CN101536243A - Electricity storage device - Google Patents
Electricity storage device Download PDFInfo
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- CN101536243A CN101536243A CNA2007800424844A CN200780042484A CN101536243A CN 101536243 A CN101536243 A CN 101536243A CN A2007800424844 A CNA2007800424844 A CN A2007800424844A CN 200780042484 A CN200780042484 A CN 200780042484A CN 101536243 A CN101536243 A CN 101536243A
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Abstract
Disclosed is an electricity storage device which can be charged/discharged at high rate and have high output, high capacity and excellent repeating charge/discharge characteristics, although it uses a non-carbon material as a negative electrode active material. Specifically disclosed is an electricity storage device comprising: a positive electrode collector; a positive electrode disposed on the positive electrode collector and including a positive electrode active material which can reversibly absorb/desorb at least anions; a negative electrode collector; and a negative electrode disposed on the negative electrode collector and including a negative electrode active material which can substantially absorb/desorb lithium ions reversibly. The negative electrode active material is composed of at least one substance selected from the group consisting of silicon, a silicon-containing alloy, a silicon compound, tin, a tin-containing alloy, and a tin compound; and the negative electrode is formed as a thin film having a thickness of 10 mum or less.
Description
Technical field
The present invention relates to have the electrical storage device of high output and high power capacity and repeated charge life characteristic excellence.
Background technology
All the time, the electrical storage device that can discharge and recharge is used to use in hybrid vehicle, the various electronic equipment, the particularly power supply of moving body communication apparatus, mancarried electronic aid etc., uninterrupted power supply etc. of gasoline and both driven by energy of electricity.Along with popularizing of recent hybrid vehicle, electronic equipment, the requirement of the high performance aspect of electrical storage device is also just being become very high.In order to tackle this demand, carried out extensive studies at double electric layer capacitor as one of electrical storage device.Double electric layer capacitor has characteristics such as high output and repeated charge life characteristic excellence, is expected to be mainly used in purposes such as high output, still, compares with secondary cell, and its capacity is that energy density is lower.
Aspect the high capacity of double electric layer capacitor, for example, negative electrode active material at the positive active material of selecting double electric layer capacitor and lithium battery carries out the optimization of positive active material and negative electrode active material self and the aspects such as optimization of combination thereof, has carried out various researchs.As negative electrode active material, study at the crystalline or the amorphous carbon material of for example graphite, polyacene etc.These material with carbon elements are to emit the material of lithium ion by discharging and recharging reversibly occlusion.About the positive active material of the double electric layer capacitor of the manufacture method of these material with carbon elements, active carbon etc. with comprise electrical storage device that these cathode of carbon material combine etc. and also have a large amount of prior aries to be disclosed (consulting for example patent documentation 1 and patent documentation 2).
In addition, at by using the negative electrode active material bigger to realize that the high capacity of electrical storage device also attempts than material with carbon element capacity density.As such negative electrode active material, can list by material with carbon element being carried out the negative electrode active material that modification obtains, the negative electrode active material except that material with carbon element etc.As material with carbon element is carried out the negative electrode active material that modification obtains, " the optical anisotropy carbonizable substance except that graphite carry out activation processing negative electrode active material, their negative electrode active material that is partly or entirely covered by material with carbon element and/or silicon materials on surface " (consult for example patent documentation 2) disclosed.As the negative electrode active material except that material with carbon element, metal oxides (consulting for example patent documentation 3 and 4) such as tin-oxide, Si oxide are disclosed.
In patent documentation 2～4, each patent documentation disclosed negative electrode active material and combination as the positive active material of active carbon are disclosed.Especially, in patent documentation 3 and 4,, can access the electrical storage device of overdischarge excellent by as non-cathode of carbon material active materials such as Si oxide, tin-oxide and combination as the positive active material of active carbon.More particularly, in the embodiment 1 of patent documentation 3, disclose will pulverize, whole grain to the silicon monoxide particle (negative electrode active material) below the particle diameter 44 μ m, graphite (conductive agent), polyacrylic acid (adhesive) prepare cathode agent by weight the mixed of 45:40:15.By this cathode agent is carried out press molding, make the schistose granular negative pole of diameter 4mm, thickness 0.19mm.This schistose granular negative pole is by also having electroconductive resin adhesive as the function of negative electrode collector simultaneously on the negative pole housing.The electrical storage device that comprises this schistose granular negative pole can be worked in the voltage range in the overdischarge zone that comprises 2V～final discharging voltage 0V, and still, its speed of discharging and recharging is 200 hour rates (0.005C speed (rate)), and very slow, output characteristic is low.
And in electronic equipments such as mancarried electronic aid widely used lithium secondary battery have the speed that discharges and recharges about 10～0.5 hour rates (0.1C speed～2C speed) usually.Therefore, patent documentation 3 and 4 electrical storage device obviously can not be used for substituting the purposes of lithium secondary battery.In addition, the double electric layer capacitor that can instantaneous large-current discharges and recharges has the speed that discharges and recharges about 0.002～0.02 hour rate (500C speed～50C speed) usually.Therefore, patent documentation 3 and 4 electrical storage device can not be used for substituting the purposes of double electric layer capacitor.As mentioned above, although patent documentation 3 and 4 disclosed electrical storage devices have high voltage and high power capacity, speed is slow, output characteristic is low because it discharges and recharges, so purposes is limited.
On the other hand, as positive active material, at have than present widely used active carbon more the organic compound of the oxidable reduction of high power capacity study.As the organic compound of oxidable reduction, the organic compound (consulting for example patent documentation 5 and 6) with pi-conjugated electron cloud, the organic compound (consulting for example patent documentation 7) with free radical etc. are disclosed.But, in these patent documentations, and the positive active material of unexposed organic compound as oxidable reduction, with combination as non-cathode of carbon material active material.
Patent documentation 1: the international brochure that discloses No. 2003/003395
Patent documentation 2: the spy opens the 2005-093777 communique
Patent documentation 3: the spy opens the 2000-195555 communique
Patent documentation 4: the spy opens the 2001-148242 communique
Patent documentation 5: the spy opens the 2004-111374 communique
Patent documentation 6: the spy opens the 2004-342605 communique
Patent documentation 7: the spy opens the 2004-193004 communique
Summary of the invention
Therefore, a kind ofly use non-material with carbon element, also can discharge and recharge at a high speed, have the electrical storage device of high output, high power capacity and excellent repeated charge life characteristic as negative electrode active material even the object of the present invention is to provide.
Present inventors have carried out positive research for addressing the above problem.Found that, double electric layer capacitor with positive active material, with as occlusion reversibly and and emit in the combination of non-cathode of carbon material active material of lithium ion, by negative pole being formed specific formation, can realize the high speed and the high outputization of the speed of discharging and recharging.That is,, directly on negative electrode collector, form the negative pole that non-material with carbon element forms, can access the electrical storage device of fast, high output of the speed of discharging and recharging and high power capacity and repeated charge life characteristic excellence, thereby finish the present invention by not using adhesive.
Promptly, electrical storage device of the present invention has: positive electrode collector, be disposed on the above-mentioned positive electrode collector and contain the positive pole that can reversibly adsorb at least with the anionic positive active material of desorb, negative electrode collector, and be disposed on the above-mentioned negative electrode collector and in fact by occlusion reversibly with emit the negative pole that the negative electrode active material of lithium ion forms, in addition, above-mentioned negative electrode active material is to be selected from by silicon, siliceous alloy, silicon compound, tin, the alloy of stanniferous, and at least a in the group formed of tin compound, above-mentioned negative pole is the following films of thickness 10 μ m.
The capacity of the unit are of above-mentioned negative pole is preferably 0.2～2.0mAh/cm
2
The thickness of above-mentioned positive pole is preferably more than 5 times of thickness of above-mentioned negative pole.
The specific area of above-mentioned negative pole is preferably more than 5.
The specific area of above-mentioned negative electrode collector is preferably more than 5.
Value that the value of the surface roughness Ra of above-mentioned negative electrode collector is preferably identical with the thickness of above-mentioned negative pole or the value bigger than the thickness of above-mentioned negative pole.
Preferably occlusion in advance has lithium in above-mentioned negative electrode active material.
The occlusion of lithium in above-mentioned negative electrode active material preferably carried out mechanically.
When the discharging and recharging of above-mentioned electrical storage device, the SOC of above-mentioned negative pole is preferably 20%～95%.
Above-mentioned negative electrode active material is preferably silicon.
Above-mentioned negative electrode active material is preferably silicon nitride or silicon-oxygen nitride.
Above-mentioned silicon compound is formula SiO preferably
x(0＜x＜2) represented Si oxide.
Above-mentioned positive active material is preferably activated carbon.
Above-mentioned positive active material is preferably the organic compound of oxidable reduction.
Above-mentioned organic compound preferably has free radical in molecule.
Above-mentioned organic compound preferably has pi-conjugated electron cloud in molecule.
Preferred above-mentioned negative electrode collector has the electrolyte maintaining part, and the volume of above-mentioned electrolyte maintaining part is more than 30% of possessive volume of above-mentioned negative electrode collector.
Preferred above-mentioned negative electrode collector has the electrolyte maintaining part, and the volume of above-mentioned electrolyte maintaining part is more than 50% of possessive volume of above-mentioned negative electrode collector.
Above-mentioned negative electrode collector preferably has along the multiple aperture plasma membrane of a plurality of through holes of thickness direction perforation.
Above-mentioned negative electrode collector does not preferably have the through hole that connects along thickness direction and has a plurality of projections on the surface, and the cross sectional shape along the thickness direction of above-mentioned negative electrode collector of above-mentioned projection is trapezoidal or accurate trapezoidal.
The height of above-mentioned projection is preferably more than 2 times of thickness of above-mentioned negative pole.
Preferably at least one portion of the top ends of above-mentioned projection, be formed with the coating that comprises negative electrode active material.
According to the present invention, can provide the electrical storage device of the repeated charge life characteristic that can discharge and recharge and have high output, high power capacity and excellence at a high speed.Even and if can provide the reduction that when height is exported, also can not cause capacity, the electrical storage device that can in long-time, stably keep high output.
Description of drawings
[Fig. 1] is the longitudinal section schematic diagram of structure of the electrical storage device 1 of embodiments of the present invention.
[Fig. 2] is the longitudinal section schematic diagram of structure of negative pole 12 that is formed at the surface of negative electrode collector 13.
[Fig. 3] is the longitudinal section schematic diagram of formation of negative pole 12a of another kind of form that is formed at the surface of negative electrode collector 13.
[Fig. 4] is the longitudinal section schematic diagram of the formation of negative electrode collector 13.
The longitudinal section schematic diagram of the formation of [Fig. 5] negative pole duplexer that to be negative pole 12 form with negative electrode collector 13.
[Fig. 6] is the longitudinal section schematic diagram of formation of the negative electrode collector 30 of another kind of form.
The longitudinal section schematic diagram of the formation of [Fig. 7] negative pole duplexer that to be negative pole 33 form with negative electrode collector 30 shown in Figure 6.
[Fig. 8] is that the thickness direction cross sectional shape of projection 36 is the longitudinal section schematic diagram of the formation of leg-of-mutton negative electrode collector 35.
[Fig. 9] is the longitudinal section schematic diagram of formation of negative pole duplexer 40 with projection 44 of rising height deficiency.
[Figure 10] is to use the stravismus sketch of the portable phone of electrical storage device of the present invention.
[Figure 11] is to use the stravismus sketch of the notebook computer of electrical storage device of the present invention.
[Figure 12] is to use the stravismus sketch of the hybrid vehicle of electrical storage device of the present invention.
[Figure 13] is the microphotograph in the thickness direction cross section of employed negative electrode collector 53 in the electrical storage device (B-1) of embodiments of the invention 6.
[Figure 14] is the microphotograph in employed negative pole 52 and the thickness direction cross section of negative electrode collector 53 formed negative pole duplexers in the electrical storage device (B-1) of embodiments of the invention 6.
[Figure 15] is the microphotograph in the thickness direction cross section of employed negative electrode collector 62 in the electrical storage device (B-3) of embodiments of the invention 6.
[Figure 16] is the microphotograph in employed negative pole 61 and the thickness direction cross section of negative electrode collector 62 formed negative pole duplexers in the electrical storage device (B-3) of embodiments of the invention 6.
[Figure 17] is the figure as a result of electrical storage device (C-1), (C-3), (C-6) and the test of repeated charge (C-8) of embodiments of the invention 8.
[Figure 18] is the electron micrograph of the major part in the thickness direction cross section of employed negative electrode collector 70 in the electrical storage device (D-1) of embodiments of the invention 10.
[Figure 19] is the electron micrograph of the major part in the thickness direction cross section of employed negative electrode collector 75 in the electrical storage device (D-6) of embodiments of the invention 10.
Embodiment
Electrical storage device of the present invention comprises positive pole, positive electrode collector, negative pole and negative electrode collector, and has following feature (i) and (ii).Other formation is identical with existing electrical storage device.
(i) maximum of the present invention is characterised in that: negative pole does not contain adhesive (binder), does not particularly contain organic adhesive, and comprises non-material with carbon element that reversibly occlusion emits lithium ion as negative electrode active material, that is, formed by negative electrode active material layer in fact.Emit the non-material with carbon element of lithium ion as occlusion reversibly, use to be selected from least a by in the alloy of silicon, siliceous alloy, silicon compound, tin, stanniferous and the group that tin compound is formed.
In using the existing electrical storage device of granular non-material with carbon element, constitute negative pole by utilizing adhesive that the particle of non-material with carbon element is combined with conductive agent as negative electrode active material.According to discovering of present inventors, in above-mentioned negative pole, the contact resistances of contact resistance, the active material particle when negative pole comprises conductive agent and the conductive agent on contact resistance, active material particle and collector body surface between the generation active material particle etc. make the internal resistance of electrical storage device increase.The decline of therefore inferring out the speed of discharging and recharging and even output becomes obvious.
In addition, do not contain adhesive by negative pole as the present invention, particularly do not contain organic adhesive, the mechanical charging method by utilizing film shaped methods such as evaporation to carry out at first can make in the negative electrode active material occlusion lithium in advance.According to the present invention, by said method with lithium mechanically occlusion in negative electrode active material, thereby make the processability of electrical storage device significantly improve.
