twice, i.e., immediately after the fabrication of the cell and after preservation at 60 C for 20 days. The cell was discharged at a current value of 10 A, 30 A, 60 A and 90 A, for 10 seconds at each value, and the resulting voltage drop was measured each time. The cell resistance was calculated form the measurements obtained.
Table 3 shows the results.
Table 3 NEGATIVE CELL RESISTANCE CELL RESISTANCE
ELECTRODE IMMEDIATELY AFTER PRESERVATION
AFTER AT 60,C FOR 20 DAYS
TERMINAL FABRICATION
INVENTION OXYGEN - FREE
CELL Cu + Ni 5.23~-5.47m 9 5.42-5.73m Q
PLATING
COMP. PURE Ni 5.30---5.51m Q 6.23-7.34m 0 The results reveal the superiority of the cell of the invention wherein the bolt providing the negative electrode terminal 81 and the nuts 55, 56 were made of oxygen-free copper and plated with nickel, over Comparative Cell 2 wherein the bolt of pure copper and the nuts 55, 56 of pure copper were used, hence the advantage of the material of the invention for the negative electrode terminal. The reason is that with Comparative Cell 2, an oxide film is formed on the surface of the negative electrode terminal, giving increased contact resistance to the connection to the external circuit.
Further studies were made on the composition of aluminum alloys for forming the positive electrode terminal 51 for use in the cylindrical lithium secondary cell according to Embodiment 1 shown in FIGS. 1 to 3. The negative electrode terminal 81 was prepared from a substrate of copper plated with nickel.
Tnvention Cells 1-8 Positive electrode terminals 51 each comprising a bolt of M8, and nuts 55, 56 were prepared from eight kinds of aluminum alloys different in composition and containing Si, Mg, Fe or Cu as an additive element as listed in Tables 4 to 7, and Invention Cells 1 to 8 were fabricated.
The cells were then checked for sealing effect after tightening up the first nut 55 with a torque of 70 kgf=cm.
The sealing effect was evaluated after subjecting the cell to 100 heat cycles of -20 C - 80 C, by filling the cell with nitrogen gas to a pressure of 5 kgf/cm2 and visually checking the cell for a leak of nitrogen gas using an aqueous solution of soap.
The cells were also checked for electric conductivity by discharging the cell at a definite current value for a specified period of time, measuring the voltage drop from the open-circuit voltage and calculating the cell resistance from the measurement.
Table 4 Al sl (wt 'o) (wt%) INVENTION CELL 1 99.00 1.00 INVENTION CELL2 98.50 1.50 Table 5 Al Mg (wt a) (wt o) INVENTION CELL 3 99.00 1.00 INVENTION CELL 4 98,50 1.50 Table 6 Al Fe (wt o) (vvt 'o) INVENTION CELL 5 99.00 1.00 INVENTION CELL 6 98.50 1.50 Table 7 Al Cu (wt%) (wt%) INVENTION CELL 7 99.00 1.00 INVENTION CELL 8 98.50 1.50 Znvention Cells 9-12 Positive electrode terminals each comprising a bolt of M8, and nuts were prepared from four kinds of aluminum alloys different in the ratio of components and containing Mg, Si, Fe, Cu, Mn, Cr, Zn and B as additive elements as listed in Table 8, and Invention Cells 9 to 12 were fabricated.
Invention Cells 13-19 Positive electrode terminals each comprising a bolt of M8, and nuts were prepared from seven kinds of aluminum alloys different in the ratio of components and containing Mg, Si, Fe, Cu, Mn, Cr, Zn and B as additive elements as listed in Table 9, and Invention Cells 13 to 19 were fabricated.
Invention Cells 20-26 Positive electrode terminals each comprising a bolt of M8, and nuts were prepared from seven kinds of aluminum alloys different in the ratio of components and containing Mg, Si, Fe, Cu, Mn, Cr, Zn and B as additive elements as listed in Table 10, and Invention Cells 20 to 26 were fabricated.
=nvention Cells 27. 28 Positive electrode terminals each comprising a bolt of M8, and nuts were prepared from two kinds of aluminum alloys different in the ratio of components and containing Mg, Si, Fe, Cu, Mn, Cr, Zn and B as additive elements as listed in Table 11, and Invention Cells 27 and 28 were fabricated.
