CN103201803B - Lithium-ion capacitor - Google Patents
Lithium-ion capacitor Download PDFInfo
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- CN103201803B CN103201803B CN201180050629.1A CN201180050629A CN103201803B CN 103201803 B CN103201803 B CN 103201803B CN 201180050629 A CN201180050629 A CN 201180050629A CN 103201803 B CN103201803 B CN 103201803B
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- lithium
- ion capacitor
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 126
- 239000003990 capacitor Substances 0.000 title claims abstract description 123
- 230000002093 peripheral Effects 0.000 claims abstract description 44
- 230000003068 static Effects 0.000 claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- -1 polyethylene Polymers 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 11
- 239000001913 cellulose Substances 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 9
- 239000004698 Polyethylene (PE) Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 238000004804 winding Methods 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 230000005611 electricity Effects 0.000 description 45
- 239000000463 material Substances 0.000 description 31
- 229910052744 lithium Inorganic materials 0.000 description 29
- 238000003466 welding Methods 0.000 description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000005755 formation reaction Methods 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
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- 239000011230 binding agent Substances 0.000 description 8
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- 239000011737 fluorine Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
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- PDHXHYRJLUNSDZ-UHFFFAOYSA-N [C].C#C Chemical compound [C].C#C PDHXHYRJLUNSDZ-UHFFFAOYSA-N 0.000 description 3
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- 229910003002 lithium salt Inorganic materials 0.000 description 3
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
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- 229910002804 graphite Inorganic materials 0.000 description 2
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- 235000013372 meat Nutrition 0.000 description 2
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- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- 229910007003 Li(C2F5SO2)2 Inorganic materials 0.000 description 1
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
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- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Even if it is an object of the invention to provide a kind of just in case occur internal short-circuit time also can suppress surface temperature become high temperature, there is high security and there is the lithium-ion capacitor of high power capacity and high output characteristic.The lithium-ion capacitor of the present invention is the lithium-ion capacitor key element that positive electrical pole piece and negative electrode sheet overlap to form to be contained in the lithium-ion capacitor in peripheral hardware container by electrolyte with across dividing plate, it is formed with porous layer on the outer surface of described lithium-ion capacitor key element, the static capacity of lithium-ion capacitor is set to C (kF), the DC resistance of lithium-ion capacitor is set to R (m Ω), and when the thickness of porous layer is set to T (μm), meet following relational expression (1) and following relational expression (2).Relational expression (1): 35≤T × R/C relational expression (2): 0.01≤R/C≤5.
Description
Technical field
The present invention relates to lithium-ion capacitor.
Background technology
In recent years, such as in the various fields such as power use, wind power generation plant, uninterrupted power supply(ups), as having height
Energy density and the electric energy storage device of high output characteristic, in peripheral hardware container, house lithium-ion capacitor key element and electrolytic solution and
Lithium-ion capacitor is become to be attracted attention (referring for example to patent documentation 1).Particularly, as requiring begging for of the high vehicle-mounted purposes exported
Opinion is advanced, and from market, the requirement performance about safety improves.
Particularly in power applications, have during accident etc., to make lithium-ion capacitor deformation (bent from outside pressure
Folding), or sting out sharp keen part etc. thus problem that internal short-circuit occurs.
Then, in order to solve such problem, it is thus proposed that: join between peripheral hardware container and lithium-ion capacitor key element
If the plate of the polyethylene about 500 μm, thus the lithium of the suppression deformation that brings of external pressure and the raising that realizes durability from
Sub-capacitor (referring for example to patent documentation 2).
But, the static capacity of the lithium-ion capacitor of such structure is little and resistance big, can obtain safety, but can not
Have both high output and the such performance of high power capacity of city's site requirements.
Additionally, in lithium-ion capacitor, energy density and output characteristics are the highest, in the feelings producing internal short-circuit
Flow under condition big electric current, is accompanied by this heating occurred drastically, the probability of (more than 150 DEG C) so surface temperature reaches a high temperature
Height, such as, have the danger of the constituent dissolving etc. of lithium-ion capacitor.Additionally, at the device possessing multiple lithium-ion capacitor
In (module), also brought by heat in the lithium-ion capacitor adjacent with the lithium-ion capacitor that surface temperature reaches a high temperature
Impact, and have the danger that no longer can play desired function etc..
Prior art literature
Patent documentation 1: Japanese Unexamined Patent Publication 2007-67105 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2008-244378 publication
Summary of the invention
The present invention is to make based on above situation, even if its object is to provide a kind of just in case occurring internal short
In the case of road, also can suppress surface temperature become high temperature, there is high security and there is high power capacity and high output characteristic
Lithium-ion capacitor.
The lithium-ion capacitor of the present invention is positive electrical pole piece and negative electrode sheet will to be overlapped to form across dividing plate
Lithium-ion capacitor key element and electrolyte be housed in the lithium-ion capacitor in peripheral hardware container, it is characterised in that
The outer surface of above-mentioned lithium-ion capacitor key element is formed with porous layer,
The static capacity of this lithium-ion capacitor is being set to C (kF), the DC resistance of this lithium-ion capacitor is being set
For R (m Ω), and when the thickness of above-mentioned porous layer is set to T (μm), meet following relational expression (1) and following pass
It is formula (2).
Relational expression (1): 35≤T × R/C
Relational expression (2): 0.01≤R/C≤5
In the lithium-ion capacitor of the present invention, the most above-mentioned porous layer is overlapped to form by Porous sheet and forms.
In the lithium-ion capacitor of the present invention, the most above-mentioned porous layer was made up of same composition of aforementioned barriers.
In the lithium-ion capacitor of the present invention, the most above-mentioned porous layer by from cellulose, staple fibre, polyethylene with
And at least one selected in polypropylene make.
In the lithium-ion capacitor of the present invention, the thickness of the most above-mentioned porous layer is more than 120 μm.
In the lithium-ion capacitor of the present invention, the outer surface of lithium-ion capacitor key element is formed with porous layer,
The thickness of this porous layer, determines in the static capacity of this lithium-ion capacitor and the relation of DC resistance, so i.e.
Making in the case of just in case producing internal short-circuit, the heat of the heating drastically produced due to stream super-high-current is by porous layer
The electrolyte of infiltration absorbs, it is possible to suppression surface temperature becomes high temperature, and can this porous layer of restraint measure and carry
The reduction of static capacity that come, this lithium-ion capacitor and high resistance.
Therefore, according to the lithium-ion capacitor of the present invention, it is possible to obtain high power capacity and high output characteristic, and producing
In the case of internal short-circuit, it is possible to suppression surface temperature becomes high temperature, thus obtains high safety.
Accompanying drawing explanation
Fig. 1 is the explanation sectional view of an example of the structure of the lithium-ion capacitor illustrating the present invention.
Fig. 2 is lithium-ion electric that illustrate the lithium-ion capacitor of pie graph 1, that be formed with porous layer on its outer surface
The explanation sectional view of the structure of tank features.
Fig. 3 is the explanatory diagram of the electrode laminated body of the lithium-ion capacitor key element of pie graph 2 and porous layer, and (a) is to bow
View, (b) is the sectional view cut off in the longitudinal direction.
Fig. 4 is the explanation of the outward appearance of the lithium-ion capacitor key element being shown on the outer surface of Fig. 2 and defining porous layer
Figure.
Fig. 5 is the explanatory diagram amplified the part of negative electricity pole piece and illustrate, (a) is top view, and (b) is at width
The sectional view cut off.
Fig. 6 is the explanatory diagram amplified the part of positive electrical pole piece and illustrate, (a) is top view, and (b) is at width
The sectional view cut off.
Fig. 7 is the lithium ion illustrating and being formed on the outer surface of Fig. 2 the lithium-ion capacitor key element defining porous layer
The explanation sectional view of source of supply.