In electrical storage device of the present invention, negative pole comes down to be made of non-material with carbon element.In addition, the present invention comprises that also negative pole also contains the execution mode of inorganic compound when containing non-material with carbon element.Inorganic compound is used to improve the purposes such as mechanical strength of negative pole.Even merging the inorganic compound that uses with non-material with carbon element is can not promote cell reaction and have the stable on heating inorganic compound that in negative pole occlusion Li can not cause the degree of deterioration etc. yet, and can list the alloy etc. of the alloy of for example iron, cobalt, ammonium, bismuth, lead, copper, silver, zinc, thallium, cadmium, gallium, germanium, indium, titanium or their compound or they and silicon or they and tin.Therefore negative pole of the present invention forms the structure of continuous connection owing to do not contain adhesive as the non-material with carbon element of negative electrode active material.By adopting such structure, what can significantly reduce negative pole and negative electrode collector electrically contacts resistance (following only abbreviate as " contact resistance ").
(ii) directly form the negative pole that constitutes by the film below the thickness 10 μ m on the surface of negative electrode collector.
In using the prior art of granular non-material with carbon element as negative electrode active material, negative pole is not directly to be formed on the negative electrode collector, but the negative pole that will make in addition is bonding or be bonded on the negative electrode collector.Negative pole is by for example the particle of non-material with carbon element, conductive agent and adhesive being mixed, and is that schistose granular is made with resulting mixture press molding.For example, if as document 3 and 4, use non-material with carbon element particle below the particle diameter 44 μ m, then obviously can not make negative pole about thickness 30 μ m, surface smoothing.Even the thickness of the schistose granular negative pole that makes by existing method also can only reach the further granular of non-material with carbon element particle about tens of microns, be difficult to realize for example following significantly filming of 10 μ m.
On the contrary, in the present invention,, compared with prior art, can significantly reduce the thickness of negative pole by directly forming the negative pole that forms by the film below the thickness 10 μ m on the negative electrode collector surface.Negative pole becomes follows the electronics that discharges and recharges generation or the passage of ion.Therefore, if the thickness attenuation of negative pole, then the displacement of electronics or ion shortens accordingly, and resistance reduces, and can reduce the internal resistance of electrical storage device.In addition, when directly forming negative pole on negative electrode collector surface, can be by formation negative poles such as for example evaporations, so the processability of electrical storage device significantly improves.
As mentioned above, electrical storage device of the present invention has above-mentioned (i) and feature (ii), compares with existing electrical storage device, and internal resistance significantly reduces, and can realize discharging and recharging at a high speed and high outputization.In addition, electrical storage device of the present invention is by using non-material with carbon element as negative electrode active material, the electrical storage device that can provide high power capacity and repeated charge life characteristic excellence and processability to significantly improve.By using this film cathode, can realize the miniaturization of electrical storage device.
In addition, the thickness of negative pole described here is meant the thickness of the negative pole of (during discharge) when electrical storage device constitutes.Since when discharging and recharging negative electrode active material reversibly occlusion emit lithium, so the thickness of negative pole changes.
As the capacity of negative plates of per unit area, can use to demonstrate 0.2～2.0mAh/cm
2The negative pole of capacity.The capacity of negative plates of preferred unit area is 0.2～1.0mAh/cm
2Wherein said capacity of negative plates is meant the capacity that can reversibly discharge and recharge as the negative pole monomer, does not comprise irreversible capacity described later.Specifically, be meant with the lithium be benchmark in the potential range of 0～1.5V, the anticathode capacity is with the reversible capacity of 0.2CA (5 hour rate) when discharging and recharging.
Below, describe with reference to the execution mode of accompanying drawing electrical storage device of the present invention.
Fig. 1 is the longitudinal section schematic diagram of formation of the Coin shape electrical storage device 1 of embodiments of the present invention.Fig. 2 is the longitudinal section schematic diagram of formation that is formed at the negative pole 12 on negative electrode collector 13 surfaces.Electrical storage device 1 comprises positive pole 10, positive electrode collector 11, negative pole 12, negative electrode collector 13, barrier film 14, hush panel 15, sealing gasket 16, liner 17 and housing 18.Electrical storage device 1 is that the duplexer of liner 17, negative electrode collector 13, negative pole 12, barrier film 14, positive pole 10 and positive electrode collector 11 is incorporated in by the Coin shape electrical storage device in hush panel 15 and the housing 18 formed inner spaces.Therefore, Fig. 1 also can be described as the diametric sectional view of electrical storage device 1.In addition, the laminated portions to the positive electrode collector 11 of electrical storage device 1, anodal 10, barrier film 14, negative pole 12 and negative electrode collector 13 applies pressure about equally.
As silicon-containing alloy, can list alloy of at least a element of silicon and chosen from Fe, cobalt, antimony, bismuth, lead, nickel, copper, zinc, germanium, indium, tin and titanium for example etc.As silicon compound, so long as the compound that comprises silicon except that silicon-containing alloy gets final product not special restriction, preferred Si oxide, silicon nitride, silicon-oxygen nitride etc.As Si oxide, can list for example formula SiO
x(0＜x＜2) represented silica.This silica also can comprise elements such as nitrogen, sulphur.As silicon nitride, can list for example formula Si
3N
y(3＜y≤4) represented silicon nitride.Wherein, preferred Si
3N
4As silicon-oxygen nitride, can use to comprise silicon, oxygen and nitrogen as principal component, comprise element (for example carbon, hydrogen etc.) except that above-mentioned 3 kinds of elements as the compound of impurity.For example, can preferably use SiO
aN
bComposition formula in, the compound about a/b=0.2～5.0.As Sn-containing alloy, can list alloy of at least a element of tin and chosen from Fe, cobalt, antimony, bismuth, lead, nickel, copper, silver, zinc, thallium, cadmium, gallium, germanium, indium and silicon for example etc.As tin compound, so long as the compound that comprises tin except that Sn-containing alloy gets final product not special restriction, particular tin oxides.As tin-oxide, can list for example formula SnO
xThe tin oxide that (x is the same) is represented.This tin oxide can also comprise elements such as nitrogen, sulphur.
These non-material with carbon elements also can further comprise nonmetalloid.As nonmetalloid, not special restriction can list for example alkali metal such as hydrogen, sodium, potassium, rubidium, alkaline-earth metals such as magnesium, calcium, carbon, boron, nitrogen, phosphorus etc.
In these non-material with carbon elements, preferred silicon compound, more preferably Si oxide, preferred formula SiO especially
x(the x definition is the same) represented silica.Non-material with carbon element can use a kind separately, also can be used in combination as required more than 2 kinds.
These non-material with carbon elements have the very large feature of energy.With respect to the energy density 500～600mAh/cc of the unit volume of existing material with carbon element (being designated hereinafter simply as " existing material with carbon element ") as negative electrode active material, non-material with carbon element has for example silicon 2400mAh/cc, such 3～5 times energy density of tin-oxide 1400mAh/cc.Therefore, different with the situation of using existing material with carbon element, can suitably adjust anodal 10 and the thickness balance of negative pole 12.For example, thickness can be set for counting the negative pole 12 of the film like about μ m.By using non-material with carbon element that negative pole 12 is made film like, can in the height outputization that realizes electrical storage device 1, realize miniaturization and high capacity.In addition, the volume energy density of the positive active material of the double electric layer capacitor of active carbon etc. is about 30mAh/cc, even compare with it, non-material with carbon element also has the great energy density about its 50～80 times.In addition, the same negative pole current potential of non-material with carbon element and existing material with carbon element is low, therefore can access the high-tension electrical storage device 1 that has about 3V.
In order directly to form the negative pole 12 of film like on negative electrode collector 13 surfaces, can adopt film build method commonly used such as vacuum vapour deposition, sputtering method, vapour deposition process, CVD method, plating method.At this moment, by suitable selection membrance casting condition, can adjust negative pole thickness.When formation comprises the negative pole of non-material with carbon element and inorganic compound, can suitably be chosen to film method according to the characteristic of inorganic compound.For example, if inorganic compound be can evaporation compound, then can be by the common evaporation formation negative pole of non-material with carbon element with inorganic compound.In addition, in the present embodiment, as shown in Figure 2, on the whole surface of negative electrode collector 13, form negative pole 12, but be not limited to this, also can form the negative pole 12 of pattern-like on negative electrode collector 13 surfaces.As the negative pole that has formed pattern-like, can list negative pole 12a for example shown in Figure 3.Fig. 3 is the longitudinal section schematic diagram of formation of negative pole 12a that is formed at the another kind of form on negative electrode collector 13 surfaces.Negative pole 12a forms striated on the surface of negative electrode collector 13.But be not limited to this, also can form for example pattern-likes such as striated of clathrate, circle.As the method for the negative pole 12 that on negative electrode collector 13, forms pattern-like, can list for example use mask carry out the method for the film forming of negative pole 12, to having method that concavo-convex negative electrode collector 13 carries out oblique side's evaporation on the surface, forming negative pole 12 is partly removed negative pole 12 then by etching etc. method etc. on the whole surface of negative electrode collector 13.
When making negative pole, can adjust the specific area of negative pole 12 by suitable selection membrance casting condition by conventional film build method such as vacuum vapour deposition, sputtering method.
In present specification, specific area is represented the surface area of the measurement range that sets and the ratio (apparent area of the surface area/measurement range of measurement range) of the apparent area of measurement range.The surface area of measurement range is to use laser microscope (trade name: super degree of depth measuring shape microscope VK-855, キ-エ Application ス company manufacturing) to measure.In the assay method of the surface area of material, the method that comprises the contour area of only measuring material, measure the outline area of material and the concave-convex surface of material, the Method for Area of be full of cracks, when measuring the area of concave-convex surface, be full of cracks of the contour area of material and material, also measure the Method for Area of the pore that extends to inside etc.And, try to achieve according to the difference of assay method and the different specific area of implication.Use the surface area test method of laser can not destroy determination object, can measure the surface area (the outline area of material and material surface concavo-convex, the area that chaps and) of institute's measurement range easily.In addition, use the surface area test method of laser have can be roughly correctly the measurement the specific area value be the advantage of the surface area of about 3～10 material.Therefore, in the present invention, be suitable for the mensuration of the surface area of negative pole 12, negative electrode collector 13 etc.On the other hand, the apparent area of measurement range is meant the area when supposition institute measurement range is the plane.Therefore, apparent area calculates automatically by setting measurement range.In addition, in assay method of the present invention, when from vertical direction top observation measurement range, the concavo-convex and be full of cracks of not observing the part of shadow is not included in the mensuration.Wherein, " do not observe " and be meant and discern by laser microscope.
Measurement range is set as follows.At first select 1 projection from the surface of determination object material, with it as the 1st projection.The width on each limit of the 1st projection periphery is designated as W.The value of W in fact each limit all changes.Then, at the central part of the 1st projection, be that part below the W/2 is as measurement range with the width that has similar shapes and each limit of periphery with the 1st projection.
In addition, by the value (Roughness value) of surface roughness (arithmetic mean surface roughness) Ra of the face of the formation negative pole 12 of negative electrode collector 13 is adjusted in the specific scope, can form negative pole 12 with specific thickness and specific area.As long as adjust the surface roughness Ra of negative electrode collector 13, even not strict control membrance casting condition also can easily form the negative pole 12 with regulation specific area.At this moment, the value of the surface roughness Ra of negative electrode collector 13 is preferably the value identical or bigger with the thickness of negative pole 12.In other words, the thickness of the negative pole 12 that does not contain lithium fully after just having formed is preferably smaller or equal to the value of the surface roughness Ra of negative electrode collector 13.Like this, the concavo-convex of negative electrode collector 13 surfaces can be reproduced in the surface of negative pole 12 with being in the main true, and can access the negative pole 12 of the specific area with regulation.If the thickness of negative pole 12 surpasses the value of the surface roughness Ra of negative electrode collector 13, then negative pole 12 also can be lost with respect to the concavo-convex tracing ability on negative electrode collector 13 surfaces.The result is, the concavo-convex meeting on negative electrode collector 13 surfaces is owing to negative pole 12 planarization that becomes, and possibly can't obtain having the negative pole 12 of the specific area of regulation.The surface roughness Ra of negative electrode collector 13 is preferably following, following, 1～2 μ m more preferably of 5 μ m more preferably of 10 μ m.The surface roughness Ra of negative electrode collector 13 can be carried out suitable adjustment by for example conventional roughened method etc.In present specification, the surface roughness Ra of negative electrode collector 13 is values of measuring by the method for the JIS B0601-1994 of Japanese Industrial Standards defined.
In addition, by the specific area with the face of the formation negative pole 12 of negative electrode collector 13 be adjusted to preferred more than 5, more preferably more than 10, also can form negative pole 12 with comparalive ease with specific thickness and specific area.At this moment, be below the value of surface roughness Ra of negative electrode collector 13 for the thickness that makes negative pole 12, can for example suitably select membrance casting conditions such as film formation time.
When the discharging and recharging of electrical storage device, the SOC of negative pole (state-of-charge (state of charge)) is preferably 20%～95%.Can access electrical storage device like this with high power capacity and high output and repeated charge life characteristic excellence.
In addition, the SOC of negative pole is not the expression electrical storage device and is the index of the charged state of expression negative pole monomer, and it is the value that capacity (reversible capacity) when completely charging with the negative pole monomer is 100%, charge volume is represented with percentage with respect to the ratio of full charge volume.Therefore, the SOC of state of discharge is 0% fully, the SOC of fully charged state is 100%.
The SOC of negative pole tries to achieve as follows.Be in the potential range of benchmark 0～1.5V with the lithium, it is 100% (full charging) that the charge volume of the negative pole of the situation that the anticathode capacity has been charged with 0.2CA (5 hour rate) is defined as SOC, is benchmark with this charge volume, can be in the hope of the value of SOC.