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Comparative Cells 3-10 Positive electrode terminals each comprising a bolt of M8, and nuts were prepared from eight kinds of aluminum alloys different in composition and containing Si, Mg, Fe or Cu as an additive element as listed in Tables 12 to 15, and Comparative Cells 3 to 10 were fabricated.
Comnarative Cells 11. 12 Positive electrode terminals each comprising a bolt of M8, and nuts were prepared from two kinds of aluminum alloys containing Mg, Si, Fe, Cu, Mn, Cr, Zn and B as additive elements as listed in Table 16, and Invention Cells 11 and 12 were fabricated.
Table 12 Al SI
(Wt.%) (Wt.%) COMP. CELL 3 99.50 0.50 COMP. CELL 4 99.10 0.90 Table 13 Al Mg (wt%) (wt%a) COMP. CELL 5 99.50 0.50 COMP. CELL 6 99.10 0.90 Table 14 Al Fe (wt%) (wt%) COMP. CELL 7 99.50 0.50 COMP. CELL 8 99.10 0.90 Table 15 Al Cu (wt%) (wt%) COMP. CELL 9 99.50 0.50 COMP. CELL 10 99.10 0.90 :32 O O
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Tables 17 to 20 show that the incidence of leak can be reduced by preparing the positive electrode terminal from an aluminum alloy containing any one of the additive elements Si, Mg, Fe and Cu in an amount of at least 1.0 wt. %. This is attributable to an increased alloy strength due to the presence of the different metal and resulting in suppressed deformation of the positive electrode terminal at the tightening torque of 70 kgf=cm.
Table 21 reveals that the use of the aluminum alloy containing Mg, Si, Fe, Cu, Mn, Cr, Zn and B as additive elements in a combined amount of at least 1.0 wt. % results in reduced cell resistance, increased power density and decreased incidence of leak.
FIG. 5 is a graph showing the relationship between the aluminum content and the incidence of leak established for Comparative Cells 11 and 12 and Invention Cells 9 to 12. The graph reveals that the incidence of leak decreases markedly when the aluminum content is lower than 99 wt. % which is a boundary value. Accordingly the combined content of additive elements other than aluminum which should be at least 1.0 wt. % has a critical significance.
Tables 22 and 24 further indicate that when the Mg content of aluminum alloys is in the range of at least 0.30 wt. % to not higher than 0.85 wt. %, reduced cell resistance is available to give an increased power density.
This result substantiates the superiority of the Mg content of aluminum alloys which should be in the range of at least 0.30 wt. % to not higher than 0.85 wt. %.
Tables 23 and 24 further show that reduced cell resistance is available to afford an increased power density when the Si content of aluminum alloys is in the range of at least 0.25 wt. % to not higher than 0.75 wt. %.
This result substantiates the superiority of the Si content of aluminum alloys which should be in the range of at least 0.25 wt. % to not higher than 0.75 wt. %.
:35 Table 17 Al Si INCIDENCE OF
(Wt%) (Wt%) LEAK
COMP. CELL 3 99.50 0.50 10//10 COMP. CELL 4 99.10 0.90 9/10 INVENTION CELL 1 99.00 1.00 1z 10 INVENTION CELL2 98.50 1.50 0/ 10 Table 18 Al Mg INCIDENCE OF
(Wt%) (Wt%) LEAK
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(wt%) (~o~1 LEAK
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(VVt%) (VYt%) LEAK
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tti While the embodiments described above are cylindrical lithium secondary cells to which the present invention is applied, the cells of the invention are not limited specifically in shape, but the present invention is applicable to lithium secondary cells of various shapes such as those of square or rectangular cross section.
As described above in detail, the use of the positive electrode terminal and/or the negative electrode terminal of the invention in lithium secondary cells ensures more reliable electrical connection between the cell and an external circuit and gives an improved sealing effect to the portions where the terminals are attached because of the enhanced mechanical strength of the terminals. Further because the formation of oxide film is inhibited over the surfaces of the positive and negative electrode terminals, these terminals are capable of retaining high conductivity to suppress the discharge voltage drop of the cell. Thus the invention is of immense industrial value.