Fig. 8 is the chart of the voltage in the discharge curve in the mensuration of static capacity and the relation of time.
Symbol description
10: capacitor key element unit；10A: electrode laminated body；11: lithium-ion capacitor key element (element)；12: positive electrical
Pole piece；12a: positive electrode collector；12b: electrode layer；12e: side edge part；13: negative electricity pole piece；13a: negative electrode collector；13b: electricity
Pole layer；13e: side edge part；14: the 1 Porous sheets；14a: one end part；14b: dividing plate formation part other end part (every
Plate end sections)；14c: other end part；15: the 2 Porous sheets；15a: one end part；15b: other end part；16,17:
Lithium ion source of supply；16a, 17b: collector body (lithium electrode collector body)；18: band；20: peripheral hardware container；21: surrounding wall portion；22: cap；
23: bottom；25: positive pole collector plate；26: negative electrode collector plate；27: insulating component；28: negative wire；30: anode electrode terminal；
31: recess；32: protuberance；35: negative electrode terminal；36: recess；37: protuberance；38: packing ring；40: porous layer
Detailed description of the invention
Hereinafter, as embodiments of the present invention, describe in detail and the lithium-ion capacitor of the present invention is set to convoluted lithium
Ionistor (hereinafter referred to as " convoluted LIC ") and situation about implementing.
Fig. 1 is the explanation sectional view of an example of the structure of the lithium-ion capacitor illustrating the present invention, and Fig. 2 is to illustrate composition
The explanation of the lithium-ion capacitor of Fig. 1, the lithium-ion capacitor key element that defines porous layer on its outer surface structure
With sectional view, Fig. 3 is the explanatory diagram of the electrode laminated body of the lithium-ion capacitor key element of pie graph 2 and porous layer, and (a) is to bow
View, (b) is the sectional view carrying out in the longitudinal direction cutting off.
This convoluted LIC has a structure that in metal peripheral hardware container 20, contain electrolyte and across every
That positive electrical pole piece 12 and negative electricity pole piece 13 are overlapped to form by plate, specifically with across dividing plate lamination positive electrical pole piece 12
And the cylindric lithium-ion capacitor key element (hereinafter also referred to as " element ") that the state of negative electricity pole piece 13 winds
11。
Here, in this manual, lithium-ion capacitor key element be by across dividing plate by positive electrical pole piece and negative pole
Electrode slice overlaps to form and obtains, but the lithium-ion capacitor key element overlapped to form by this electrode slice refers to shown in Fig. 1
As, have: form with winding anode electrode sheet 12 and negative electricity pole piece 13 under the state that dividing plate carries out lamination
Structure or any configuration in the structure of dividing plate alternately lamination positive electrical pole piece and negative electricity pole piece.
Further, in element 11, being formed with porous layer 40 on its outer surface, this porous layer 40 is between element 11 and outer
If between container 20.
Here, the outer surface of element 11 refers to be positioned at the outer surface of outermost electrode slice in element 11.
In the example in the figures, porous layer 40 is provided along being positioned at outermost electrode slice in element 11 (specifically
Ground is for negative electricity pole piece 13) outer peripheral face cover the outer surface of this electrode slice, element 11 and porous layer 40 define electricity
Tank features unit 10.This capacitor key element unit 10 utilizes the element portion being made up of element 11 and is made up of porous layer 40
Porous layer portion and constitute.
Additionally, in the convoluted LIC of the present invention, the static capacity of lithium-ion capacitor is set to C (kF), by lithium ion
When the DC resistance of capacitor is set to R (m Ω) and the thickness of porous layer 40 is set to T (μm), need to meet following
Relational expression (1) and following relational expression (2).
In the example in the figures, the thickness T of porous layer 40 is positioned at outermost in representing the outer peripheral face of element 11, i.e. element 11
The outer surface of the electrode slice (negative electricity pole piece 13 in example illustrated) of side is sowed discord with the outer surface of capacitor key element unit 10
Distance.
Relational expression (1): 35≤T × R/C
Relational expression (2): 0.01≤R/C≤5
Here, " static capacity C of lithium-ion capacitor " refers to: discharge current is set to Id (A), will be set to discharge time
Td (s), final discharging voltage is set to the voltage in V2 (V), and the expression discharge curve D as shown in Fig. 8 and time
Between relation chart on, by this discharge curve D from the elapsed time that electric discharge starts, (following also referred to as " electric discharge is through out-of-date
Between ") it is the near linear L1 between the time point of 1 (s) and the time point that the electric discharge elapsed time is 3 (s) and electric discharge elapsed time
It is the magnitude of voltage on the intersection point of the straight line L2 that 0 (s) i.e. discharges when starting when being set to V1, by the value shown in following numerical expression (1).
Numerical expression (1):
Static capacity C (kF)=(Id+td) of lithium-ion capacitor/[(V1-V2) × 1000]
Additionally, " the DC resistance R of lithium-ion capacitor " is discharge ionization voltage to be set to V0 (V), by discharge current
It is set to Id (V), and on the chart of voltage in expression discharge curve D as shown in Figure 8 and the relation of time, this is put
The approximation between the time point that the electric discharge elapsed time is 1 (s) and the time point that the electric discharge elapsed time is 3 (s) in electricity curve D is straight
When line L1 and the magnitude of voltage discharged in the intersection point that the elapsed time is the straight line L2 that 0 (s) i.e. discharges when starting are set to V1, by following
The value that represents of numerical expression (2).
Numerical expression (2):
DC resistance R (m Ω)=(V0-V1)/Id × 1000 of lithium-ion capacitor
In lithium-ion capacitor, by meeting relational expression (1) and relational expression (2), obtain high power capacity and high output spy
Property, and obtain high security while obtaining the performance of such lithium-ion capacitor.
" T × R/C " in relational expression (1) is the value of the relation representing the performance of lithium-ion capacitor and safety.
" T × R/C " more than 35 should be set to, but preferably 35～1000.
In lithium-ion capacitor, owing to " T × R/C " is in above-mentioned scope, thus in porous layer 40, by inside
The thermal conversion that short circuit occurs is heat of gasification, thereby, it is possible to make to be maintained surface temperature the electrolysis of the amount of the state comparing low temperature
Liquid carries out protecting liquid, it is possible to suppression results from the generation of internal short-circuit and makes surface temperature become the situation of high temperature.
Additionally, " R/C " in relational expression (2) is i.e. that DC resistance R is for static capacity C in lithium-ion capacitor
Ratio, is the value of the performance representing lithium-ion capacitor.The value being somebody's turn to do " R/C " is the least, lithium-ion capacitor high-performance.
In lithium-ion capacitor, owing to " R/C " is in above-mentioned scope, it is possible to obtain low resistance and static capacity is big
High-performance.
The thickness T of porous layer 40, according to static capacity C of the performance of lithium-ion capacitor, i.e. lithium-ion capacitor with
And the difference of DC resistance R and different, but be such as usually more than 120 μm, more than preferably 120 μm and less than 1000 μm.
Porous layer 40 is preferably has durability to electrolyte, positive active material or negative electrode active material, by having
The Porous sheet that the electrical conductance of the connection pore that can infiltrate electrolyte is little is constituted.
Additionally, porous layer 40 is from the viewpoint of the easy modulability and being easily formed property of thickness T, preferably by Porous sheet
The structure overlapped to form, the structure i.e. formed by the laminate of Porous sheet.
And then, from the viewpoint of the produceability of capacitor key element unit 10, porous layer 40 is preferably and constitutes unit
The dividing plate of part 11 is same composition.I.e., preferably porous layer 40 is to be formed to be formed with portion and porous layer and use portion by having dividing plate
Composition and the structure that formed.