By having through hole, can make the electrolyte impregnation or remain in this through hole 20.That is,, can keep anion, cationic electrolyte (electrolyte) contact negative electrode collector 13 inside that are provided with negative pole 12.Even negative pole 12 portion within it fully keeps electrolyte, keep the fully electrolyte of amount by inside at negative electrode collector 13, also can guarantee the fully electrolyte of amount in the inside of protecting electrical storage device 1.In Fig. 5, on a face of the thickness direction of negative electrode collector 13, form negative pole 12 with a plurality of through holes 20.After negative pole 12 film forming are on negative electrode collector 13,, preferably make the aperture of the thickness of negative pole 12 less than through hole 20 in order to make the electrolyte solution impregnation by through hole 20 or to remain on negative electrode collector 13 inside.In other words, the aperture of preferred through hole 20 is greater than the thickness of negative pole 12.Specifically, the aperture of through hole 20 be preferably more than 2 times of thickness of negative pole 12, more preferably more than 5 times, more preferably 5 times～100 times.In addition, the aperture of through hole 20 can be measured by for example gas absorption mensuration or mercury porosimeter.In addition, because therefore the distribution that the aperture of through hole 20 as a rule has mostly can be the aperture of typical value as through hole 20 with volume reference intermediate value fine pore.
The volume of electrolyte maintaining part is preferably more than 30% with respect to the ratio (following only be designated as " the volume ratio of electrolyte maintaining part ") of the possessive volume (summation of the internal capacity of through hole 20) of negative electrode collector 13.
The volume ratio of electrolyte maintaining part more preferably more than 50%, more preferably 50～95%.When the volume ratio of electrolyte maintaining part was lower than 30%, near the electrolytic salt quantitative change the negative pole 12 got insufficient, and the charge/discharge capacity of electrical storage device 1 reduces sometimes.In addition, in the mensuration of the volume ratio of electrolyte maintaining part, can measure or mercury porosimeter be measured by for example gas absorption.As the example that gas absorption is measured, can list the mensuration of for example using specific area pore measure of spread device (trade name: ASAP2010, (strain) Shimadzu Seisakusho Ltd. makes).This determinator is to utilize the adsorption-desorption of gas to measure the device of pore volume, can measure the pore diameter number
Pore about～0.1 μ m.In addition, as another example, can list the mensuration of using mercury porosimeter (trade name: オ-ト Port ア III9410, (strain) Shimadzu Seisakusho Ltd. makes).This determinator utilize mercury to pore clamp-on the mensuration pore volume, and can measure pore diameter and count pore about nm～500 μ m.These determinators can be selected to use according to the pore diameter of object.
As negative electrode collector 13, can use for example porous body such as foaming body, sieve aperture body with through hole 20.In addition, as the material that constitutes negative electrode collector 13,,, then preferably use metal materials such as copper, nickel if consider the processability etc. of porous materialization though can use the material of the negative electrode collector that is used for lithium ion battery.In addition, in foaming body, the continuous air bubbles that is formed at foaming body inside is the electrolyte maintaining part, and the summation of the volume of continuous air bubbles is the volume of electrolyte maintaining part, and the porosity of foaming body is the ratio of the volume of electrolyte maintaining part with respect to the possessive volume of negative electrode collector 13.
Wherein, Fig. 6 is the longitudinal section schematic diagram of formation of the negative electrode collector 30 of another kind of form.The longitudinal section schematic diagram of the formation of Fig. 7 negative pole duplexer that to be film cathode 33 form with negative electrode collector 30 shown in Figure 6.Negative electrode collector 30 is characterised in that and comprises current collection film 31, projection 32.Current collection film 31 is that the material that uses in the negative electrode collector by lithium ion battery constitutes.Projection 32 is according to two faces at the thickness direction of current collection film 31, a plurality of projections that the mode of extending towards the outer direction of current collection film 31 from current collection film 31 surfaces forms.Current collection film 31 does not have the through hole that connects along thickness direction.
In negative electrode collector 30, the top ends in projection 32 forms negative pole 33 at least.If by negative pole 33 this negative electrode collector 30 contact with barrier film 14 by being situated between, then because the existence of projection 32, the space that formation negative electrode collector 30 and barrier film 14 directly do not contact.By making the electrolyte impregnation or remaining in this space, can near negative pole 33, keep the necessary electrolytic salt amount of negative reaction.That is, this space forms the electrolyte maintaining part.
The volume of electrolyte maintaining part can multiply by rising height with respect to the non-occupied area of collector body area by projection and calculate.Wherein, projection is meant with respect to the non-occupied area of collector body area, and in the area of current collector film, the collector body surface does not form the ratio of the gross area of the part of projection.Rising height and projection can be by using laser microscope or electron microscope with respect to the non-occupied area of collector body area the surface observation and the cross-section of current collector film measure.Specifically, for example can use laser microscope (trade name: VK-855, キ-エ Application ス company makes) etc.
Projection 32 is preferably according to by being situated between by being arranged on its surperficial negative pole 33, is not some contact but mode that face contacts forms with barrier film 14.Therefore, projection 32 preferred its tops (distance set electrolemma 31 part farthest) formation face, more preferably its top forms and the parallel face in current collection film 31 surfaces.Form face by the top that makes projection 32, make this top end face support barrier film 14 really, therefore, at the whole life expectancy of electrical storage device 1, it is identical that the volume of electrolyte maintaining part almost keeps.In addition, the top of projection 32 connects barrier film 14 and makes the both positive and negative polarity short circuit, and the product percent of pass of electrical storage device 1 can not reduce.If projection 32 tops are faces, then, can form different shape to the not special restriction of the shape outside this.But if consider stably to support barrier film 14, the cross section character of the thickness direction of negative electrode collector 30 is preferably formed trapezoidal or accurate trapezoidal.The accurate trapezoidal cross section that is meant thickness direction is the shape of approximate trapezoid roughly, compare with the limit (hereinafter referred to as " top ") that distance set electrolemma 31 is far away, longer and top, the limits (hereinafter referred to as " bottom ") that contact with current collection film 31 surfaces is with respect to the slightly uneven shape of bottom.At this moment, the angle at the extended line of top and the following formed angle of extended line is for about several times.In addition, at least a portion of the top in the cross section of thickness direction also can comprise curve.Even accurate trapezoidal,, also can access above-mentioned effect so long as can support barrier film 14 by face.
Wherein, the longitudinal section schematic diagram of the formation of the negative electrode collector 35 of another kind of form as shown in Figure 8.In the negative electrode collector 35, as shown in Figure 8, the thickness direction cross sectional shape of projection 36 is that the top of triangle, projection 36 forms cusp.If the projection top forms point, at least a portion on its top enters in the barrier film 14, may connect barrier film 14 according to circumstances.In addition, the top of projection 36 connects barrier film 14 can make the both positive and negative polarity short circuit, may reduce the qualification rate of the product of electrical storage device 1.
The possessive volume of negative electrode collector 30 is values that the thickness t of the area on surface of thickness direction of current collection film 30 and negative electrode collector 30 multiplies each other and obtains.Wherein, the thickness t of negative electrode collector 30 is meant from the top of the projection 32 of a face being formed at current collection film 31 to the length at the top of the projection 32 that is formed at another face.In order to make the ratio with respect to the possessive volume of negative collector electrode 30 of electrolyte maintaining part reach more than 30%, can suitably adjust projection 32 for example height, be formed at summation, the interval between the projection 32, the quantity of projection 32 etc. of area of face on the top of projection 32.The height of projection 32 is meant the length at the top from current collection film 31 surfaces to projection 32.
Negative electrode collector 30 can be by for example implementing machinings to current collection film 31, forms a plurality of projections 32 on the surface of the thickness direction of current collection film 31 and make.Machining comprises for example press process, roller processing etc.In addition, also can blow attached processing etc., obtain negative electrode collector 30 by what Surface Machining, the plating of current collection film 31 being implemented grindings, etching, compositionization etc. were handled (plating, electroless plating, electro-deposition plating etc.), particulate.Wherein, current collection film 31 can use for example Copper Foil, nickel foil etc.
In addition, when forming negative poles 33, preferably note the relation between the height of the thickness of negative pole 33 and projection 32 on negative electrode collector 30 surface.As shown in Figure 7, preferred negative pole 33 is that the shape of following negative electrode collector 30 surfaces forms, and can reproduce the shape of projection 32 on negative pole 33 surfaces.Like this, after negative pole 33 forms, can guarantee on negative pole 33 surfaces as being used to keep the electrolyte maintaining part in electrolytical space.Therefore, with respect to the height of the negative electrode collector 30 surperficial projections 32 that exist, the thickness of negative pole 33 must be very thin.Specifically, the height of projection 32 is preferably more than 2 times of thickness of negative pole 33, more preferably more than 5 times of thickness, more preferably 5～10 times of negative pole 33.
When the height of projection 32 during less than 2 times of the thickness of negative pole 33, the space of the electrolyte maintaining part of being guaranteed by projection 32 reduces.Fig. 9 is the longitudinal section schematic diagram of the formation of negative pole duplexer 40.Negative electrode collector 40 comprises negative pole 41 and negative electrode collector 42.Negative electrode collector 42 comprises current collection film 43 and projection 44.In negative electrode collector 40, the height of projection 44 is less than 2 times of the film forming thickness of negative pole 41.Negative pole 41 not only can be formed at the face on projection 44 tops, but also can be formed at the side of projection 44, therefore particularly and the space between the adjacent projection 44 narrow down.Consequently, because the existence of projection 44, the space of the feasible electrolyte maintaining part that should form becomes minimum, and the electrolyte content that negative electrode collector 42 can keep reduces.
In addition, in negative electrode collector 30, form projection 32 on the two sides of thickness direction, but be not limited to this, also can be only on negative electrode collector 30 and face that barrier film 14 contact a plurality of projections 32 of formation.At this moment, can only on the face that has formed projection 32, film cathode 33 be set.
In addition, after forming negative pole 12 on negative electrode collector 13 surfaces, preferred anticathode 12 fills the electric weight of regulation in advance.That is, preferred in advance at the lithium of negative pole 12 occlusion ormal weights.In this manual, be meant in negative pole 12 pre-charges, in the making of finishing electrical storage device 1 (installation) before, anticathode 12 charging in advance, occlusion lithium in advance in negative electrode active material.This is to have irreversible capacity etc. because electrical storage device 1 has just been made negative pole 12 afterwards.Irreversible capacity is meant in the charge capacity of negative pole 12, is equivalent to the capacity that side reaction consumed except that reaction is emitted in the occlusion of the lithium that discharges and recharges reaction that is used for negative electrode active material.That is, although irreversible capacity is meant the capacity that can not reversibly discharge that charged, and only can be observed in initial discharging and recharging, this point is well-known.
When the electric weight of anticathode 12 pre-charges regulations, can adopt known method, for example can list mechanical mise-a-la-masse method, electrochemical charge method, chemical mise-a-la-masse method etc.If adopt mechanical mise-a-la-masse method, then can charge by for example making current potential material lower (lithium metal etc.) and negative electrode active material Mechanical Contact than negative electrode active material.More particularly, lithium metal that for example can be by attaching ormal weights on negative pole 12 surface or by evaporation equal vacuum method on negative pole 12 surfaces with the direct film forming of lithium metal, perhaps, the lithium metal that will make on the plastic base of having implemented demoulding processing charges after being transferred on negative pole 12 surfaces.In addition, in mechanical mise-a-la-masse method, contacts than low material of negative electrode active material and negative pole 12 surfaces by making current potential, add antilogous pole 12 then, carrying out that can the accelerated charging reaction shortens charging and reacts the needed time.
Utilize the electrochemical charge method, for example, by with negative pole 12 with the utmost point is immersed in the electrolyte, at negative pole 12 with feed the electric current energising between to the utmost point, come anticathode 12 to charge.At this moment, as to the utmost point, can use for example lithium metal.As electrolyte, can use the nonaqueous solvents that for example is dissolved with lithium salts.In addition, also can use employed common electrolyte in the lithium ion battery.After making electrical storage device 1, if inside at electrical storage device 1, except that positive pole 10 and negative pole 12, also importing is used for the 3rd not shown electrode that anticathode 12 is implemented the electrochemical charge processing, then can constitute anticathode 12 enforcement charging processes afterwards at the battery of electrical storage device 1.
According to chemical mise-a-la-masse method, the compound that for example butyl lithium etc. is contained lithium ion is dissolved in the organic solvent, this solution is contacted with negative pole 12 produce chemical reaction, and anticathode 12 charges.The solution that comprises the compound of lithium ion can be undertaken by for example negative pole 12 being immersed in this solution with contacting of negative pole 12.
In these charging methods, in electrochemical charge method and chemical mise-a-la-masse method, necessary is to take out negative pole 12 after charging, removes in solvent, electrolytic salt and other charging processes attached to the surface of negative pole 12 employed compound etc. by washing.In addition, charging process itself also needs the long time.In addition, the low-down current potential that the negative pole 12 after charging forms near the lithium current potential, reactive high, therefore, during the washing of the negative pole 12 after charging, deterioration takes place in the surface of negative pole 12 sometimes.In contrast, in mechanical charging method, because negative pole 12 only contacts with lithium, therefore do not need washing, in addition, the needed time is also short.Deterioration does not take place in the surface of negative pole 12 yet.
Therefore, consider the preferred mechanical mise-a-la-masse method from the angle of manufacturing and from the angle of characteristic.Particularly in mechanical mise-a-la-masse method, most preferably by directly form the method for the film of lithium metal by film forming methods such as evaporations on negative pole 12 surfaces.This be because, the negative pole 12 of electrical storage device of the present invention is the following film cathodes of thickness 10 μ m, and the lithium that therefore needs charging must be controlled to be following, the following film of 5 μ m according to circumstances of thickness 10 μ m too, therefore, in fact the attaching processing of lithium metal etc. is difficult to control.Therefore, consider from controlled, process time of the equal angles of thickness, preferably the mechanical mise-a-la-masse method that is undertaken by film forming methods such as evaporations.By implementing mechanical mise-a-la-masse method, the processability of electrical storage device is significantly improved.
In addition, when the electric weight of anticathode 12 charging regulations, the negative pole 12 that does not contain the direct formation of adhesive on negative electrode collector 13 of electrical storage device 1 of the present invention is effective.Its reason is described as follows.For example, when forming the lithium film by vapour deposition method on negative pole 12, carrying out machinery when charging, because the fusing point of lithium is 179 ℃, therefore, negative pole 12 is exposed to the lithium that is heated to the high temperature about at least 179 ℃.At this moment, if form the lithium film comprising on the negative pole of adhesive, then as the majority of the resin material of the principal component of adhesive, thereby material generation chemical reaction active with the such chemical reactivity of lithium and that be heated to about 179 ℃ causes deterioration.On the other hand, in electrical storage device 1 of the present invention, because negative pole 12 directly is being formed under the state that does not contain adhesive on negative electrode collector 13 surfaces, therefore, suitable use utilizes the mechanical mise-a-la-masse method of film forming method such as evaporation, and is very effective.