Claims (19)
1. ~A lithium secondary cell comprising a battery can having two ends and at least one lid at one end, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals attached as electrically insulated from each other to the battery can and lid, and the positive and negative electrode terminals extending through a hole in the lid of the can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals, respectively, the lithium secondary cell being characterized in that the positive electrode terminal is formed from an aluminum alloy containing additive elements selected from the group consisting of Mg, Si, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains at least magnesium and silicon as the additive elements and wherein the additive elements cumulatively total at least 1.0 wt. % of the aluminum alloy.
2. ~A lithium secondary cell comprising a battery can having two ends and at least one lid at one end, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals attached as electrically insulated from each other to the battery can and lid, and the positive and negative electrode terminals extending through a hole in the lid of the can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals, respectively, the lithium secondary cell being characterized in that the positive electrode terminal is formed from an aluminum alloy containing at least 1.0 wt. % in total of at least one additive element selected from the group consisting of Si, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains 0.30 wt. % to not greater than 0.85 wt. % of Mg.
3. ~A lithium secondary cell comprising a battery can having two ends and at least one lid at one end, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals attached as electrically insulated from each other to the battery can and lid, and the positive and negative electrode terminals extending through a hole in the lid of the can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals, respectively, the lithium secondary cell being characterized in that the positive electrode terminal is formed from an aluminum alloy containing at least 1.0 wt. % in total of at least one additive element selected from the group consisting of Mg, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains 0.25 wt. % to not greater than 0.75 wt. % of Si.
4. A lithium secondary cell comprising a battery can having two ends and at least one lid at one end, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals attached as electrically insulated from each other to the battery can and lid, and the positive and negative electrode terminals extending through a hole in the lid of the can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals, respectively, the lithium secondary cell being characterized in that the positive electrode terminal is formed from an aluminum alloy having a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B and the balance Al.
5. A lithium secondary cell according to claim 1 wherein the negative electrode terminal is formed by plating a substrate of copper with a nickel.
6. A lithium secondary cell according to claim 5 wherein the substrate of the negative electrode terminal is made of oxygen-free copper.
7. A positive electrode terminal for use in a lithium secondary cell, wherein the positive electrode terminal is formed from an aluminum alloy containing at least 1.0 wt. % in total of at least one additive element selected from the group consisting of Si, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains 0.30 wt. %
to not greater than 0.85 wt. % of Mg; and the secondary cell comprises a battery can, having two ends and a lid attached to one end, wherein the electrode terminal extends through a hole in the can, and the electrode terminal is attached to the lid.
to not greater than 0.85 wt. % of Mg; and the secondary cell comprises a battery can, having two ends and a lid attached to one end, wherein the electrode terminal extends through a hole in the can, and the electrode terminal is attached to the lid.
8. A positive electrode terminal for use in a lithium secondary cell, wherein the positive electrode terminal is formed from an aluminum alloy containing at least 1.0 wt. % in total of at least one additive element selected from the group consisting of Mg, Fe, Cu, Mn, Zn, Cr and B, wherein the aluminum alloy contains 0.25 wt.%
to not greater than 0.75 wt. % of Si; and the secondary cell comprises a battery can, having two ends and a lid attached to one end, wherein the electrode terminal extends through a hole in the can, and the electrode terminal is attached to the lid.
to not greater than 0.75 wt. % of Si; and the secondary cell comprises a battery can, having two ends and a lid attached to one end, wherein the electrode terminal extends through a hole in the can, and the electrode terminal is attached to the lid.
9. A positive electrode terminal for use in a lithium secondary cell, wherein the positive electrode terminal is formed from an aluminum alloy having a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B and the balance Al; and the secondary cell comprises a battery can, having two ends and a lid attached to one end, wherein the electrode terminal extends through a hole in the can, and the electrode terminal is attached to the lid.