In the example in the figures, dividing plate and porous layer 40 are made up of, specifically by the 1st Porous sheet 14 shape same
Become, this porous layer 40 have formed by the porous layer in the 1st Porous sheet 14 with portion constitute winding laminate structure,
I.e. carry out the structure of lamination by the porous layer formation portion of the 1st Porous sheet 14 at the outer peripheral face winding of element 11.
As the Porous sheet constituting porous layer 40, it is possible to use well known materials, but be preferably from cellulose (paper), people
Make at least one constituent material selected in fiber, polyethylene and polypropylene.In these, cellulose and staple fibre is mixed
Zoarium, specifically cellulose/staple fibre hybrid nonwoven cloth are preferred in durability and this aspect of economy.
Additionally, constitute the thickness of the Porous sheet of porous layer 40 without particular limitation of, but amassed by the winding of Porous sheet
In the case of layer body constitutes porous layer 40, it is usually preferred to about 15～50 μm.
Capacitor key element unit 10, in the one side of the 1st Porous sheet 14 of banding, positive electrical pole piece 12, more than the 2 of banding
The electrode laminated body 10A that hole matter sheet 15 and negative electricity pole piece 13 are laminated with this order is wound into cylindrical shape from its one end
And constitute.
Herein, positive electrical pole piece 12 and negative electricity pole piece 13 be configured to respective electrode layer 12b, 13b (with reference to Fig. 5 with
And Fig. 6) across the 2nd Porous sheet 15 opposite one another.
In the example in the figures, electrode laminated body 10A is wound in the way of negative electricity pole piece 13 becomes inner side.This
Outward, the 1st Porous sheet the 14 and the 2nd Porous sheet 15 is than positive electrical pole piece 12 and the knot of the long size of negative electricity pole piece 13
Structure.Additionally, the 1st Porous sheet 14 has the dividing plate formation portion for constituting dividing plate and for forming porous layer more than 40
Matter layer formation portion, hole, is the structure of the 2nd long size of Porous sheet 15 formed than dividing plate.In this electrode laminated body 10A,
Positive electrical pole piece 12 is laminated in except one end part 14a from the dividing plate formation portion of the 1st Porous sheet 14 and dividing plate are formed
Other end part with other end part (hereinafter also referred to " divider ends the part ") 14b in portion to porous layer formation portion
Part side, one end middle body beyond the region of 14c position, additionally, negative electricity pole piece 13 is laminated in except the 2nd Porous sheet
Middle body beyond one end part 15a of 15 and other end part 15b.
In the present invention, " positive pole " mean to flow out when electric discharge electric current, when charging the pole of side of inflow current,
" negative pole " means inflow current during electric discharge, flows out the pole of the side of electric current when charging.
Between one end part 14a and one end part 15a of the 2nd Porous sheet 15 of the 1st Porous sheet 14, with positive pole
Each mode being not directly contacted with of electrode slice 12 and negative electricity pole piece 13, in (the unit of element portion of capacitor key element unit 10
Part 11) substantially wind 1 week state under, be configured with the lithium ion source of supply 16 being made up of membranaceous lithium metal.Additionally, the 1st
Between divider ends part 14b and other end part 15b of the 2nd Porous sheet 15 of Porous sheet 14, with positive electrical pole piece
12 and each mode being not directly contacted with of negative electricity pole piece 13, in the porous layer portion (porous of capacitor key element unit 10
Matter layer 40) in substantially wind 1 week state under be configured with the lithium ion source of supply 17 being made up of membranaceous lithium metal.
As illustrated in fig. 4, at the 1st Porous sheet of the outer peripheral face of capacitor key element unit 10, i.e. composition porous layer 40
Two bands that the outer surface of other end part 14c of 14 is provided with fixed capacity device key element unit 10, that simultaneously there is adhering agent layer
18。
By arranging such band 18, it is possible to make the operation being housed in peripheral hardware container 20 by capacitor key element unit 10 become
Easily, it is possible to realize the raising of the assembling operation of convoluted LIC.
Negative electricity pole piece 13, as it is shown in figure 5, at least one side of negative electrode collector 13a in banding, is formed and lives containing negative pole
The electrode layer 13b of property material.
In the example in the figures, electrode layer 13b is formed as covering except the cap 22 being located adjacent in negative electrode collector 13a
Side edge part 13e beyond the surface of part, become to expose the state on the surface of the side edge part 13e of negative electrode collector 13a.
On the other hand, positive electrical pole piece 12, as shown in Figure 6, at least one side at the positive electrode collector 12a of banding is formed and contains
There is the electrode layer 12b of positive active material.
In the example in the figures, electrode layer 12b be formed as covering in positive electrode collector 12a except being located adjacent to bottom 23
Position side edge part 12e beyond the surface of part, become to expose the state on the surface of the side edge part 12e of positive electrode collector 12a.
Further, in electrode laminated body 10A, positive electrical pole piece 12, on the 1st Porous sheet 14 in dividing plate formation portion
Point, by side edge part 12e stacking in the way of another lateral margin protrusion of the 1st Porous sheet 14 of positive electrode collector 12a, negative electricity
Pole piece 13, on the 2nd Porous sheet 15, the side edge part 13e with negative electrode collector 13a is convex from a lateral margin of the 2nd Porous sheet 15
The mode stacking gone out.
Additionally, in capacitor key element unit 10, the positive electrode collector protruded from another lateral margin of the 1st Porous sheet 14
The side edge part 12e of 12a is tortuous to inner side middle protrusion of the other end (lower end in Fig. 1) of this capacitor key element unit 10, another
Aspect, from the side edge part 13e of the negative electrode collector 13a of a lateral margin protrusion of the 2nd Porous sheet 15 from this capacitor key element unit
One end (upper end in Fig. 1) of 10 is protruded and tortuous to inner side.
(collector body)
Positive electrode collector 12a and negative electrode collector 13a (the most also they being become " electrode collector ") passes through by having
The porous material in the hole on logical the exterior and the interior two sides is constituted.
As the form of the porous material constituting electrode collector, XPM, punch metal, wire netting can be enumerated, send out
Foam or define the Porous paper tinsel etc. of through hole by etching or electrolytic etching.
The shape in the hole of electrode collector can be set as circle, rectangle, other suitable shape.
Additionally, the thickness of electrode collector is preferably 1～50 μm from the viewpoint of intensity and lightweight.
The porosity of electrode collector is usually 10～79%, preferably 20～60%.
Herein, the porosity is calculated by following numerical expression (3).
Numerical expression (3):
The porosity (%)=[1-(true specific gravity of the quality/electrode collector of electrode collector)/(regarding of electrode collector
At volume)] × 100
By such porous material is used as electrode collector, the lithium ion released from lithium ion source of supply 16,17 passes through
The hole of electrode collector and freely move between each electrode, so can anticathode electrode slice 13 and/or positive electrical pole piece
Electrode layer 12b, 13b doped lithium ion in 12.
Material as electrode collector, it is possible to it is various that use typically uses in the purposes of organic electrolyte cell etc.
Material.
As the concrete example of the material of negative electrode collector 13a, rustless steel, copper, nickel etc. can be enumerated.Additionally, as positive pole collection
The concrete example of the material of electricity body 12a, can enumerate aluminum, rustless steel etc..
(electrode layer of negative electricity pole piece)
(negative electrode active material)
Electrode layer 13b in negative electricity pole piece 13 contains the negative electrode active material reversibly supporting lithium ion.
As constituting the negative electrode active material of electrode layer 13b, be preferably able to use such as graphite, difficult graphitized carbon or
Coalescence benzene series organic semiconductors (hereinafter also referred to " PAS ") etc., this coalescence benzene series organic semiconductor is fragrance family condensation polymer
Heat treatment thing, have the atomic number ratio (being designated as " H/C " below) of hydrogen atom/carbon atom be 0.05～1 coalescence benzene series substantially tie
Structure.