As negative electrode collector 13, can use the negative electrode collector that is used for various electrical storage devices, wherein, preferably be used for the negative electrode collector of lithium ion battery.As the instantiation of such negative electrode collector, can list for example metal metal forming such as copper, nickel.Wherein, consider preferred Copper Foil from the angle of processability etc.As the form of negative electrode collector 13, can list the film like of surface smoothing, the mesh-like that makes through the film like of roughening, thin metallic fiber on the surface, porous film shape etc.When using the surface through the negative electrode collector 13 of the film like of roughening, if from the adhesiveness of negative pole 12, the considerations such as output characteristic of electrical storage device, the surface roughness of negative electrode collector 13 (Ra) is preferably 1～2 μ m, in addition, preferred specific area is more than 5, more preferably more than 10.
The positive pole 10 of stratiform is that a face according to thickness direction contacts with barrier film 14 and another face is provided with the mode that positive electrode collector 11 contacts, and comprises positive active material.In addition, anodal 10 also comprise ionic conduction auxiliary material, electrical conductivity auxiliary material, adhesive etc. when comprising positive active material.
As positive active material, can use when discharging and recharging can reversibly adsorb at least, the anionic material of desorb.For example can list in the double electric layer capacitor employed positive active material etc. in employed positive active material, the electrochemical capacitor.In the above-mentioned positive active material employed material also can reversibly adsorb, the desorb cation.
To the not special restriction of employed positive active material in the double electric layer capacitor, and can preferably use the organic compound etc. of active carbon, oxidable reduction.As active carbon, the preferred high active carbon of specific area.For example,, in this system, import steam then, obtain maximum 2000m by material with carbon element (cocoanut shell, organic resin, petroleum asphalt etc.) is carried out carbonization under 900～1000 ℃ temperature in inert gases such as nitrogen
2The active carbon that specific area about/g is high.To the not special restriction of the shape of active carbon, for example can list Powdered, fibrous, laminar shapes such as (perhaps flakeys).
As the organic compound of oxidable reduction, can list the organic compound that for example has free radical, organic compound, indoles series organic compound etc. with pi-conjugated electron cloud.As organic compound, can list the organic compound that for example in molecule, has at least a free radical that is selected from NO free radical, boron free radical and oxygen radical with free radical.As the instantiation of these organic compounds, for example can list 2,2,6,6-tetramethyl piperidine-1-oxygen radical, 2,2,5,5-tetramethyl-3-imidazoles-1-oxygen radical etc. comprises the compound of NO free radical, quinones such as quinone, benzoquinones etc.As organic compound, can list the organic compound that for example has the represented structure of following general formula (1) with pi-conjugated electron cloud
In the general formula (1), 4 X represent sulphur atom or oxygen atom independently of one another.R
1～R
4Represent chain aliphatic group, cyclic aliphatic group, hydrogen atom, hydroxyl, cyano group, amino, nitro or nitroso independently of one another.R
5And R
6Represent hydrogen atom, chain aliphatic group or cyclic aliphatic group independently of one another.Wherein, R
1～R
6Represented chain aliphatic group and cyclic aliphatic group can comprise at least a atom that is selected from oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, boron atom and halogen atom.
Can list organic compound with the represented structure of following general formula (2).
R in the general formula (2)
1～R
6Definition and the R of general formula (1)
1～R
6Identical.Can list organic compound with following (3) represented structure.
In the general formula (3), X
1～X
4Represent sulphur atom, oxygen atom, selenium atom or tellurium atom independently of one another.R
7And R
8Represent the chain aliphatic group of divalent or the cyclic aliphatic group of divalent independently of one another.Wherein, R
7～R
8The chain aliphatic group of represented divalent and the cyclic aliphatic group of divalent can comprise at least a atom that is selected from oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, boron atom and halogen atom.
In addition, in above-mentioned general formula (1)～(3), R
1～R
8The 1 represented valency or the chain aliphatic group of divalent and cyclic aliphatic group can also comprise atoms such as oxygen atom, nitrogen-atoms, sulphur atom, phosphorus atoms in its strand.Wherein, what is called can also comprise atoms such as oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, is meant to have at least a group that comprises in these atoms.As group, can list for example amino, imido grpup, cyano group, nitro etc. with nitrogen-atoms.As group, can list for example alkoxyl, hydroxyl, alkyl, oxo (oxo) base etc. with hydroxyl with oxygen atom.As group, can list for example sulfo group, sulfonyl, sulfonic group, thiocarbonyl, sulfamoyl, alkyl sulphonyl etc. with sulphur atom.As group, can list for example silicyl etc. with silicon atom.In addition, also can comprise at least a kind of these atom in the middle of the saturated or unsaturated carbon chains at alkyl, alkenyl etc.Boron atom and halogen atom can be incorporated into various substituting groups.Boron atom and halogen atom can directly be replaced in R
1～R
8The 1 represented valency or the chain aliphatic group and the cyclic aliphatic group of divalent.
As the indoles series organic compound, can list indoles triploid, its derivative of 5-cyanoindole etc. etc.
In addition, as employed positive active material in the electrochemical capacitor, the positive active material of in double electric layer capacitor, being used always, also comprise having and to demonstrate the material of intending double-deck capacity by redox reaction.As the instantiation of these positive active materials, can list for example metal oxides such as ruthenium-oxide, yttrium oxide, manganese oxide, nano-carbon materials such as nanometer door carbon (nanogate carbon), carbon nano-tube etc.Positive active material can use a kind or be mixed with two or more as required separately.
The ionic conduction auxiliary material for example are used to improve ionic conductivity.As the instantiation of ionic conduction auxiliary material, for example can list solid electrolyte such as polyoxyethylene, comprise gel electrolyte of polymethyl methacrylate etc. etc.
The electrical conductivity auxiliary material for example are used to improve electronic conductivity.As the instantiation of electrical conductivity auxiliary material, can list for example material with carbon elements such as carbon black, graphite, acetylene black, electroconductive polymers such as polyaniline, polypyrrole, polythiophene etc.
Adhesive is used to improve the associativity of positive active material.As adhesive, can list for example polyvinylidene fluoride, vinylidene difluoride-hexafluoropropylene copolymer, vinylidene fluoride-polytetrafluoroethylene, polytetrafluoroethylene, polyethylene, polyimides, polyacrylic acid, carboxymethyl cellulose, acrylic-nitrile rubber, butadiene rubber, styrene butadiene ribber etc.
The not special restriction of anodal 10 thickness (below be designated as " anodal thickness "), for example, if consider electrolyte retentivity etc., be preferably more than 5 times of thickness (below be designated as " negative pole thickness ") of negative pole 12, negative pole thickness more than 10 times more preferably.In addition, anodal thickness is with respect to being limited to about 50～100 times on the negative pole thickness.Blocked up at anodal thickness, be that the capacitance of storage of electrical storage device is subjected to the control of negative pole, can cause that capacity reduces in 50～100 times the situation with respect to negative pole thickness.In electrical storage device 1 of the present invention, as mentioned above, directly form negative pole 12 by surface at negative electrode collector 13, can reduce the thickness of negative pole.Therefore, the electrolyte retentivity of negative pole 12 inside can reduce.In order to remedy this point, preferably increase anodal thickness.
Specifically, preferred negative pole thickness is about 2～10 μ m, anodal thickness is for about its 20～100 μ m more than 10 times.More preferably negative pole thickness is about 2～5 μ m, anodal thickness is for about its 20～50 μ m more than 10 times.
Layered cathode collector body 11 is that face according to its thickness direction contacts with anodal 10, and another face mode of contacting with housing 18 is provided with.As positive electrode collector 11, can use the employed general material of anodal collector plate of lithium ion battery, for example, can list aluminium, stainless steel etc.Positive electrode collector 11 is preferably formed film like or laminar.In addition, the configuration of surface of positive electrode collector 11 both can be level and smooth also can be asperitiesization.The internal structure of positive electrode collector 11 can be the screen cloth body that comprises metallic fiber, porous plastid etc.
In barrier film 14, load or impregnation electrolyte as required.As electrolyte, not special restriction can list and for example support salt (electrolytic salt), support salt to be dissolved in the electrolyte (perhaps nonaqueous electrolytic solution) of the liquid state in the nonaqueous solvents, gel electrolyte, solid electrolyte etc.
Support salt from known support salt, suitably to select according to the type of electrical storage device 1.For example, when electrical storage device 1 is used as lithium ion battery, can use to comprise lithium and anionic salt.As anion, as long as can form salt, just have no particular limits with lithium, for example, can list halide anions, perchloric acid anion, trifluoromethanesulfonic acid anion, tetrafluoro boric acid anion (BF
4 -), phosphorus hexafluoride acid anion (PF
6 -), two (trifyl) acid imide anion, two (perfluor ethylsulfonyl) acid imide anion etc.Support that salt can use a kind separately, also can be mixed with two or more as required.
Dissolving supports the nonaqueous solvents of salt also can suitably select from known nonaqueous solvents according to the type of electrical storage device 1.For example, when electrical storage device 1 is lithium ion battery, non-water system double electric layer capacitor etc., as nonaqueous solvents, can use for example ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, oxolane, dioxane, sulfolane, dimethyl formamide, acetonitrile etc.Nonaqueous solvents can use a kind separately, also can be mixed with two or more as required.
Gel electrolyte is that aqueous electrolyte gelization obtains.Aqueous electrolytical gelation can be undertaken by for example add gelating agent in aqueous electrolyte.Gelating agent can use this area gelating agent commonly used, for example can list polyacrylonitrile, comprise acrylate compounds or methacrylate compound as the copolymer of polymer, ethene and the acrylonitrile of monomer component etc.Solid electrolyte is the electrolyte of solid, shaped.As solid electrolyte, can list for example Li
2S-SiS
2, Li
2S-B
2S
5, Li
2S-P
2S
5-GeS
2, sodium and aluminium oxide (Al
2O
3) mixture, amorphous polyethers, the polyethers that phase inversion temperature (Tg) is low, amorphous vinylidene difluoride-hexafluoropropylene copolymer, the poly(ethylene oxide) of different macromolecule mixtures etc.When using gel electrolyte and solid electrolyte, can not use barrier film 14, can only constitute electrical storage device 1 by configuration electrolyte between positive pole 10 and negative pole 12.
As hush panel 15, sealing gasket 16, liner 17 and housing 18, can use this area material commonly used.
Electrical storage device 1 can be by for example stacked along thickness direction according to the order of liner 17, negative electrode collector 13, negative pole 12, barrier film 14, positive pole 10 and positive electrode collector 11, by hush panel 15 and the resulting duplexer of housing 18 clampings, come the method for buckle hush panel 15 and housing 18 to make by sealing gasket 16 by being situated between.In addition, when the contact pressure of each parts such as the negative electrode collector 13 of electrical storage device 1, negative pole 12, barrier film 14, anodal 10, positive electrode collector 11 is abundant, liner 17 needn't be set.That is, whether liner 17 is set, should waits suitably according to the contact pressure of above-mentioned each parts and select.
Electrical storage device of the present invention is suitable as for example power supply of hybrid vehicle, various electronics electricity equipment (the particularly mancarried electronic aid of moving body communication apparatus, notebook computer, portable phone etc.) etc., the generating equalization electrical storage device of thermal power generation, wind power generation, fuel cell power generation etc., general family and condominium are with the power supply of non-common accumulating system, late into the night electric power accumulating system etc., uninterrupted power supply etc.
Below, the electrical storage device that provides embodiments of the present invention is used for the use-case that makes of portable phone etc.
Execution mode 1
With reference to Figure 10 an example of the portable phone that uses electrical storage device of the present invention is described.Figure 10 is the concise and to the point oblique view that uses the portable phone 100 of electrical storage device of the present invention in power supply.As shown in figure 10, portable phone 100 has display part 166 and input parts 168 such as liquid crystal panel, in the framework 160 that is provided with input part 168, be provided with electronic control circuit portion (not shown) and as the electrical storage device of the present invention 150 of power supply unit.The demonstration of the charge volume of control circuit portion control example such as electrical storage device (SOC), panel.Voltage when in addition, control example such as electrical storage device charge.
As electrical storage device 150, electrical storage device of the present invention and existing electrical storage device can be used in combination.So-called existing electrical storage device can list lithium ion battery, nickel-hydrogen accumulator, capacitor or fuel cell.
Because electrical storage device of the present invention can small-sized slimming, therefore can reduce the needed space of being provided with of electrical storage device, can make portable phone miniaturization slimming.Because electrical storage device of the present invention can charge at a high speed, therefore the charging interval can be shortened.Because electrical storage device of the present invention has high output and high power capacity, the therefore contour performanceization of continuous air time that can realize prolonging portable phone.
Execution mode 2
With reference to Figure 11 an example of the notebook computer that uses electrical storage device of the present invention is described.Figure 11 is the concise and to the point oblique view that uses the notebook computer 200 of electrical storage device of the present invention in power supply.As shown in figure 11, notebook computer 200 framework 260 that has display parts 266 such as liquid crystal panel and have keyboard operation portion 210.In framework 260, be provided with the electronic control circuit portion (not shown) that possesses CPU etc., cooling fan (not shown) and as the electrical storage device of the present invention 270 of power supply unit.
As electrical storage device 270, electrical storage device of the present invention and existing electrical storage device can be used in combination.So-called existing electrical storage device can list lithium ion battery, nickel-hydrogen accumulator, capacitor or fuel cell.
Because electrical storage device of the present invention can small-sized slimming, therefore can reduce the needed space of being provided with of electrical storage device, can make notebook computer miniaturization slimming.Because electrical storage device of the present invention can charge at a high speed, therefore the charging interval can be shortened.Because electrical storage device of the present invention has high output and high power capacity, therefore can realize the long-time use of notebook computer or high-speed starting etc.