10. The lithium secondary cell of claim 1, further comprising:
an insulating member fitted in the hole of the lid, and a nut fitted around the positive electrode terminal on the side of the lid facing outside the battery can, whereby the nut tightens to seal a gap between the lid and the positive electrode terminal.
an insulating member fitted in the hole of the lid, and a nut fitted around the positive electrode terminal on the side of the lid facing outside the battery can, whereby the nut tightens to seal a gap between the lid and the positive electrode terminal.
11. The lithium secondary cell of claim 10, wherein the nut has a tightening torque less than 60 kgf cm.
12. A lithium secondary cell comprising:
a battery can, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals which are attached as electrically insulated from each other to the battery can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals respectively, the lithium secondary cell being characterized in that the negative electrode terminal is formed by plating a substrate of oxygen-free copper with nickel, and the positive electrode terminal having an aluminum alloy having a composition comprising:
0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B, and the balance Al.
a battery can, an electrode unit serving as an electricity generating element and housed in the battery can, and positive and negative electrode terminals which are attached as electrically insulated from each other to the battery can, the electrode unit having positive and negative electrodes electrically connected to the positive and negative electrode terminals respectively, the lithium secondary cell being characterized in that the negative electrode terminal is formed by plating a substrate of oxygen-free copper with nickel, and the positive electrode terminal having an aluminum alloy having a composition comprising:
0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B, and the balance Al.
13. A positive electrode terminal for use in lithium secondary cells which is formed from an aluminum alloy, being characterized in that the aluminum alloy has a composition comprising 0.35 to 0.8 wt. % of Mg, 0.30 to 0.7 wt. % of Si, 0.50 wt. % of Fe, 0.10 wt. % of Cu, 0.03 wt.% of Mn, 0.10 wt. % of Zn, 0.03 wt. % of Cr, 0.06 wt. % of B and the balance Al.
14. A lithium secondary cell according to claim 2 wherein the negative electrode terminal is formed by plating a substrate of copper with nickel.
15. A lithium secondary cell according to claim 3 wherein the negative electrode terminal is formed by plating a substrate of copper with nickel.
16. A lithium secondary cell according to claim 4 wherein the negative electrode terminal is formed by plating a substrate of copper with nickel.
17. A lithium secondary cell according to claim 14 wherein the substrate of the negative electrode terminal is made of oxygen-free copper.
18. A lithium secondary cell according to claim 15 wherein the substrate of the negative electrode terminal is made of oxygen-free copper.
19. A lithium secondary cell according to claim 16 wherein the substrate of the negative electrode terminal is made of oxygen-free copper.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24845498 | 1998-09-02 | ||
| JPHEI.10-248454 | 1998-09-02 | ||
| JP22260199A JP3759564B2 (en) | 1998-09-02 | 1999-08-05 | Lithium secondary battery |
| JPHEI.11-222601 | 1999-08-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2281136A1 CA2281136A1 (en) | 2000-03-02 |
| CA2281136C true CA2281136C (en) | 2008-07-22 |
Family
ID=26524965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002281136A Expired - Fee Related CA2281136C (en) | 1998-09-02 | 1999-08-31 | Lithium secondary cell |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6521374B1 (en) |
| JP (1) | JP3759564B2 (en) |
| KR (1) | KR100466767B1 (en) |
| CA (1) | CA2281136C (en) |