In the present invention, negative electrode active material is preferably pore diameter in more than 3nm, pore volume at more than 0.10mL/g
Material, the upper limit of this pore diameter is not defined, but usually 3～50nm scope.
Additionally, about the scope of pore volume, it is common that 0.10～0.5mL/g, it is preferable that be 0.15～0.5mL/g.
(formation of the electrode layer of negative electricity pole piece)
Electrode layer 13b in negative electricity pole piece 13 utilizes the negative electrode active material containing above-mentioned material with carbon element, PAS etc. to form
Material, be formed on negative electrode collector 13a, but its method the most specific, it is also possible to and utilize known method.
Specifically, by formed body being pasted on the surface of negative electrode collector 13a, it is possible to form electrode layer 13b, this one-tenth
Body is by being modulated in water-medium or organic solvent dispersion negative electrode active material powder, binding agent and as required
The slurry of dispersed electro-conductive auxiliary agent, and this slurry is coated the surface of negative electrode collector 13a and is dried, or in advance
First above-mentioned slurry is configured to lamellar, and the formed body obtained.
(binding agent)
As the binding agent of the modulation for slurry, can enumerate, the elastomeric adhesive such as such as butadiene-styrene rubber (SBR), third
The thermoplastic resins such as fluorine resin, polypropylene, polyethylene such as alkene system binding agent, politef, polyvinylidene fluoride.They it
In, the preferred fluorine resin as binding agent, particularly preferably use the atomic ratio (being designated as " F/C " below) of fluorine atom/carbon atom
Being more than 0.75 and fluorine resin less than 1.5, more preferably F/C is more than 0.75 and fluorine resin less than 1.3.
The usage amount of binding agent is different according to the difference of the kind of negative electrode active material, electrode shape etc., but for negative
Pole active substance, is 1～20 mass %, preferably 2～10 mass %.
(electric conductivity auxiliary agent)
Additionally, as the electric conductivity auxiliary agent used as desired, can enumerate such as acetylene carbon black, section's qin superconduction white carbon black,
Graphite, metal dust etc..
The usage amount of electric conductivity auxiliary agent according to the difference of the electric conductivity of negative electrode active material, electrode shape etc. and different, but
It is the ratio of 2～40 mass % preferably for negative electrode active material.
The thickness of the electrode layer 13b in negative electricity pole piece 13, puts down with the thickness with the electrode layer 12b in positive electrical pole piece 12
The mode of weighing apparatus is designed, and guarantees enough energy density with the convoluted LIC for obtaining, but from the convoluted LIC obtained
Output density, energy density and industrial productivity etc. from the viewpoint of, in the situation of the one side being formed at negative electrode collector 12a
Under, it is common that 15～100 μm, preferably 20～80 μm.
(electrode layer of positive electrical pole piece)
Electrode layer 12b in positive electrical pole piece 12 contains can reversibly support lithium ion and/or such as tetrafluoro boron
The positive active material of anion as hydrochlorate.
As the positive active material constituting electrode layer 12b, it is possible to it is the coalescence benzene series base of 0.05～1 that use has H/C
The PAS etc. of this structure, this PAS are such as activated carbon, electroconductive polymer, the heat treatment thing of fragrance family condensation polymer.
Electrode layer 12b in positive electrical pole piece 12 can be by the side as the electrode layer 13b in negative electricity pole piece 13
Method and formed.
The thickness of the electrode layer 12b in positive electrical pole piece 12 is put down with the thickness with the electrode layer 13b in negative electricity pole piece 13
The mode of weighing apparatus designs, and guarantees enough energy density with the convoluted LIC to gained, but from the output of the convoluted LIC of gained
From the viewpoint of density, energy density and industrial productivity etc., in the case of the one side being formed at positive electrode collector 12a, logical
It is often 40～80 μm, preferably 50～70 μm.
(dividing plate)
As the Porous sheet of composition dividing plate, use and electrolyte, positive active material or negative electrode active material are had
There is durability, there is the structure that the electrical conductance of the connection pore that can infiltrate electrolyte is little.
It addition, in the example in the figures, constitute the 2nd Porous sheet 15 in the Porous sheet of dividing plate and be mainly used for being formed
The component of dividing plate, the 1st Porous sheet 14, is the dual-purpose structure for forming porous layer 40 while forming dividing plate as previously mentioned
Part.
As the material of Porous sheet constituting dividing plate, it is possible to use cellulose (paper), staple fibre, polyethylene, poly-third
Alkene and material known to other.Among them, cellulose and the mixture of staple fibre, specifically cellulose/staple fibre
Hybrid nonwoven cloth is preferred in durability and this aspect of economy.
The thickness of the Porous sheet constituting dividing plate is not particularly limited, but about generally preferable 20～50 μm.
(lithium ion source of supply)
Such as Fig. 7, lithium ion source of supply 16,17 preferably crimps or is laminated in metal collector body (following also referred to as " lithium
Electrode current collector ") 16a, 17a.
In such a configuration, by lithium electrode collector body 16a, 17a being arranged lithium electrode terminal (omitting diagram), or pass through
To arrange lithium electrode collector body 16a, 17a in the way of the respective lateral margin of the 1st Porous sheet the 14 and the 2nd Porous sheet 15 protrusion
Side edge part, it is possible to electrically connect with negative electrode terminal 35.
As this lithium electrode collector body 16a, 17a, the formation of vesicular structure with electrode collector as is preferably used, so that
The lithium metal constituting lithium ion source of supply 16,17 is easily deposited with or crimps, and makes lithium ion pass through as required.Additionally, lithium
The material of electrode current collector 16a, 17a is preferably used the material do not reacted with the lithium ion source of supply 16,17 of rustless steel etc., particularly
The preferably material as negative electrode collector.By by the material of vesicular structure be used as lithium electrode collector body 16a, 17a, and by lithium from
Sub-source of supply is disposed in porous layer portion, thus also can be using the lithium electrode collector body of this lithium ion source of supply of composition as porous layer
The structural wood of 40 and utilize.
Additionally, in the case of using the conductive porous materials such as stainless (steel) wire as lithium electrode collector body 16a, 17a, preferably will
Constitute lithium metal at least some of of lithium ion source of supply 16,17, more than particularly 80 mass % be embedded to lithium electrode collector body
The hole of 16a, 17a.
Additionally, the thickness of lithium electrode collector body 16a, 17a is preferably about 10～200 μm.
Additionally, the thickness to the lithium metal of lithium electrode collector body 16a, 17a crimping considers negative electricity pole piece 13 and/or just
The amount of the lithium ion supported in advance in pole electrode slice 12 and suitably determine, but about generally preferable 100～300 μm.
Constitute the amount of the lithium metal of lithium ion source of supply 16,17, so that positive electrical pole piece 12 and negative electricity pole piece 13 short circuit
Time the mode that current potential is below 2.0V of positive electrical pole piece 12, it is preferable to set the amount being doped for lithium ion,.
(carrying)
As with 18 the material of base material, as long as electrolyte to be had durability, and will not be to the convoluted LIC obtained
Bring bad influence, be then not particularly limited.
Furthermore it is preferred that the thickness with 18 is about 25～100 μm, width is 5～about 10mm, because can stably consolidate
Determine capacitor key element unit 10, and improve workability.
Additionally, can arrange in the way of more than 1 week of wound capacitor key element unit 10 with 18, it is also possible to wind electricity
The mode less than 1 week of tank features unit 10 is arranged.
(peripheral hardware container: peripheral hardware body mechanism)
Constitute the metal peripheral hardware container 20 of convoluted LIC, at the two ends of cylindric surrounding wall portion 21 the most integratedly
Form discoideus cap 22 and bottom 23 and constitute.