Execution mode 3
With reference to Figure 12 an example of the hybrid vehicle that uses electrical storage device of the present invention is described.Figure 12 is the figure that shows the formation of the hybrid vehicle 300 that has used electrical storage device of the present invention.As shown in figure 12, hybrid vehicle 300 has engine 302, a plurality of motor 303,304 and 305, the converter 306,307 and 308 that is connected with them respectively, and as the electrical storage device of the present invention 309 of the power supply unit of supplying electric power and the controller 310 of control system integral body.Motor 303 is that engine 302 starts the auxiliary motor of using of using or starting car, has the function as generator.Motor 304 is that vehicle traction is to handle (energy adjustment) to use motor with motor, motor 305.By the discharge (supply of electric power) of electrical storage device 309, CD-ROM drive motor 303 drives, and starts or assists propulsion motor 305.The charging of electrical storage device 309 uses motor 303 as generator, and the actuating force of engine 302 is converted into electric power.
As electrical storage device 309, electrical storage device of the present invention and existing electrical storage device can be used in combination.So-called existing electrical storage device can list lithium ion battery, nickel-hydrogen accumulator, capacitor or fuel cell.
Because electrical storage device of the present invention can small-sized slimming, therefore can realize the lightweight of automobile.In addition, can reduce the needed space of being provided with of electrical storage device, can guarantee to increase accommodation space, the space of attending a banquet.Electrical storage device of the present invention can charge at a high speed, has high output and high power capacity, therefore can tackle various driving modes, can help the fuel cost of automobile.
Embodiment
Below, embodiments of the invention are described in detail, but the present invention is not limited to these embodiment.
Embodiment 1
Make same Coin shape electrical storage device as shown in Figure 1 in the following order.
(1) Zheng Ji making
Will be as active carbon powder (the specific area 1700m of positive active material
2/ g, number average bead diameter 2 μ m) 100mg, evenly mix with acetylene black 20mg as electrically conductive material.In this mixture, add 20mg polyvinylpyrrolidone and 800mg methyl alcohol, preparation anode mixture slurry.This anode mixture slurry is applied on the positive electrode collector (thick 15 μ m) of aluminium foil formation, vacuumize then is at the positive pole of aluminium foil surface formation stratiform.This is comprised positive electrode collector become with anodal anodal duplexer stamping-out that diameter 13.5mm's is discoid.At this moment, the coating weight of positive active material is 6.1mg/cm
2, anodal thickness is 45 μ m.Wherein, be by being that material with carbon element is placed in the nitrogen after the carbonization with phenol resin as the active carbon powder of positive active material, import steam and carry out that activation processing obtains.
In addition, when the duplexer that uses this positive pole duplexer and use complete same structure as the double electric layer capacitor that the utmost point (negative pole) is obtained, (as electrical storage device, when operating (discharging and recharging) in 0～2V) the scope, this electrical storage device capacity is 0.08mAh at single electrode potential 0～1V.
(2) making of negative pole
In negative electrode collector, use Copper Foil (specific area 11.6, arithmetic mean surface roughness (Ra) 2.0 μ m, thickness 43 μ m).By electron beam heating vapour deposition method, on this Copper Foil, form the negative pole (thickness 6 μ m, specific area 4.2) that Si oxide (SiOx) film constitutes.Specific area and arithmetic mean surface roughness are to use laser microscope (trade name: super degree of depth measuring shape microscope VK-855, キ-エ Application ス society makes) to measure.The thickness of negative electrode collector and negative pole is to use scanning electron microscope (SEM) to measure.The V/V of the electrolyte maintaining part of negative electrode collector is to try to achieve by the method identical with aftermentioned embodiment 10.
Obtain comprising the negative pole duplexer of negative electrode collector and negative pole by such method.The adjustment of negative pole thickness is undertaken by adjusting the evaporation time.The condition of electron beam heating evaporation is as follows.As vapor deposition source, use purity 99.9999% silicon metal (manufacturing of (strain) high-purity chemical research institute), in vacuum chamber, import the oxygen (japanic acid element (strain) manufacturing) of purity 99.7%, vacuum degree is adjusted into 3 * 10
-3Pa.In addition, with shine in the accelerating voltage of the electron beam of irradiation source be made as 8kV, radiation (emission) is made as 500mA.After negative pole forms, analyze composition by x-ray fluorescence analysis, the result is that the ratio of Si and O is Si:O=1:0.6 (mol ratio) in the negative pole.Hence one can see that, constitutes the silica (SiO of negative pole
x) the x value be 0.6.
Then, confirm the capacity of the above-mentioned negative pole that obtains by method as described below.To obtain by the negative pole duplexer stamping-out that method same as described above is made diameter 13.5mm discoid negative pole duplexer, with lithium metallic plate (thickness 300 μ m) form to the utmost point by barrier film (thickness 20 μ m) the subtend configuration that porous matter polyethylene sheets forms, make the Coin shape electrical storage device.This electrical storage device is carried out 3 times to discharge and recharge.At this moment, current value is 0.5mA, upper voltage limit 1.5V and lower voltage limit 0V.Discharge and recharge by this, confirm: the reversible capacity that can discharge and recharge is the 1.8mAh (capacity of unit are: 1.3mAh/cm
2), to discharge and recharge do not have the contribution irreversible capacity be 0.5mAh.
Because the above-mentioned negative pole of just having made that obtains does not contain lithium, be complete discharge condition therefore, that is, SOC (state of charge) is 0% state.The SOC of so-called negative pole, be not expression as electrical storage device integral body but the index of the charged state of expression negative pole monomer, the capacity when being the full charging with the negative pole monomer is 100%, the value that charge volume is represented with percentage with respect to the ratio of full charge volume.Therefore, the SOC of the state that has discharged fully is 0%, and the SOC of fully charged state is 100%.
In the present embodiment, on the above-mentioned negative terminal surface that obtains, form the lithium metal level of thickness 4.5 μ m, the SOC of negative pole is adjusted to 50% by vapour deposition method.Wherein, in the potential range of 0～1.5V that with the lithium is benchmark, the charge volume of the negative pole under the situation that the anticathode capacity has charged with 0.2CA (5 hour rate) is tried to achieve the SOC of negative pole as SOC100% (full charging) as benchmark with this value.In addition, evaporation can not be absorbed in the electrolyte in the negative pole even negative pole is immersed at the lithium metal of negative terminal surface yet, and negative pole is recharged (lithium charging).In addition, this lithium charge volume is equivalent to, and the negative pole irreversible capacity adds the charge capacity till 50% (SOC50%) that charges to reversible capacity.The thickness of the negative pole of SOC50% is 9 μ m.After SOC adjusted, the negative pole duplexer was punched into the discoid of diameter 13.5mm.
(3) assembling of electrical storage device
By being situated between,, make electrode body with above-mentioned anodal duplexer that obtains and the configuration of negative pole duplexer subtend by as containing the barrier film (thickness 20 μ m) that is soaked with electrolytical porous matter polyethylene sheets.In electrolyte, use the nonaqueous electrolytic solution that in the mixed solvent (volume ratio 1:3) of ethylene carbonate and carbonic acid Methylethyl ester, is dissolved with phosphorus hexafluoride acid lithium (supporting salt or electrolytic salt) with the ratio of 1.25mol/L.This electrode body is to be that downside is housed in the housing according to the positive electrode collector side.By press, the edge part by sealing gasket seal casinghousing open end and hush panel seals housing, makes Coin shape electrical storage device of the present invention shown in Figure 1.In addition,, press when insufficient, the liner with suitable thickness can be set between negative electrode collector and hush panel when the contact of each parts in the electrical storage device according to the thickness of positive pole.
Embodiment 2
In negative electrode collector, use electrolytic copper foil (specific area 11.6, arithmetic mean surface roughness (Ra) 1.8 μ m, thickness 43 μ m).By the RF sputtering method, on this Copper Foil, form the negative pole (thickness 1.5 μ m, specific area 11.4) that silicon thin film constitutes.Like this, obtain comprising the negative pole duplexer of negative electrode collector and negative pole.
Carry out the RF sputter by following method.Use the molten silicon target (silicon purity 99.99%) of 10 inches of diameters, the distance between target and the substrate is made as 7cm, import argon gas 50sccm.Vacuum atmosphere pressure 1.1Pa, apply power 1kW, film formation time 5 hours.
The result who confirms capacity of negative plates by the method identical with embodiment 1 is that the reversible capacity that can discharge and recharge is that (capacity of unit are is 1.5mAh/cm to 2.1mAh
2), to discharge and recharge do not have the contribution irreversible capacity be 0.1mAh.
In the present embodiment, form the lithium metal level of thickness 4 μ m in the above-mentioned negative terminal surface that obtains, the SOC of negative pole is adjusted into 50% by vapour deposition method.In addition, also can not be absorbed in the electrolyte in the negative pole even the lithium metal negative pole of evaporation on negative terminal surface is immersed in, negative pole is recharged (lithium charging).In addition, this lithium charge volume is equivalent to, and the negative pole irreversible capacity adds the charge capacity that charges to SOC 50%.The negative pole of the SOC 50% that obtains like this has the film forming thickness of 4 μ m.Except that the negative pole duplexer that uses this negative pole and negative electrode collector, by the method making electrical storage device identical with embodiment 1.
Comparative example 1
As negative electrode active material, use SiO particle (high-purity Science Institute (strain) manufacturing), to particle diameter 44 μ m, be used as negative electrode active material by automatic mortar crushing and pelletizing.This negative electrode active material, graphite (electrical conductivity auxiliary material) and polyacrylic acid (adhesive) obtain cathode agent according to the mixed of weight ratio 45:40:15 respectively.This cathode agent is crimped onto on the nickel screen cloth as the thickness 100 μ m of negative electrode collector, forms the negative pole (mixture layer) of thickness 75 μ m.
At the above-mentioned negative pole that obtains, carry out the affirmation of capacity and the charging process of adopting the electrochemical charge method by following method.With the above-mentioned negative pole that obtains, with as the barrier film (thickness 20 μ m) that the utmost point is formed by clamping porous matter polyethylene sheets of lithium metal (thickness 300 μ m) and the subtend configuration, making Coin shape electrical storage device.And, this electrical storage device is carried out 3 times discharges and recharges.At this moment, current value is that 0.5mA, upper voltage limit are that 1.5V and lower voltage limit are 0V.Discharge and recharge by this, the reversible capacity that affirmation can discharge and recharge is 14mAh, is 9mAh to discharging and recharging the irreversible capacity that does not have to contribute.At 50% (SOC 50%) that charges to reversible capacity afterwards, the Coin shape charging device is decomposed, take out the negative pole duplexer that comprises negative electrode collector and negative pole.Except using this negative pole duplexer, make electrical storage device by the method identical with embodiment 1.
Comparative example 2
Except negative pole thickness is become the 50 μ m from 75 μ m, form the negative pole of the thickness 50 μ m that comprise adhesive on nickel screen cloth (negative electrode collector) surface by the method identical with comparative example 1.At resulting negative pole,, carry out the affirmation and the charging process of capacity by the method identical with comparative example 1.The reversible capacity that discharges and recharges of confirming resulting negative pole be 9mAh, to discharge and recharge do not have the contribution irreversible capacity be 6mAh.At 50% (SOC50%) that charges to reversible capacity afterwards, the Coin shape charging device is decomposed, only take out the negative pole duplexer that comprises negative electrode collector and negative pole.Except using this negative pole duplexer, make electrical storage device by the method identical with embodiment 1.
Comparative example 3
The same with comparative example 2, carry out charging process by mechanical charging method anticathode.That is, on negative pole, form the Li metal level of thickness 38 μ m by vapour deposition method.This layer comprises the lithium amount that is equivalent to following electric weight, and described electric weight is the electric weight that the irreversible capacity of negative pole adds the 50%SOC that can charge to the reversible capacity that negative pole has.After the Li evaporation, the whole face colouring of negative terminal surface becomes silver color, confirms separating out of Li, does not cause the charging reaction of the Li on negative pole fully.In addition, if the negative pole duplexer of this negative pole and negative electrode collector is immersed in the nonaqueous electrolytic solution, then negative pole peels off from negative electrode collector, can not carry out the evaluation as electrical storage device.This can think because the evaporation of Li causes the deterioration of the adhesive in the negative pole to cause.
Electrical storage device at embodiment 1～2 and comparative example 1～2 carries out the charge/discharge capacity evaluation.Wherein, the positive electrode capacity of the electrical storage device of embodiment 1～2 and comparative example 1～2 is 0.08mAh, and use has the negative pole with respect to the reversible capacity of the abundant excess quantity of positive electrode capacity, and capacity of negative plates is abundant bigger than positive electrode capacity.Therefore, the theoretical charge/discharge capacity of these electrical storage devices is 0.08mAh.
The evaluation of charge/discharge capacity is following carrying out, and, carries out constant current charge-discharge with the current value of 0.5mA, 4mA or 12mA that is, and the charging upper voltage limit is that 3.75V, discharge lower voltage limit are 2.75V, and charging off time and discharge off time were respectively 1 minute.The charging off time is to the time of discharging till beginning next time behind the charging termination.The discharge off time is to the time of charging and beginning next time behind the discharge off.Carry out repeatedly 3 times this discharge and recharge, with the 3rd discharge capacity as charge/discharge capacity.Its evaluation result is as shown in table 1 below.
[table 1]
As shown in Table 1: as the comparative example 1 of existing electrical storage device and 2 electrical storage device, when current value little, during for 0.5mA, although can discharge and recharge with the roughly theoretical capacity of 0.08mA, but, when the current value when discharging and recharging increases to 4mA, 12mA, find that charge/discharge capacity reduces.Particularly when current value was 12mA, charge/discharge electricity amount extremely reduced.
By comparison, use and do not contain adhesive, the embodiment 1 of the negative pole below the thickness 10 μ m that directly form on the negative electrode collector and 2 electrical storage device of the present invention, even current value increases to 0.5mA, 4mA, 12mA, also can keep most charge/discharge electricity amount.That is the electrical storage device of compared with prior art high output, can be provided.In addition, comprise in the electrical storage device of organic bond in the use of comparative example 3, can't be by vapour deposition method occlusion lithium in negative pole in advance.In contrast, in the electrical storage device of embodiment 1 and 2, can by vapour deposition method before assembling in negative pole the occlusion lithium, therefore, consider also more excellent from the angle of processability.