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| WO2001059856A1 (en) * | 2000-02-09 | 2001-08-16 | Ngk Insulators, Ltd. | Lithium secondary cell and method for producing the same |
| JP4623812B2 (en) * | 2000-10-06 | 2011-02-02 | Ｎｅｃエナジーデバイス株式会社 | LiMn secondary battery, battery manufacturing method, electric mobile vehicle |
| US20030113622A1 (en) * | 2001-12-14 | 2003-06-19 | Blasi Jane A. | Electrolyte additive for non-aqueous electrochemical cells |
| JP4032958B2 (en) * | 2001-12-18 | 2008-01-16 | トヨタ自動車株式会社 | Storage element and method for manufacturing the same |
| US20030162099A1 (en) | 2002-02-28 | 2003-08-28 | Bowden William L. | Non-aqueous electrochemical cell |
| JP4834952B2 (en) * | 2003-10-02 | 2011-12-14 | 株式会社Ｇｓユアサ | battery |
| US7459234B2 (en) * | 2003-11-24 | 2008-12-02 | The Gillette Company | Battery including aluminum components |
| US7544384B2 (en) * | 2003-11-24 | 2009-06-09 | The Gillette Company | Methods of making coated battery components |
| US7279250B2 (en) * | 2003-11-24 | 2007-10-09 | The Gillette Company | Battery including aluminum components |
| USD503674S1 (en) * | 2004-02-27 | 2005-04-05 | Yang Eng Huey | Battery pack |
| KR100599714B1 (en) | 2004-06-25 | 2006-07-12 | 삼성에스디아이 주식회사 | Secondary battery |
| US7285356B2 (en) * | 2004-07-23 | 2007-10-23 | The Gillette Company | Non-aqueous electrochemical cells |
| TWI290781B (en) | 2004-09-02 | 2007-12-01 | Lg Chemical Ltd | Electrode active material with multi-element based oxide layers and preparation method thereof |
| US7479348B2 (en) * | 2005-04-08 | 2009-01-20 | The Gillette Company | Non-aqueous electrochemical cells |
| CN101305481B (en) * | 2005-09-02 | 2011-01-12 | A123系统公司 | Battery cell design and method of its construction |
| US8084158B2 (en) | 2005-09-02 | 2011-12-27 | A123 Systems, Inc. | Battery tab location design and method of construction |
| KR100792954B1 (en) * | 2006-09-12 | 2008-01-08 | 엘에스전선 주식회사 | Electrical double layer capacitors |
| US8236441B2 (en) | 2007-07-24 | 2012-08-07 | A123 Systems, Inc. | Battery cell design and methods of its construction |
| KR20110133257A (en) * | 2010-06-04 | 2011-12-12 | 에스비리모티브 주식회사 | Secondary battery |
| DE112013004439T5 (en) | 2012-09-12 | 2015-06-18 | Kabushiki Kaisha Toyota Jidoshokki | Electric storage device |
| WO2014042135A1 (en) | 2012-09-13 | 2014-03-20 | 株式会社 豊田自動織機 | Power storage device |
| FR3016478B1 (en) * | 2014-01-16 | 2017-09-08 | Commissariat Energie Atomique | ELECTROCHEMICAL BATTERY WITH HOUSING AND ALUMINUM ALLOY OUTPUT TERMINAL, BATTERY PACK AND METHOD OF MAKING THE SAME |
| FR3075477B1 (en) * | 2017-12-14 | 2021-07-30 | Commissariat Energie Atomique | TRAVERSE FORMING TERMINAL FOR METAL-ION ELECTROCHEMICAL ACCUMULATOR, ASSOCIATED ACCUMULATOR |
| EP3872894A4 (en) * | 2018-10-23 | 2021-12-15 | Panasonic Intellectual Property Management Co., Ltd. | Battery and protective tape for batteries |
| EP4723314A1 (en) * | 2023-06-21 | 2026-04-08 | Contemporary Amperex Technology Co., Limited | Battery cell, battery, electric device and energy storage device |
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| US5773164A (en) | 1996-10-15 | 1998-06-30 | Ovonic Battery Company, Inc. | Robust terminal for rechargeable prismatic batteries |
| JP3428336B2 (en) | 1996-12-26 | 2003-07-22 | 松下電器産業株式会社 | Square sealed storage battery |
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- 1999-08-05 JP JP22260199A patent/JP3759564B2/en not_active Expired - Lifetime
- 1999-08-31 CA CA002281136A patent/CA2281136C/en not_active Expired - Fee Related
- 1999-09-01 KR KR10-1999-0036784A patent/KR100466767B1/en not_active Expired - Fee Related
- 1999-09-01 US US09/387,833 patent/US6521374B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR100466767B1 (en) | 2005-01-24 |
| KR20000022825A (en) | 2000-04-25 |
| US6521374B1 (en) | 2003-02-18 |
| JP2000149915A (en) | 2000-05-30 |
| CA2281136A1 (en) | 2000-03-02 |
| JP3759564B2 (en) | 2006-03-29 |
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