Herein, " integrally " comprise the weld seam that brought by welding etc., connection carries out the situation of integration.
In the example in the figures, bottom 23 is continuously formed by integrally formed and with surrounding wall portion 21 the other end is one
Body, cap 22, the formation that forms as one by the periphery welding with one end of surrounding wall portion 21.
In in the receiving space formed by surrounding wall portion 21, cap 22 and bottom 23, with this capacitor key element unit 10
The other end, i.e. the side edge part 12e of positive electrode collector 12a be positioned at 23 sides, bottom, one end of this capacitor key element unit 10, the most negative
The side edge part 13e of electrode current collector 13a is positioned at the mode of cap 22 side, and the direction of principal axis along this peripheral hardware container 20 configures capacitor and wants
Element unit 10, and the electrolysis that filling is made up of the non-proton organic solvent electrolyte solution of lithium salts in this peripheral hardware container 20
Liquid.
At the cap 22 of peripheral hardware container 20, by arrange with sowing discord mutually in the way of the outer surface of cap 22 protrusion respectively by
Anode electrode terminal 30 that recess 31,36 and protuberance 32,37 are constituted and negative electrode terminal 35, at this anode electrode terminal
The middle body of the cap 22 between 30 and negative electrode terminal 35 defines relief valve (not shown).
Specifically, anode electrode terminal 30 is set to be fixed on cap 22 state that electrically connects by welding
Put.On the other hand, negative electrode terminal 35 is arranged, at through cap 22 in the way of stretching at the through cap of thickness direction 22
Part, the packing ring 38 being made up of Ins. ulative material, thus, negative electrode are set between negative terminal electrode 35 and cap 22
Terminal 35 is set as and the state of cap 22 electric insulation.
As the metal of composition peripheral hardware container 20, it is not particularly limited, such as, can use the metal material such as ferrum, aluminum, but
From the viewpoint of the lightweight of the convoluted LIC obtained, preferably aluminum.
The size of peripheral hardware container 20 is set accordingly with the size of the capacitor key element unit 10 being configured at inside, example
If total length is 120～150mm, internal diameter is 30～60mm.Additionally, the meat thickness for example, 0.3～1.2mm of peripheral hardware container 20, preferably
It is 0.4～0.8mm.
As anode electrode terminal 30, it is possible to use the structure being made up of aluminum aptly, on the other hand, as negative terminal
Electrode 35 can be advantageously employed in the structure of the plating nickel on surface of the matrix being made up of copper.
Additionally, the external diameter of anode electrode terminal 30 and negative electrode terminal 35 is such as 5～12mm.
Additionally, the protrusion height of the cap 22 from anode electrode terminal 30 and negative electrode terminal 35 be such as 5～
30mm。
The anode electrode terminal 30 of the cap 22 being located in peripheral hardware container 20 and negative electrode terminal 35 and capacitor are wanted
Element unit 10 is electrically connected by structure as shown in Figure 1.
That is, in one end of capacitor key element unit 10, by the discoideus negative electrode collector plate 26 that is made up of metal to pass through
Such as infrared ray welding (laser welding etc.), ultrasonic fusing or electric resistance welding and be fused to the lateral margin of negative electrode collector 13a
Portion 13e the state electrically connected and utilize the insulating component 27 being made up of insulative resin and the shape insulated with peripheral hardware container 20
State and arrange, in this negative electrode collector plate 26, be electrically connected with negative wire 28, and then, this negative wire 28 and negative electrode terminal
35 electrical connections.So, on the side edge part 13e of negative electrode collector 13a, via negative electrode collector plate 26 and negative wire 28
It is electrically connected with negative electrode terminal 35.
Additionally, at the other end of capacitor key element unit 10, the discoideus positive pole collector plate 25 being made up of metal with
The side edge part 12e of positive electrode collector 12a is by such as infrared ray welding (laser welding etc.), ultrasonic fusing or electric resistance welding
And configure under welding the state that electrically connects, and then, this positive pole collector plate 25 inner face to the bottom 23 of peripheral hardware container 20
The welding electrically connecting by such as infrared ray welding (laser welding etc.), ultrasonic fusing or electric resistance welding.So,
Anode electrode terminal has been electrically connected by positive pole collector plate 25 and peripheral hardware container 20 at the side edge part 12e of positive electrode collector 12a
30。
As positive pole collector plate 25, it is possible to use the collector plate that aluminum is constituted, as negative electrode collector plate 26, it is possible to use at copper
The collector plate of the plating nickel on surface of the matrix constituted.
Additionally, the thickness of positive pole collector plate 25 and negative electrode collector plate 26 is such as 0.4～1.0mm.
(electrolyte)
The electrolyte being made up of the non-proton organic solvent electrolyte solution of lithium salts it is filled with in peripheral hardware container 20.
As constituting the lithium salts of electrolyte, being to transfer lithium ion, be not electrolysed, lithium ion can be steady
Surely the electrolyte existed, as its concrete example, can enumerate LiCLO4、LiAsF6、LiBF4、LiPF6、Li(C2F5SO2)2N
Deng.
As the concrete example of non-proton organic solvent, can enumerate ethylene carbonate, ethylene carbonate, dimethyl carbonate,
Diethyl carbonate, gamma-butyrolacton, acetonitrile, dimethoxy-ethane, oxolane, dioxolane, dichloromethane, sulfolane etc..This
A little non-proton organic solvents, can be used alone or mix two or more use.
Electrolyte is by mixing above-mentioned electrolyte and solvent with the state after being dehydrated fully, and is modulated, but is
Making the internal resistance based on electrolyte reduce, the concentration of the electrolyte in electrolyte is preferably at least 0.1 mole/more than L, more
It is preferably 0.5～1.5 mole/L.
It is inserted into capacitor key element unit 10, and filling electrolyte to peripheral hardware container 20, thus obtains such structure
Convoluted LIC.
Further, in the convoluted LIC so made, in peripheral hardware container 20, the electrolysis that can transfer lithium ion it is filled with
Liquid, if so placing suitable period, then by negative electricity pole piece 13 and/or positive electrical pole piece 12 and lithium ion supply
The electrochemical contact in source 16,17, the lithium ion released from lithium ion source of supply 16,17 is to negative electricity pole piece 13 and/or just
Pole electrode slice 12 adulterates.
Additionally, by advance the 1st Porous sheet the 14 and the 2nd Porous sheet 15 be configured with lithium ion source of supply 16,
Wind electrode laminated body 10A under the state of 17, and making and the lithium of capacitor key element unit 10 can be carried out in same operation
The configuration of ion source of supply 16,17, so obtaining higher productivity.
In the convoluted LIC of such structure, the outer surface at element 11 is formed with porous layer 40, this porous layer
The thickness T of 40 determines in static capacity C of this convoluted LIC and the relation of DC resistance R, even if so there is inside
In the case of short circuit, also there is the heat energy that the heating drastically produced due to stream super-high-current is brought by porous layer 40
The electrolyte of infiltration absorbs, it is possible to the surface temperature of suppression peripheral hardware container 20 becomes high temperature, and, it is possible to this porous is set
Matter layer 40 makes the static capacity of this convoluted LIC diminish, the problem of high resistance etc. does not produces.
Therefore, according to convoluted LIC, obtain high power capacity and high output characteristic, and the situation of internal short-circuit is occurring
Under, surface temperature can be suppressed to be heated.Thus obtain high safety.
Additionally, in convoluted LIC, by by being that same the 1st Porous sheet 14 formed constitutes porous layer with dividing plate
40, it is possible in same operation, carry out formation and the formation of Porous portion (porous layer 40) in element portion (element 11), so
Its manufacture becomes simple.