Compare with embodiment 1 (negative pole thickness 9 μ m), the electrical storage device of embodiment 2 (negative pole thickness 4 μ m), the discharge capacity during current value 12mA increases, and can access the electrical storage device of higher output.This can be considered to because negative pole thickness of the electrical storage device of embodiment 2 is 4 μ m, than the thinner cause of negative pole thickness of the electrical storage device of embodiment 1.Therefore, negative pole thickness is preferably below the 5 μ m.
In the electrical storage device of embodiment 1 and 2, owing to can in the high pressure range of operating voltage (discharge lower voltage limit～charging upper voltage limit) 2.75～3.75V, discharge and recharge, therefore, compare with in two sides of positive active material and negative electrode active material, using the existing electrical storage device of active carbon, can realize higher energy densityization.In addition, employed negative pole is that thickness is the following films of 10 μ m in the electrical storage device of the present invention.Therefore, in the present invention, can realize the high capacity and the miniaturization of electrical storage device simultaneously.
Embodiment 3
Except that using following anodal layer laminate, make electrical storage device by the method identical with embodiment 1.
As constituting anodal positive active material, use organic compound polymer as the homopolymers of the represented monomeric unit of chemical structural formula (4) (below be designated as " pi-conjugated polymer ") with pi-conjugated electron cloud.This pi-conjugated polymer is by polyvinyl alcohol, synthetic with the compound dehydrating condensation of the molecular structure with chemical structural formula (5) of introducing carboxyl in tetrathiafulvalene (tetrathiofulvalene).The number-average molecular weight of this pi-conjugated polymer is about 15000, theoretical heap(ed) capacity is 200mA/g.
Pi-conjugated polymer and the 100mg acetylene black of 37.5mg are mixed, further add the 25mg polytetrafluoroethylene and mix, the modulation anode mixture.This anode mixture pressed tie on the positive electrode collector that the aluminum wire netting makes vacuumize.Its stamping-out is become the discoid of diameter 13.5mm, make duplexer anodal and positive electrode collector.At this moment, the coating weight of positive active material is every anodal unit are 0.5mg/cm
2, anodal thickness is that 90 μ m, anodal theoretical capacity are 0.14mAh.
Embodiment 4
Except that using following anodal layer laminate, make electrical storage device by the method identical with embodiment 1.
As constituting anodal positive active material, use organic compound polymer as the homopolymers of the represented monomeric unit of chemical structural formula (6) (below be designated as " free radical polyalcohol ") with free radical.This free radical polyalcohol is by after making the represented monomeric compound of chemical structural formula (7) carry out radical polymerization, makes the hydrogen atom oxidation of nitrogen-atoms institute combination and synthetic.The number-average molecular weight of this free radical polyalcohol is about 100000, theoretical heap(ed) capacity is 110mA/g.
Free radical polyalcohol and the 100mg acetylene black of 37.5mg are mixed, further add the 25mg polytetrafluoroethylene and mix, the modulation anode mixture.This anode mixture pressed tie on the positive electrode collector that the aluminum wire netting makes vacuumize.Its stamping-out is become the discoid of diameter 13.5mm, make duplexer anodal and positive electrode collector.At this moment, the coating weight of positive active material is every anodal unit are 0.5mg/cm
2, anodal thickness is that 90 μ m, anodal theoretical capacity are 0.08mAh.
At the electrical storage device of embodiment 3～4, carry out the evaluation of charge/discharge capacity.The evaluation of charge/discharge capacity is following to be carried out, and, carries out constant current charge-discharge with the current value of 0.5mA, 4mA or 12mA that is, and the upper voltage limit of charging is that 3.75V, discharge lower voltage limit are 2.75V, and the charging off time was respectively 1 minute with the discharge off time.The charging off time is meant that charging finishes the time till beginning discharge is next time arrived in the back.The discharge off time is meant that discharge finishes the time till beginning charging is next time arrived in the back.Carry out repeatedly 3 times this discharge and recharge, be charge/discharge capacity with the 3rd discharge capacity.Its evaluation result is as shown in table 2.
[table 2]
As shown in Table 2, embodiment 3 and 4 electrical storage device even current value increases to 0.5mA, 4mA, 12mA, also can be kept most charge/discharge electricity amount.That is the electrical storage device of compared with prior art high output, can be provided.In addition, in the electrical storage device of embodiment 3 and 4, can by vapour deposition method before assembling in negative pole the occlusion lithium, therefore, consider it is excellent from the angle of processability.By this result as can be known, though use can the situation of redox organic compound as positive active material in, also can access the electrical storage device of high output.
In addition, have higher capacity as the organic compound specific activity charcoal of the oxidable reduction of positive active material, and can carry out the operation under the high voltage, therefore can access and have the more electrical storage device that is rich in practicality of high power capacity.
Embodiment 5
In the present embodiment, study with the relation of the thickness of positive pole at the thickness of negative pole.
Make negative pole by the following method.
In negative electrode collector, use Copper Foil (specific area 11.6, surface roughness (Ra) 2.0 μ m, thickness 43 μ m).By electron beam heating vapour deposition method, on this Copper Foil, form Si oxide (SiO
x) negative pole (thickness 6 μ m, specific area 4.2) that forms of film.
Obtain comprising the negative pole duplexer of negative electrode collector and negative pole like this.The adjustment of negative pole thickness can be undertaken by adjusting the evaporation time.The condition of electron beam heating evaporation is as follows.As vapor deposition source, use purity 99.9999% silicon metal (manufacturings of (strain) high-purity chemical research institute), by the oxygen (japanic acid element (strain) manufacturing) of importing purity 99.7% in vacuum chamber vacuum degree is adjusted to 3 * 10
-3P.In addition, the accelerating voltage of the electron beam of irradiation vapor deposition source is that 8kV, radiation are 500mA.After negative pole forms, analyze composition by x-ray fluorescence analysis, the result is: the molar ratio of Si and O is 1:0.6 in the negative pole.Hence one can see that, constitutes the silica (SiO of negative pole
x) the x value be 0.6.
Then, confirm the capacity of the above-mentioned negative pole that obtains by method as described below.The barrier film (thickness 20 μ m) that the utmost point is made up of porous matter polyethylene sheets by being situated between that will obtain the discoid negative pole duplexer of diameter 13.5mm by the negative pole duplexer stamping-out that above-mentioned same procedure is made, form with lithium metallic plate (thickness 300 μ m) and configuration in opposite directions, making Coin shape electrical storage device.This electrical storage device is carried out 3 times to discharge and recharge.At this moment, current value is 0.5mA, upper voltage limit 1.5V and lower voltage limit 0V.By discharging and recharging, confirm: the reversible capacity that can discharge and recharge is the 1.8mAh (capacity of unit are: 1.3mAh/cm
2), to discharge and recharge do not have the contribution irreversible capacity be 0.5mAh.
At last, adjust the SOC of negative pole by following method.That is, anticathode carries out machinery charging, and then, the SOC by the electrochemical charge anticathode carries out fine adjustment.Specifically, form the lithium metal of the thickness 2.6 μ m that are equivalent to irreversible capacity (0.5mAh) by vapour deposition method in the negative terminal surface of the above-mentioned negative pole duplexer that obtains.In addition,, evaporation can not be absorbed in the electrolyte in the negative pole even being immersed at the lithium metal negative pole of negative terminal surface yet, in negative pole, and the suitable amount of irreversible capacity of having charged.In addition, the negative pole duplexer stamping-out after the machinery charging is become diameter 13.5mm discoid negative pole duplexer, with lithium metal (thickness 300 μ m) make subtend makes the Coin shape electrical storage device by the clamping barrier film to the utmost point.And,, reach 50% (charge capacity 0.05mAh) until the SOC of negative pole with the constant current charge of 0.5mA.In addition, wherein employed barrier film is identical with embodiment 1 with electrolyte.
Like this, charging reaches 50% until the SOC of negative pole, then the Coin shape electrical storage device is decomposed, and obtains SOC and be 50% negative pole.The thickness of the negative pole that at this moment obtains is 9 μ m.
The active material weight and the electrode capacity of the unit are of the positive pole when electrical storage device constitutes are identical with embodiment 1, except anodal thickness becomes the value shown in the table 3, make anodal duplexer (A-1)～(A-7) by the method identical with embodiment 1.
In addition, when anodal thickness is 45,60,70,100,125,30 and 35 μ m, respectively will be as the acetylene black of electrical conductivity auxiliary material with respect to 100mg active carbon powder (specific area 1700m
2/ g, average grain diameter 2 μ m) the cooperation ratio adjust to 20,30,35,50,62,15 and 18mg.
And, use above-mentioned negative pole duplexer that obtains and anodal duplexer (A-1)～(A-7), make electrical storage device (A-1)～(A-7) by the method identical with embodiment 1.
(A-1)～(A-7) carries out the charge/discharge capacity evaluation at electrical storage device.
The evaluation of charge/discharge capacity is following to be carried out, promptly, carry out constant current charge-discharge with 4mA or 12mA, the upper voltage limit that charges is that 3.75V, discharge lower voltage limit are 2.75V, and the discharge off time that finishes the charging off time till discharging to beginning in the back next time and finish till charging to beginning in the back from discharging next time of charging was respectively 1 minute.Carry out repeatedly 3 times this discharge and recharge, be charge/discharge capacity with the 3rd discharge capacity.
Its evaluation result is as shown in table 1.Similarly, in table 1, put down in writing the thickness and the ratio thereof of employed positive pole and negative pole in each electrical storage device.
[table 3]
As shown in table 3, when the current value with 4mA charges to electrical storage device, at anodal thickness is in the electrical storage device (A-1)～(A-5) of negative pole thickness more than 5 times, compares with (A-7) with 5 times electrical storage device (A-6) of the not enough negative pole thickness of anodal thickness, obtains the high power capacity of 0.08mAh.
As from the foregoing, preferred anodal thickness is more than 5 times of negative pole thickness.Wherein, the positive electrode capacity of electrical storage device (A-1)～(A-7) is 0.08mAh, and capacity of negative plates has the reversible capacity fully superfluous with respect to positive electrode capacity, and therefore, theoretic charge/discharge capacity is 0.08mAh.
In addition, when electrical storage device being discharged and recharged with the 12mA current value, anodal thickness be negative pole thickness more than 10 times electrical storage device (A-4) and (A-5) in, compare with (A-7) with 10 times electrical storage device (A-1)～(A-3), (A-6) of the not enough negative pole thickness of anodal thickness, obtain higher capacity.
Even at high current charge-discharge situation in also can access high power capacity, this means it is electrical storage device with high power capacity and output characteristic excellence.That is, can think owing to can therefore can provide the electrical storage device of the conductibility and the diffusivity excellence of ion at the inner fully anion and the cation of amount of keeping of electrical storage device.
As shown in the above, more preferably anodal thickness is more than 10 times of negative pole thickness.
Embodiment 6
In the present embodiment, study at the specific area of negative pole.
Use following negative electrode collector (B-1)～(B-3),, make electrical storage device (B-1)～(B-3) by the method identical with embodiment 1.
Make negative pole duplexer (B-1) by following method.
In negative electrode collector, use electrolytic copper foil (specific area 11.6, arithmetic mean surface roughness (Ra) 1.8 μ m, thickness 43 μ m).On this Copper Foil,, form the negative pole that silicon thin film is made by the RF sputter.Like this, obtain comprising the negative pole duplexer of negative electrode collector and negative pole.
Carry out the RF sputter by following method.Use the molten silicon target (silicon purity 99%) of 10 inches of diameters, the distance between target and the substrate is made as 7cm, import argon gas 50sccm.Vacuum atmosphere pressure 1.1Pa, apply power 1kW, film formation time 1 hour.
(SEM) observes resulting negative pole by scanning electron microscope, and the result is that negative pole is that thickness is the film of 0.3 μ m.Figure 13 is the microphotograph in the thickness direction cross section of negative electrode collector 53.Negative pole 14 is the microphotograph in cross section of thickness direction of the duplexer of negative pole 52 and negative electrode collector 53.As shown in Figure 14, on the surface (upper surface) of the electrolytic copper foil of negative electrode collector 53, concavo-convex according to this electrolytic copper foil surface forms the film as negative pole 52.In addition, the specific area on the surface of negative pole 52 is 11.4.The concavo-convex of negative electrode collector 53 surfaces reproduced on the surface of negative pole 52 with being in the main true, therefore, and value that can be approximate with the specific area on the surface that obtains negative electrode collector 53.
Then, confirm the capacity of the above-mentioned negative pole that obtains by following method.By the negative pole duplexer stamping-out of above-mentioned identical method manufacturing become diameter 13.5mm discoid negative pole duplexer, with lithium metallic plate (thickness 300 μ m) make to the utmost point, the barrier film of making by clamping porous polyethylene sheet (thickness 20 μ m) and subtend makes the Coin shape electrical storage device.This electrical storage device is carried out 3 times to discharge and recharge.This moment, current value was that 0.1mA, upper voltage limit 1.5V and lower voltage limit are 0V.Discharge and recharge by this, the reversible capacity that can discharge and recharge is 0.44mAh/cm
2, to discharge and recharge do not have the contribution irreversible capacity be 0.03mAh/cm
2
Then, the SOC with negative pole adjusts to 50%.That is, form the lithium metal level of thickness 1.3 μ m in negative terminal surface by vapour deposition method.Its stamping-out is become the duplexer of discoid formation lithium metal, negative pole and the negative electrode collector of diameter 13.5mm.In addition, also can not be absorbed in the electrolyte in the negative pole even evaporation is immersed in the lithium metal negative pole of negative terminal surface, negative pole is recharged (lithium charging).In addition, this lithium charge volume is equivalent to, and the irreversible capacity of negative pole adds the charge capacity that charges to SOC 50%.The adjusted negative pole thickness of SOC is 0.6 μ m.
Negative pole duplexer (B-2) is made by the following method.
In negative electrode collector, use rolled copper foil (specific area 7.0, arithmetic mean surface roughness (Ra) 1.24 μ m, thickness 15 μ m).On this Copper Foil, under above-mentioned the same terms, carry out the RF sputter, form the negative pole that silicon thin film is made.Like this, obtain comprising the negative pole duplexer of negative electrode collector and negative pole.
(SEM) observes resulting negative pole by scanning electron microscope, and the result is that negative pole is that thickness is the film of 0.7 μ m.The specific area of negative terminal surface is 7.1.Reproduced the concavo-convex of negative electrode collector surface in negative terminal surface with being in the main true, therefore, obtained the value approximate with the specific area on negative electrode collector surface.