And then, convoluted LIC can be used as to constitute the electric energy storage device device (mould possessing multiple lithium-ion capacitor aptly
Block).In such electric energy storage device device, though the situation of a generation internal short-circuit in multiple lithium-ion capacitors
Under, the surface temperature that the lithium-ion capacitor of this internal short-circuit occurs also can be suppressed to become high temperature, so the lithium adjoined can be prevented
Ionistor is affected by the torrid zone.
This concludes the description of embodiments of the present invention, but be not limited to above-mentioned embodiment, and can increase various
Change.
Such as, porous layer can by constitute the dividing plate of lithium-ion capacitor key element multiple compositions (such as at Fig. 1～
In convoluted LIC shown in Fig. 7, it is the 1st Porous sheet the 14 and the 2nd Porous sheet 15) formed, it is also possible to only by constituting
A composition or a part in multiple compositions of dividing plate form and are formed.
Additionally, porous layer can also utilize the group different from the composition of the dividing plate constituted in lithium-ion capacitor key element
Become, the most special composition and formed.
Additionally, in lithium-ion capacitor, lithium-ion capacitor key element can be so-called stack-up type, i.e. have multiple just
Pole electrode slice and negative electricity pole piece are across the structure of dividing plate alternately lamination, additionally, peripheral hardware container can be weight mutually
The container of the structure mutually engaged airtightly in the junction surface that the peripheral hardware laminated film closed is formed on each edge, periphery.
Hereinafter, illustrate embodiments of the invention, but the present invention is not limited to such embodiment.
<embodiment 1>
According to the structure of Fig. 2～Fig. 7, make element and porous layer as described below.
(1) manufacture of negative electricity pole piece:
The phenolic resin forming board of thickness 0.5mm is put in siliconit electric furnace, in a nitrogen atmosphere with 50 DEG C/h
Speed is warmed up to 500 DEG C, then is warmed up to 660 DEG C with the speed of 10 DEG C/h, carries out heat treatment, thus manufactures PAS plate.Pass through
PAS plate obtained by pulverizing with disc mill, and modulate PAS powder body.The H/C of this PAS powder body is 0.8.
It follows that by PAS powder body 100 Quality Mgmt Dept after modulation and polyvinylidene fluoride powder 10 Quality Mgmt Dept are added to
Dispersion is also dissolved in N-Methyl pyrrolidone 80 Quality Mgmt Dept, thus modulates negative pole slurry.Utilize die slot coating machine by this negative pole
With slurry interval be coated in by thickness be 32 μm, the porosity be copper XPM (Nippon Metal Ind of 50%
Produce) two sides of negative electrode collector material that constitutes, and be dried, obtained film is applied punch process, thus forms length
280.0cm, the electrode layer of width 11.7cm.Further, by cutting off negative electrode collector material, at a length of 280.0cm, width it is
The two sides of the negative electrode collector of 12.7cm forms a length of 280.0cm, width is the electrode layer of 11.7cm, manufactures at negative pole current collection
Body does not forms the negative electricity pole piece with the side edge part that width is 10mm of electrode layer.
Obtained by the thickness (negative electrode collector and be formed at the aggregate thickness of electrode layer on its two sides) of negative electricity pole piece
It is 80 μm.
(2) manufacture of positive electrical pole piece:
By being 1950m by specific surface area2Active carbon powder 100 Quality Mgmt Dept of/g, acetylene carbon black 10 Quality Mgmt Dept, propylene
Binding agent 6 Quality Mgmt Dept and carboxymethyl cellulose 4 Quality Mgmt Dept add in water and disperse, and have modulated positive pole slurry.
On the other hand, utilize die slot coating machine thickness be 35 μm, the porosity be the aluminum XPM (Japan of 50%
Metal industry Co., Ltd. produces) two sides of positive electrode collector material that constitutes, interval coats the carbon series conductive coating (day of non-water system
EB-815) and be dried this Acheson Co., Ltd. produces:, thus form a length of 260cm, width is the substrate of 11.2cm
Layer.Positive electrode collector is 52 μm with the aggregate thickness of the substrate layer being formed at its two sides, and the hole of positive electrode collector material is by substrate layer
Close.
It follows that utilize die slot coating machine the positive pole slurry interval after modulation to be coated in be formed at positive electrode collector material
The two sides of substrate layer is also dried, and obtained film is applied punch process, thus forms a length of 260.0cm, width
Electrode layer for 11.2cm.Further, by cutting off positive electrode collector material, it is the positive pole of 12.2cm at a length of 260.0cm, width
The two sides of collector body forms a length of 260.0cm, width is the electrode layer of 11.2cm, manufactures and does not forms electrode at positive electrode collector
Layer, the side edge part that there is width is 10mm positive electrical pole piece.
Obtained by the thickness (positive electrode collector and be formed at the substrate layer on its two sides and electrode layer of positive electrical pole piece
Aggregate thickness) it is 210 μm.
(3) element and the making of porous layer:
As dividing plate formed Porous sheet, preparation length 340.0cm, width 13.5cm, thickness 30 μm by fiber
1st Porous sheet of element/staple fibre hybrid nonwoven cloth composition and the 2nd Porous sheet.
Back side configured length in one end part of the 1st Porous sheet of preparation is 5cm, width is 10.0cm, thickness is
The lithium ion source of supply that the lithium metal foil of 170 μm is constituted, is fixed by crimping, joins on this lithium ion source of supply
Put a length of 5cm, width is 12.7cm, thickness is 32 μm, the porosity be 50% copper XPM constitute lithium electrode collection
Electricity body, is fixed by crimping.Additionally, the back side of the other end part at the 1st Porous sheet, configured length is
The lithium ion source of supply that the lithium metal foil that 38cm, width are 10.0cm, thickness is 170 μm is constituted, is crimped and is fixed,
On these lithium ion sources of supply, configured length is 38cm, width is 12.7cm, thickness is 32 μm, the porosity is the copper of 50%
The lithium electrode collector body that XPM processed is constituted, is fixed by crimping.Further, on the surface of the 1st Porous sheet
In two lithium ion sources of supply between position protrude from another lateral margin of the 1st Porous sheet with the side edge part of positive electrode collector
Mode configure positive electrical pole piece.Then, by this positive electrical pole piece with the side edge part of positive electrode collector from the 2nd Porous
Mode stacking the 2nd Porous sheet that another lateral margin of sheet protrudes, on the 2nd Porous sheet with the side edge part of negative electrode collector from
The mode stacking negative electricity pole piece that one lateral margin of the 2nd Porous sheet protrudes, thus constitute electrode laminated body.Herein, positive electrical
Pole piece and negative electricity pole piece are the most right across the 2nd Porous sheet with the electrode layer being formed in the electrode layer on respective two sides
The mode put configures.
By this electrode laminated body for the plug of the stainless steel of diameter 8mm, in the way of negative electricity pole piece becomes inner side
From one end of this electrode laminated body wind, thus formed internal diameter be 8mm, external diameter be the element of 38mm, and then, outside this element
Which floor the Porous sheet that the porous layer of the material as the 1st Porous sheet is formed wound by side face, forms thickness 180 μm
Winding laminate constitute porous layer, thus, be produced on outer surface and define element (the capacitor key element list of porous layer
Unit).Further, by the outer peripheral face at capacitor key element unit, one side is set there is adhering agent layer, size in length and breadth is 5.0cm
× 1.0cm, thickness are two bands of the polypropylene composition of 35 μm, and fix this capacitor key element unit.
The side edge part of the negative electrode collector in obtained element is tortuous, at the lateral margin of this negative electrode collector to inner side
Portion, is that the made of copper discoideus negative electrode collector plate after the nickel plating of 0.4mm is melted by electric resistance welding by a diameter of 35mm, thickness
Connect and be electrically connected.And then, in negative electrode collector plate, by a length of 20mm, width be 15mm, thickness be 0.4mm, after nickel plating
Negative wire made of copper utilize laser welding and welding being electrically connected, and be configured to and peripheral hardware in negative electrode collector plate
The polyacrylic insulating component of container insulation.