In addition, by the capacity of said method affirmation negative pole, the reversible capacity that affirmation can discharge and recharge is 0.53mAh/cm
2, to discharge and recharge do not have the contribution irreversible capacity be 0.04mAh/cm
2
Then, form the lithium metal level of thickness 1.6 μ m in negative terminal surface by vapour deposition method.Thus, the SOC with negative pole adjusts to 50%.The adjusted negative pole thickness of SOC is 1.4 μ m.
Make negative electrode collector (B-3) by following method.
On negative electrode collector, use rolled copper foil (specific area 1.0, arithmetic mean surface roughness (Ra) 0.12 μ m, thickness 15 μ m).On this Copper Foil, under above-mentioned the same terms, carry out the RF sputter, form the negative pole that silicon thin film is made.Like this, obtain comprising the negative pole duplexer of negative electrode collector and negative pole.
(SEM) observes resulting negative pole by scanning electron microscope, and the result is that negative pole is that thickness is the film of 0.7 μ m.Figure 15 is the microphotograph in the thickness direction cross section of negative electrode collector 62.Figure 16 is the microphotograph in cross section of thickness direction of the duplexer of negative pole 61 and negative electrode collector 62.As shown in Figure 16, on the surface as the rolled copper foil of negative electrode collector 62, concavo-convex according to this rolled copper foil surface forms the film as negative pole 61.In addition, the specific area on the surface of negative pole 61 is 1.1.The concavo-convex of negative electrode collector 62 surfaces reproduced on negative pole 61 surfaces with being in the main true, therefore, obtains the value approximate with the specific area on negative electrode collector 62 surfaces.
In addition, confirm the capacity of negative pole by above-mentioned same method, the reversible capacity that affirmation can discharge and recharge is 0.53mAh/cm
2, to discharge and recharge do not have the contribution irreversible capacity be 0.04mAh/cm
2
Then, by vapour deposition method, form the lithium metal level of thickness 1.6 μ m in negative terminal surface.Like this, the SOC with negative pole adjusts to 50%.The thickness of the adjusted negative pole of SOC is 1.4 μ m.
At electrical storage device (B-1)～(B-3), carry out the charge/discharge capacity evaluation.Wherein, the positive electrode capacity of electrical storage device (B-1)～(B-3) is 0.08mAh, and use has the negative pole with respect to the reversible capacity of the abundant excess quantity of positive electrode capacity, and capacity of negative plates is abundant bigger than positive electrode capacity.Therefore, the theoretical charge/discharge capacity of these electrical storage devices is 0.08mAh.
The evaluation of charge/discharge capacity is following to be carried out, and, carries out constant current charge-discharge with the current value of 0.6mA, 1.8mA or 3mA that is, and the charging upper voltage limit is that 3.75V, discharge lower voltage limit are 2.75V.Charging off time and discharge off time were respectively 1 minute.The charging off time is to the time of discharging and beginning next time behind the charging termination.The discharge off time is to the time of charging and beginning next time behind the discharge off.Carry out repeatedly 3 times this discharge and recharge, with the 3rd discharge capacity as charge/discharge capacity.Its evaluation result is as shown in table 4 below.In addition, in table 4, also put down in writing the negative pole specific area of each electrical storage device simultaneously.
[table 4]
As shown in Table 4, when the current value when discharging and recharging is 0.6mA, in any one of electrical storage device (B-1)～(B-3), all can access the design capacity of 0.08mAh.In addition, even when the current value when discharging and recharging is 1.8mA or 3mA, electrical storage device (B-1) and (B-2) also demonstrate good capacity near design capacity.Especially, (B-2) compares with electrical storage device, and electrical storage device (B-1) also demonstrates more excellent characteristic in the such big electric current situation of 3mA.
Like this, at electrical storage device (B-1) with (B-2), even in the situation that the big electric current such with 3mA discharges and recharges, also can access high power capacity.This means, these electrical storage devices be high power capacity and the output characteristic excellence.
Measure the impedance of each electrical storage device, the resistance value of electrical storage device (B-3) is than big 30 Ω of resistance value of electrical storage device (B-1).Electrical storage device (B-1) is except that negative pole, and (B-3) is identical for structure and electrical storage device, therefore by increasing the specific area of negative pole, confirms that the impedance of electrical storage device reduces.
By The above results as can be known, comprise in use under the situation of the film cathode that specific non-material with carbon element and thickness as the very large negative electrode active material of unit materials energy is 10 μ m, the specific area of negative pole is preferably more than 5.Like this, can access the electrical storage device of high power capacity and output characteristic excellence, that is, and high capacity capacitor.In addition, because the output characteristic of electrical storage device significantly improves, so the specific area of negative pole is more preferably more than 10.
Embodiment 7
Use the identical anodal duplexer of embodiment 3 that has used above-mentioned pi-conjugated polymer with positive active material, in addition, with the same electrical storage device (B-4) of making of electrical storage device (B-1) of embodiment 6.
Use the identical anodal duplexer of embodiment 4 that has used above-mentioned free radical polyalcohol with positive active material, in addition, with the same electrical storage device (B-5) of making of electrical storage device (B-1) of embodiment 6.
At electrical storage device (B-4) and (B-5), carry out the charge/discharge capacity evaluation.The evaluation of charge/discharge capacity is carried out under the following conditions, that is, charging and discharging currents 4mA, charging upper voltage limit 4.2V, discharge lower voltage limit 2.75V, charging off time and discharge off time were respectively 1 minute.The charging off time is to the time of discharging and beginning next time behind the charging termination.Carry out repeatedly 3 times this discharge and recharge, with the 3rd discharge capacity as charge/discharge capacity.
Resulting charge/discharge capacity, electrical storage device (B-4) are that 0.14mAh, electrical storage device (B-5) are 0.08mAh, can access the high power capacity as design capacity.That is, in any situation, use the situation of active carbon the same with positive active material, the electrical storage device that can both obtain to have high power capacity and output characteristic excellence.In addition, as the organic compound of the oxidable reduction of positive active material, compare with active carbon and to have high power capacity, and can under high voltage, operate, therefore can obtain the electrical storage device of high-capacitance more and practicality excellence.
Embodiment 8
The SOC of the negative pole when constituting at electrical storage device in the present embodiment, studies.
Negative electrode collector uses Copper Foil (arithmetic mean surface roughness (Ra) 2.0 μ m, thickness 43 μ m, specific area 11.6).By electron beam heating vapour deposition method, on this Copper Foil, form Si oxide (SiO
x) negative pole (thickness 7 μ m, specific area 4.0) that constitutes of film.Obtain comprising the negative pole duplexer of negative electrode collector and negative pole by such method.The adjustment of negative pole thickness is undertaken by adjusting the evaporation time.The condition of electron beam heating evaporation is as follows.As vapor deposition source, use purity 99.9999% silicon metal (manufacturing of (strain) high-purity chemical research institute), in vacuum chamber, import the oxygen (japanic acid element (strain) manufacturing) of purity 99.7%, vacuum degree is adjusted into 3 * 10
-3Pa.In addition, the accelerating voltage of electron beam with the irradiation irradiation source is made as 8kV, radiation is made as 500mA.After negative pole forms, analyze composition by x-ray fluorescence analysis, the result is that the ratio of Si and O is Si:O=1:0.6 (mol ratio) in the negative pole.Hence one can see that, constitutes the silica (SiO of negative pole
x) the x value be 0.6.
Then, confirm the capacity of the above-mentioned negative pole that obtains by method as described below.To obtain by the negative pole duplexer stamping-out that above-mentioned same procedure is made diameter 13.5mm discoid negative pole duplexer, with lithium metallic plate (thickness 300 μ m) form to barrier film (thickness 20 μ ms) the subtend configuration of the utmost point by being situated between and forming, making Coin shape electrical storage device by porous matter polyethylene sheets.This electrical storage device is carried out 3 times to discharge and recharge.At this moment, current value is 0.5mA, upper voltage limit 1.5V and lower voltage limit 0V.Discharge and recharge by this, confirm: the reversible capacity that can discharge and recharge is the 2.1mAh (capacity of negative plates of unit are: 1.5mAh/cm
2), to discharge and recharge do not have the contribution irreversible capacity be 0.5mAh.
In the present embodiment, anticathode carries out the machinery charging, comes the SOC of anticathode to regulate by electrochemical charge then.Negative pole SOC obtains according to method similarly to Example 1.
Specifically, on the negative terminal surface of the above-mentioned negative pole duplexer that obtains, form the lithium metal level of the thickness 3 μ m that are equivalent to irreversible capacity (0.6mAh) by vapour deposition method.In addition, also can not be absorbed in the electrolyte in the negative pole even evaporation is immersed at the lithium metal negative pole of negative terminal surface, negative pole has been recharged (lithium charging) and has been equivalent to the amount of irreversible capacity.
And then, with the negative pole duplexer stamping-out after the machinery charging become diameter 13.5mm discoid negative pole duplexer, with lithium metallic plate (thickness 300 μ m) make subtend makes the Coin shape electrical storage device by the clamping barrier film to the utmost point.
And,, make the SOC of negative pole reach value as shown in table 5 with the constant current charge official hour of 0.5mA.Specifically, adjust the charging interval, the SOC of negative pole is become 20%, 40%, 50%, 70%, 80%, 90%, 0% or 10% respectively, obtain negative pole (C-1)～(C-8) respectively.In addition, be used for that negative pole SOC is controlled at 20%, 40%, 50%, 70%, 80%, 90%, 0% or 10% charge capacity and be respectively 0.42mAh, 0.84mAh, 1.05mAh, 1.47mAh, 1.68mAh, 1.89mAh, 0mAh or 0.21mAh.In addition, the thickness of the adjusted negative pole of above-mentioned SOC (C-1)～(C-8) is respectively 6.8 μ m, 7.6 μ m, 8.1 μ m, 8.7 μ m, 9.2 μ m, 9.6 μ m, 6.0 μ m and 6.5 μ m, is below the 10 μ m.In addition, use barrier film and the electrolyte identical with the electrical storage device of embodiment 1.
In addition, use the negative pole duplexer comprise (anticathode does not carry out machinery charging and electrochemical charge) negative pole (thickness 7 μ m) of not adjusting SOC, in addition, make electrical storage device (C-9) by the method identical with embodiment 1.Wherein, this negative pole is equivalent to the charging process of amount of 30% irreversible capacity correspondence of reversible capacity, and therefore, the SOC of the negative pole when electrical storage device is constituted is-30%.
Except using above-mentioned negative pole duplexer (C-1)～(C-9),, make electrical storage device (C-1)～(C-9) by the method identical with embodiment 1.
At electrical storage device (C-1)～(C-9), carry out the evaluation of charge/discharge capacity evaluation and impedance.
The evaluation of charge/discharge capacity is by carrying out constant current charge-discharge under the current value of 4mA, and the charging upper voltage limit is that 3.75V, discharge lower voltage limit are 2.75V, and charging off time and discharge off time were respectively 1 minute.The charging off time is to the time of discharging till beginning next time behind the charging termination.Carry out repeatedly 3 times this discharge and recharge, with the 3rd discharge capacity as charge/discharge capacity.
In addition, the evaluation of impedance is by using AC impedence method, carrying out under the discharge condition after the charge/discharge capacity evaluation finishes.Condition determination is: beginning with amplitude 10mV, frequency range from open circuit voltage is 10
6～0.1Hz tests, the resistance value of reading frequency 10Hz.
In addition, the impedance of wherein said electrical storage device is the index that shows the output characteristic of electrical storage device.For example, when the impedance of electrical storage device hour, the resistance of electrical storage device is low, then means to have high output characteristic, and when impedance was big, the resistance height of electrical storage device did not possess high output characteristic.
Above-mentioned evaluation result is as shown in table 5.The SOC (%) of the negative pole when the negative pole SOC (%) of (when making the discharge when just having finished) and device charge when in addition, also showing the device formation in table 5.
[table 5]
| Electrical storage device (negative pole) No. | The negative pole SOC (%) of (during discharge) when electrical storage device constitutes | Negative pole SOC (%) during the electrical storage device charging | The charge/discharge capacity of electrical storage device (mAh) | The impedance of electrical storage device (Ω) |
| C-1 | 20 | 24 | 0.09 | 5.0 |
| C-2 | 40 | 45 | 0.10 | 4.4 |
| C-3 | 50 | 55 | 0.10 | 4.4 |
| C-4 | 70 | 75 | 0.10 | 4.8 |
| C-5 | 80 | 85 | 0.10 | 5.1 |
| C-6 | 90 | 95 | 0.10 | 6.2 |
| C-7 | 0 | 4 | 0.08 | 52.8 |
| C-8 | 10 | 14 | 0.09 | 10.0 |
| C-9 | -30 | - | 0 | - |
As shown in table 5, electrical storage device (C-1)～(C-8) demonstrates the charge/discharge capacity of 0.08～0.10mAh, can confirm the operation as electrical storage device.Voltage when this electrical storage device discharges and recharges is 2.75～3.75V, more than about 3V, then can accesses the voltage higher than existing double electric layer capacitor.That is, can access the electrical storage device that under high voltage, to operate and to have high power capacity.
Can not obtain charge/discharge capacity in electrical storage device (C-9), this is considered to because the irreversible capacity of negative pole causes.That is, this is considered to can't discharge owing to the irreversible capacity of a part of making the charge capacity after just having finished as negative pole is consumed.In addition, in electrical storage device (C-1)～(C-8), in the SOC of negative pole adjustment process, all carry out the precharge of the suitable amount of the irreversible capacity of negative pole and handled, therefore obtained the favorable charge-discharge capacity.
In addition, because the reversible capacity of the negative pole of electrical storage device is 2.1mAh, so the utilance of negative electrode active material is 4～5%, that is, in the electrical storage device, the difference of the SOC of the negative pole during charging during with discharge is 4～5%.Therefore as can be known, the electrical storage device of the high power capacity that when employed negative pole SOC was 0～95% in the electrical storage device, can to obtain at operating voltage be 2.75～3.75V, approximately operate under the high voltage more than the 3V.