Additionally, the opposite side edge of positive electrode collector is tortuous to inner side, at the side edge part of this positive electrode collector by diameter
For the welding being electrically connected by electric resistance welding of the positive pole collector plate of aluminum that 35mm, thickness are 0.4mm.
(4) manufacture of winding LIC:
Preparation external diameter is 40mm, internal diameter is 39.2mm (meat thickness is 0.4mm), total length be 140mm aluminum have round-ended cylinder
The peripheral hardware container material of shape, in this peripheral hardware container material, configuration is provided with the capacitor key element list of positive pole collector plate and negative electrode collector plate
Unit, and positive pole collector plate is fused to by ultrasonic fusing the inner face of the bottom of peripheral hardware container material and is electrically connected.
On the other hand, the discoideus lid component of the aluminum that a diameter of 40mm, thickness are 1.2mm forms electrolyte note
Entrance and the through hole of electrode terminal configuration, the through hole of this lid component is inserted in matrix made of copper plating nickel on surface and
Become, external diameter is 10mm, the recess of a length of 15mm, by the protuberance after nickel plating on the surface of the matrix formed at copper, bearing
The mode that pole electrode terminal is configured to protrude from the one side of this lid component is to this recesses fit, and is utilizing polyphenylene sulfide to make
The insulation of packing ring and lid component state under fix this negative electrode terminal.Additionally, by the one side at lid component with from lid component
The mode protruded of one side configure anode electrode terminal, and the cardinal extremity of this anode electrode terminal by electric resistance welding welding and is consolidated
Due to lid component, thus be electrically connected, this anode electrode terminal to aluminum, external diameter be 10mm, the recess of a length of 15mm
Coordinate the protuberance formed on the surface of matrix made of copper by aluminum.
It follows that the negative wire of the negative electrode collector plate cardinal extremity at negative electrode terminal will be fused to by laser welding
Welding after being electrically connected, carries out integration by lid component by welding to peripheral hardware container member and forms cap, and then, from
The electrolyte inlet being formed at this cap is infused in ethylene carbonate the concentration dissolving LiPF with 1 mole/L6Electricity
Solve liquid, then, utilize electrolyte inlet capping plug to live this electrolyte inlet, thus manufacture shown in Fig. 1 at peripheral hardware container
The convoluted LIC (the most also referred to as " convoluted LIC (1) ") of the structure of interior collecting capacitor key element unit and electrolyte.
The static capacity of obtained convoluted LIC (1) is 3.5 (kF).
(5) D.C. resistance measures
About obtained convoluted LIC (1), the resistance measurement device produced with HIOKI company measures in peripheral hardware container
Cap and bottom between electrical resistance value (DC resistance (DC-IR)) time be 1 (m Ω).
(6) puncture test measures
About obtained convoluted LIC (1), according to following puncture test condition, it is configured such that peripheral hardware container
Pipe axle become level, separate the position of 70mm from top vertical in the bottom from peripheral hardware container towards the direction of cap
On direction puncture, measure the most immediately the spaced up 60mm towards the side of bottom from the position of this puncture position (from
Bottom in peripheral hardware container is towards the position of the spaced up 10mm in side of cap) surface temperature time, its surface temperature is 84 DEG C.
[puncture test condition]
Thorn footpath: φ 2.5
Puncture speed: 1mm/s
On-test voltage: 3.8V
Temperature measuring equipment: thermocouple
<embodiment 2>
In embodiment 1, except the length of negative electrode collector is set to 510.0cm, the length of positive electrode collector is set to
480.0cm, adjusts the thickness of electrode layer so that the aggregate thickness of positive electrode collector and the electrode layer that is formed at its two sides is 100 μ
M, and the length of the 1st Porous sheet and the 2nd Porous sheet is set to 534.0cm, then the thickness of porous layer is set to 120 μm
In addition, convoluted LIC (hereinafter also referred to " convoluted LIC (2) ") is made in the same manner as this embodiment 1.
About obtained convoluted LIC (2), measure static capacity and direct current by maneuver similarly to Example 1
Resistance value, and carry out puncture test mensuration by maneuver similarly to Example 1.Result is illustrated in Table 1.
<embodiment 3>
In example 2, the length of the 1st Porous sheet and the 2nd Porous sheet is set to 546.0cm, by porous layer
Thickness be set to 180 μm, make convoluted LIC (hereinafter also referred to " convoluted LIC in the same manner as this embodiment 2 beyond this
(3)”)。
About obtained convoluted LIC (3), by maneuver similarly to Example 1, measure static capacity and direct current
Resistance value, and carry out puncture test mensuration by maneuver similarly to Example 1.Result is illustrated in Table 1.
<embodiment 4>
In embodiment 1, except the length of negative electrode collector is set to 550.0cm, the length of positive electrode collector is set to
520.0cm, adjusts the thickness of electrode layer so that the aggregate thickness of positive electrode collector and the electrode layer that is formed at its two sides becomes 100
μm, and the length of the 1st Porous sheet and the 2nd Porous sheet is set to 586.0cm, then the thickness of porous layer is set to 120 μ
Beyond m, make convoluted LIC (hereinafter also referred to " convoluted LIC (4) ") in the same manner as this embodiment 1.
About obtained convoluted LIC (4), measure static capacity and direct current by maneuver similarly to Example 1
Resistance value, and carry out puncture test mensuration by maneuver similarly to Example 1.Result is illustrated in Table 1.
<comparative example 1>
In embodiment 1, except the length of the 1st Porous sheet and the 2nd Porous sheet is set to 316.0cm, and will be many
The thickness of hole matter layer is set to beyond 60 μm, and the convoluted LIC of comparison (" compare by following being also referred to as in the same manner as this embodiment 1
With convoluted LIC (1) ").
About obtained comparison with convoluted LIC (1), by maneuver similarly to Example 1 measure static capacity with
And DC resistance, and carry out puncture test mensuration by maneuver similarly to Example 1.Result is illustrated in Table 1.
<comparative example 2>
In embodiment 1, except the length of the 1st Porous sheet and the 2nd Porous sheet is set to 328.0cm, and will be many
The thickness of hole matter layer is set to beyond 120 μm, and the convoluted LIC of comparison is (hereinafter also referred in the same manner as this embodiment 1
" compare with convoluted LIC (2) ").
About obtained comparison with convoluted LIC (2), by maneuver similarly to Example 1 measure static capacity with
And DC resistance, and carry out puncture test mensuration by maneuver similarly to Example 1.Result is illustrated in Table 1.
<comparative example 3>
In example 2, except the length of the 1st Porous sheet and the 2nd Porous sheet is set to 522.0cm, and will be many
The thickness of hole matter layer is set to beyond 60 μm, the convoluted LIC (hereinafter also referred to " ratio of comparison in the same manner as this embodiment 2
Relatively with convoluted LIC (3) ").
About obtained comparison with convoluted LIC (3), by maneuver similarly to Example 1 measure static capacity with
And DC resistance, and carry out puncture test mensuration by maneuver similarly to Example 1.Result is illustrated in Table 1.
<comparative example 4>
In example 4, except the length of the 1st Porous sheet and the 2nd Porous sheet is set to 562.0cm, by thickness
Being set to 40 μm and be set to beyond 40 μm by the thickness of porous layer, comparison is convoluted in the same manner as this embodiment 4
LIC (hereinafter also referred to " compares with convoluted LIC (4) ").
About obtained comparison with convoluted LIC (4), by maneuver similarly to Example 1 measure static capacity with
And DC resistance, and carry out puncture test mensuration by maneuver similarly to Example 1.Result is illustrated in Table 1.
<comparative example 5>
In example 4, except the length of the 1st Porous sheet and the 2nd Porous sheet is set to 574.0cm, and will be many
The thickness of hole matter layer is set to beyond 80 μm, the convoluted LIC (hereinafter also referred to " ratio of comparison in the same manner as this embodiment 4
Relatively with convoluted LIC (5) ").
About obtained comparison with convoluted LIC (5), by maneuver similarly to Example 1 measure static capacity with
And DC resistance, and carry out puncture test mensuration by maneuver similarly to Example 1.Result is illustrated in Table 1.
<comparative example 6>
As follows, the stack-up type lithium-ion capacitor about comparison (hereinafter also referred to " compares and uses stack-up type
LIC (6) ") and obtained comparison stack-up type LIC, with the constant-current charge of 1.5A until no-voltage becomes 3.8V, then exist
Carry out 1 hour applying 3.8V determine voltage determine electric current-constant-voltage charge after, repeating the electric current of determining with 1.5A, to carry out electric discharge straight
Become the circulation of the 3.8V-2.2V of 2.2V to no-voltage, with zero static capacity in the electric discharge of the 10th time (lithium-ion capacitor
Static capacity), measure internal resistance (DC resistance of lithium-ion capacitor).In addition by maneuver similarly to Example 1
Carry out puncture test mensuration.Result is illustrated in Table 1.
(1) manufacture of negative electricity pole piece:
By the maneuver as the manufacture of (1) negative electricity pole piece of embodiment 1, formed on the two sides of negative electrode collector material
Electrode layer, cuts off it in the way of size in length and breadth becomes 6.0cm × 7.5cm (except terminals fuse portion) thus manufactures negative electrode
Sheet.
(2) manufacture of positive electrical pole piece:
By mixing ratio surface area 2000m2Active carbon powder 85 Quality Mgmt Dept of/g, acetylene carbon black powder body 5 Quality Mgmt Dept, propylene
It is resin binder 6 Quality Mgmt Dept, carboxymethyl cellulose 4 Quality Mgmt Dept and water 200 Quality Mgmt Dept, and modulates the slurry of positive pole.
On the other hand, in aluminum XPM (Nippon Metal Ind of thickness 35 μm (porosity 50%)
Produce) constitute positive electrode collector material two sides with spray regime apply non-water system carbon series conductive coating (Japan Acheson's strain formula
Commercial firm produces: EB-815), and is dried, thus forms conductive layer.Positive electrode collector material and the conductive layer being formed at its two sides
Aggregate thickness be 52 μm, on positive electrode collector material, hole is closed by conductive layer substantially.
It follows that by being formed at the positive pole obtained by the two sides of conductive layer of positive electrode collector material applies with roll coater
Slurry, and be vacuum dried, thus form electrode layer, and be cut to the most a size of 5.8cm × 7.3cm and (remove
Terminals fuse portion), thus manufacture positive electrical pole piece.In obtained positive electrical pole piece, positive electrode collector and be formed at its two
The conductive layer in face and the aggregate thickness of electrode layer are 152 μm, and the thickness of electrode layer is 100 μm on two sides.
(3) manufacture of stack-up type lithium-ion capacitor:
Cellulose/staple fibre mixing the nothing using the most a size of 6.2cm × 7.7cm, thickness to be 35 μm as dividing plate
Spinning cloth, lamination positive electrical pole piece and negative electricity pole piece, to be consisted of the outermost layer of two sides and to make opposed faces become negative electricity pole piece
It is 40 layers, fixing with band at this outermost layer configuration dividing plate, and melted by the terminal of ultrasonic fusing positive electrode collector respectively
Meet the terminals fuse portion (21) of portion (20), negative electrode collector, and make electrode laminate.
Upper surface and lower surface at obtained electrode laminate respectively configure one by metallic lithium foil to thickness 80 μm
The lithium electrode of stainless (steel) wire crimping, and configured thereon thickness 0.5mm polyethylene making sheet, with band fixing three
Pole lamination unit.Utilize top peripheral hardware film laminated film and the bottom peripheral hardware film laminated film that this central part is applied constriction processing
And inject this three pole lamination unit, after 3 limit hot melts to this laminated film, make electrolyte (to by ethylene carbonate, carbonic acid two
The mass ratio of ethyl ester and ethylene carbonate is set to the mixed solvent of 3: 4: 1 and dissolves LiPF with the concentration of 1 mole/L6Solution)
After vacuum infiltration, under reduced pressure hot melt remaining 1 limit, thus the stack-up type lithium-ion capacitor of comparison (compares use
Stack-up type LIC (6)).
[table 1]
In table 1, in comparative example 6, the hurdle to " the thickness T of porous layer ", additional bracket represents and is disposed in electrode lamination
The thickness of the polyethylene making sheet on body.
According to table 1 as a result, it is possible to the lithium-ion capacitor confirmed in embodiment 1～embodiment 4 has high static capacity,
DC resistance is little, moreover it is possible to confirm that carrying out puncturing rear surface temperature is than relatively low temperature.Therefore, it is known that this embodiment 1～reality
Executing the lithium-ion capacitor in example 4 is high static capacity, low resistance and the lithium-ion capacitor with safety.
The lithium-ion capacitor from comparative example 1～comparative example 5 surface temperature after puncturing becomes more than 150 DEG C
This situation of high temperature understand, safety is relatively low.Additionally, the lithium-ion capacitor understood in comparative example 6 is after puncturing
Although surface temperature is the relatively low temperature of ratio, but its lithium-ion capacitor low, high-resistance that is static capacity.
Claims (5)
1. a lithium-ion capacitor, is positive electrical pole piece and negative electrode sheet to be overlapped to form by electrolyte with across dividing plate
Lithium-ion capacitor key element be contained in the lithium-ion capacitor in peripheral hardware container, it is characterised in that
It is formed with porous layer on the outer surface of described lithium-ion capacitor key element,
The static capacity of this lithium-ion capacitor is being set to C, the DC resistance of this lithium-ion capacitor is being set to R and by institute
State the thickness of porous layer when being set to T, meet following relational expression (1) and following relational expression (2), and described porous layer
Thickness T less than 1000 μm, wherein the unit of C be the unit of kF, R be m Ω, the unit of T is μm,
Relational expression (1): 35≤T × R/C；
Relational expression (2): 0.01≤R/C≤5.
2. according to the lithium-ion capacitor described in claim 1, it is characterised in that described porous layer is 15～50 by thickness
The winding laminate of the Porous sheet of μm is constituted.
3. according to the lithium-ion capacitor described in claim 1 or 2, it is characterised in that described porous layer by with described every
Plate same parts is constituted.
4. according to the lithium-ion capacitor described in claim 1 or 2, it is characterised in that described porous layer by from cellulose,
At least one selected in staple fibre, polyethylene and polypropylene is constituted.
5. according to the lithium-ion capacitor described in claim 1 or 2, it is characterised in that the thickness of described porous layer is 120
More than μm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-234276 | 2010-10-19 | ||
| JP2010234276 | 2010-10-19 | ||
| PCT/JP2011/064773 WO2012053256A1 (en) | 2010-10-19 | 2011-06-28 | Lithium ion capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103201803A CN103201803A (en) | 2013-07-10 |
| CN103201803B true CN103201803B (en) | 2016-11-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1855327A (en) * | 2005-04-21 | 2006-11-01 | 三菱电机株式会社 | Electric double layer capacitor |
| CN101517774A (en) * | 2006-07-26 | 2009-08-26 | 永备电池有限公司 | Electrochemical cell with positive container |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1855327A (en) * | 2005-04-21 | 2006-11-01 | 三菱电机株式会社 | Electric double layer capacitor |
| CN101517774A (en) * | 2006-07-26 | 2009-08-26 | 永备电池有限公司 | Electrochemical cell with positive container |
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