In addition, as shown in Table 5, the impedance of electrical storage device depends on the SOC of negative pole largely.Negative pole SOC when discharging and recharging is that impedance is reduced to below 6.2 Ω in 20～95% the electrical storage device (C-1)～(C-6).Relative therewith, the SOC of negative pole be below 20% electrical storage device (C-7) and (C-8) in, impedance increases to more than 10 Ω.By this result as can be known, when the SOC of the negative pole of electrical storage device is 20～95%, can access that impedance is little, the electrical storage device of high output.In addition, for electrical storage device that can not determine charge/discharge capacity (C-9), do not carry out the mensuration of impedance.
Then, use electrical storage device (C-1), (C-3), (C-6) and (C-8), carry out repeated charge and test.The condition of discharging and recharging is: charging and discharging currents is 4mA, and the upper voltage limit of charging is that 3.75V, discharge lower voltage limit are 2.75V.In addition, charging finish the back till the beginning discharge next time the charging off time and, be respectively 1 minute from the discharge off time that discharge finishes till charging to beginning in the back next time.Carry out repeatedly 500 times this discharge and recharge.Carry out this repeatedly and discharge and recharge test 6 times, that is, test repeatedly until amounting to period and reach 3000 times.
In above-mentioned repetition test, whenever carry out repeatedly discharging and recharging for 500 times, the charging and discharging currents value is made as 0.5mA, in addition, under above-mentioned the same terms, carry out discharging and recharging for 3 times, obtain discharge capacity the 3rd time.
The result of this repetition test as shown in figure 17.Capacity sustainment rate among Figure 17 is the percentage of each circulation time discharge capacity of trying to achieve with respect to first discharge capacity.As shown in Figure 17, the repeated charge characteristic of electrical storage device depends on the negative pole SOC of electrical storage device to a great extent.Specifically, the electrical storage device (C-1) of negative pole SOC when discharging and recharging in 20～95% scope, (C-3) and (C-6) in, when the number of occurrence is 3000 times, the capacity sustainment rate is more than 50%, with respect to this, the negative pole SOC when discharging and recharging is in 10% the electrical storage device (C-8), is 3000 times the moment in the number of occurrence, the capacity sustainment rate is reduced to 20%, and characteristic is low repeatedly.
By The above results as can be known, in order to obtain having the electrical storage device of high power capacity and output characteristic and repeated charge excellent, the SOC of the negative pole during the discharging and recharging of electrical storage device is preferably 20～95%.
Embodiment 9
Use the identical anodal duplexer of embodiment 3 that uses above-mentioned pi-conjugated polymer with positive active material, in addition the same with the electrical storage device (C-3) of embodiment 11, making electrical storage device (C-10).
In addition, use the identical anodal duplexer of embodiment 4 that uses above-mentioned free radical polyalcohol with positive active material, in addition the same with the electrical storage device (C-3) of embodiment 11, making electrical storage device (C-11).
To electrical storage device (C-10) and (C-11), carry out the charge/discharge capacity evaluation according to following method.The condition of discharging and recharging is: the charging and discharging currents value is 4mA, the upper voltage limit of charging is that 4.2V, discharge lower voltage limit are 2.75V, charging finish the back to charging off time of beginning discharge next time and, finish the discharge off time of back till begin next time to charge from discharge and be respectively 1 minute.Carry out repeatedly 3 times this discharge and recharge, be charge/discharge capacity with the 3rd discharge capacity.The result of its evaluation result and electrical storage device (C-3) is as shown in table 6.
[table 6]
| Electrical storage device (negative pole) No. | The negative pole SOC (%) of (during discharge) when electrical storage device constitutes | Negative pole SOC (%) during the electrical storage device charging | The charge/discharge capacity of electrical storage device (mAh) |
| C-3 | 50 | 55 | 0.10 |
| C-10 | 50 | 70 | 0.40 |
| C-11 | 50 | 60 | 0.22 |
At electrical storage device (C-10) with (C-11), obtain than the higher capacity of electrical storage device (C-3).In these electrical storage devices, voltage 2.75～4.2V that can be when discharging and recharging, approximately operate under the high voltage more than the 3V.
At electrical storage device (C-10) and (C-11), use the situation of active carbon the same with positive active material, can access high power capacity and excellent output characteristic and repeated charge characteristic.
In addition, at electrical storage device (C-10) and (C-11), though in being 50～70% scope, negative pole SOC discharges and recharges,, as long as negative pole SOC in 20～95% the scope, just can access above-mentioned same result.
In the present embodiment, study at the form of negative electrode collector.
On the stratiform negative electrode collector,, form silica (SiO by electron beam heating vapour deposition method
x) negative pole (thickness 3.0 μ m) made of film.Adjust the thickness of negative pole by the adjustment evaporation time.The condition of electron beam heating evaporation is as follows.As vapor deposition source, use purity 99.9999% silicon metal (manufacturing of (strain) high-purity chemical research institute), in vacuum chamber, import the oxygen (japanic acid element (strain) manufacturing) of purity 99.7%, vacuum degree is adjusted into 3 * 10
-3Pa.In addition, the accelerating voltage of electron beam with the irradiation irradiation source is made as 8kV, radiation is made as 500mA.After negative pole formed, the result who analyzes composition by x-ray fluorescence analysis was that the ratio of Si and O is Si:O=1:0.6 (mol ratio) in the negative pole.Hence one can see that, constitutes the silica (SiO of negative pole
x) the x value be 0.6.
Then, confirm the capacity of the above-mentioned negative pole that obtains by method as described below.With the negative pole of above-mentioned same making, with as lithium metal (thickness 300 μ m) to barrier film (thickness 20 μ ms) the subtend configuration of the utmost point by being situated between and forming, making Coin shape electrical storage device by porous matter polyethylene sheets.This electrical storage device is carried out 3 times to discharge and recharge.At this moment, current value is 0.1mA, upper voltage limit 1.5V and lower voltage limit 0V.Discharge and recharge by this, the reversible capacity that can discharge and recharge is 0.72mAh/cm
2, to discharge and recharge do not have the contribution irreversible capacity be 0.22mAh/cm
2
The above-mentioned negative pole that obtains because the negative electrode active material in the negative pole of just having made does not contain lithium, is complete discharge condition therefore, that is, SOC is 0% state.The SOC of negative pole is not the index of expression as the charged state of electrical storage device integral body, but the index of the charged state of expression negative pole monomer, and be 100% with the capacity in full when charging of negative pole monomer, the value that charge volume is represented with percentage with respect to the ratio of full charge volume.Therefore, the SOC of Fang Dian state is 0% fully, and the SOC of fully charged state is 100%.In addition, the SOC of negative electrode active material tries to achieve by the following method.In the potential range of 0～1.5V that with the lithium is benchmark, the charge volume of the negative pole under the situation that the anticathode capacity has been charged with 0.2CA (5 hour rate) is defined as SOC 100% (full charging), tries to achieve the SOC value with this value as benchmark.
In the present embodiment, on the above-mentioned negative terminal surface that obtains, form the lithium metal level of thickness 3.0 μ m, the SOC of negative pole is adjusted to 50% by vapour deposition method.In addition, also can not be absorbed in the electrolyte in the negative pole even evaporation is immersed at the lithium metal negative pole of negative terminal surface, negative pole is recharged (lithium charging).In addition, this lithium charge volume is equivalent to, and the irreversible capacity of negative pole adds the charge capacity that charges to SOC 50%.The thickness of the negative pole of the SOC 50% that obtains like this is the film forming thickness of 4.5 μ m.
Except using above-mentioned negative pole duplexer, make electrical storage device by the method identical with embodiment 1.And, when the stacked system of above-mentioned negative pole is done, use following various negative electrode collector (D-1)～(D-7).
In negative electrode collector (D-1), use the Copper Foil (specific area 1.4) that has projection on the surface.This negative electrode collector is made by rolled copper foil is carried out the pattern plating.The pattern plating is to be coated with negative type photoresist on the rolled copper foil of thickness 20 μ m, use accounts for the minus mask that 92% of copper foil surface disposes like that according to the square pattern of 10 μ m, resist film on the Copper Foil is exposed, develops, by electrolysis copper particle is separated out in formed ditch, remove resist then, obtain having the Copper Foil of the projection that trapezoidal shape is arranged on the surface.
Wherein, Figure 18 is scanning electron microscope (SEM) photo of the major part in the thickness direction cross section of employed negative electrode collector 70 in the electrical storage device (D-1).Negative electrode collector 70 comprises current collection film 71 as rolled copper foil, is formed at a plurality of projections 72 on current collection film 71 surfaces.Projection 72 is formed at the two sides of the thickness direction of current collection film 71.The cross sectional shape of the thickness direction of projection 72 is as the criterion trapezoidal, and the height of projection 72 is 15 μ m.In addition, the thickness that comprises the negative electrode collector 70 of projection 72 is 50 μ m, and the occupied area of projection 72 on current collector film 71 surfaces be 8%, be 55% with respect to the volume ratio of the electrolyte maintaining part of the possessive volume of negative electrode collector 70.Wherein, the occupied area of projection 72 is meant that the gross area of the part that is formed with projection 72 on negative electrode collector 70 surfaces is with respect to the ratio of the area on negative electrode collector 70 surfaces.
The thickness of the height of projection 72 and negative electrode collector 70 is to measure by the cross section electron microscope observation of collector body.In addition, the occupied area of projection 72 on collector body 71 surfaces is to measure by the surface electronic microscopic examination of collector body.Use these values to calculate V/V with respect to the electrolyte maintaining part of the possessive volume of negative electrode collector 70.
In negative electrode collector (D-2), use the Copper Foil (specific area 1.4) that has a plurality of projections on the two sides of thickness direction.This negative electrode collector is made by rolled copper foil is carried out the pattern plating.The pattern plating is to be coated with negative type photoresist on the rolled copper foil of thickness 20 μ m, use accounts for the minus mask that 85% of copper foil surface disposes like that according to the square pattern of 10 μ m, resist film on the Copper Foil is exposed, develops, by electrolysis copper particle is separated out in formed ditch, remove resist then, obtain having the Copper Foil of the projection that trapezoidal shape is arranged on the surface.The cross sectional shape of the thickness direction of projection is as the criterion trapezoidal, and the height of projection is 15 μ m.In addition, the thickness that comprises the negative electrode collector of projection is that 50 μ m, the occupied area of projection on current collection film surface are 15%, is 51% with respect to the V/V of the electrolyte maintaining part of the possessive volume of negative electrode collector.
In negative electrode collector (D-3), use the Copper Foil (specific area 1.4) that has a plurality of projections on the two sides of thickness direction, this negative electrode collector is made by rolled copper foil is carried out the pattern plating.The pattern plating is to be coated with negative type photoresist on the rolled copper foil of thickness 18 μ m, use accounts for the minus mask that 85% of copper foil surface disposes like that according to the square pattern of 10 μ m, resist film on the Copper Foil is exposed, develops, by electrolysis copper particle is separated out in formed ditch, remove resist then, obtain having the Copper Foil of the projection that trapezoidal shape is arranged on the surface.The cross sectional shape of the thickness direction of projection is as the criterion trapezoidal, and the height of projection is 12 μ m.In addition, the thickness that comprises the negative electrode collector of projection is that 42 μ m, the occupied area of projection on current collection film surface are 15%, is 49% with respect to the V/V of the electrolyte maintaining part of the possessive volume of negative electrode collector.
In negative electrode collector (D-4), use the Copper Foil (specific area 1.4) that has a plurality of projections on the two sides of thickness direction.This negative electrode collector is made by rolled copper foil is carried out the pattern plating.The pattern plating is to be coated with negative type photoresist on the rolled copper foil of thickness 22 μ m, use accounts for the minus mask that 92% of copper foil surface disposes like that according to the square pattern of 10 μ m, resist film on the Copper Foil is exposed, develops, by electrolysis copper particle is separated out in formed ditch, remove resist then, obtain having the Copper Foil of the projection that trapezoidal shape is arranged on the surface.The cross sectional shape of the thickness direction of projection is as the criterion trapezoidal, and the height of projection is 10 μ m.In addition, the thickness that comprises the negative electrode collector of projection is that 42 μ m, the occupied area of projection on current collection film surface are 8%, is 44% with respect to the V/V of the electrolyte maintaining part of the possessive volume of negative electrode collector.
In negative electrode collector (D-5), the foaming metal (thickness 200 μ m, average pore size 100 μ m, the porosity (the electrolyte maintaining part V/V that is equivalent to the negative electrode collector possessive volume) 80%, Mitsubishi's マ テ リ ア Le (strain) is made) that uses copper to form.
In negative electrode collector (D-6), use rolled copper foil (arithmetic average roughness (Ra) 0.12 μ m, thickness 25 μ m, specific area 1.0) with smooth surface.Wherein, Figure 19 is scanning electron microscope (SEM) photo as the major part in the thickness direction cross section of the negative electrode collector 75 of negative electrode collector (D-6).Negative electrode collector 75 does not have projection on the thickness direction surface, in addition, does not have the through hole that connects along thickness direction yet.Therefore, the volume with respect to the electrolyte maintaining part of the collector body possessive volume of negative electrode collector 75 is 0%.In addition, the specific area of the negative pole under the situation of use negative electrode collector (D-6) is 1.1.
In negative electrode collector (D-7), use the Copper Foil (specific area 1.4) that has a plurality of projections on the two sides of thickness direction.This negative electrode collector is made by rolled copper foil is carried out the pattern plating.The pattern plating is to be coated with negative type photoresist on the rolled copper foil of thickness 26 μ m, use accounts for the minus mask that 70% of copper foil surface disposes like that according to the square pattern of 10 μ m, resist film on the Copper Foil is exposed, develops, by electrolysis copper particle is separated out in formed ditch, remove resist then, obtain having the Copper Foil of the projection that trapezoidal shape is arranged on the surface.The cross sectional shape of the thickness direction of projection is as the criterion trapezoidal, and the height of projection is 8 μ m.In addition, the thickness that comprises the negative electrode collector of projection is that 42 μ m, the occupied area of projection on current collection film surface are 30%, is 27% with respect to the V/V of the electrolyte maintaining part of the possessive volume of negative electrode collector.
Use above-mentioned negative electrode collector (D-1)～(D-7), make electrical storage device (D-1)～(D-7) respectively.
At electrical storage device (D-1)～(D-7), carry out the charge/discharge capacity evaluation.Wherein, the positive electrode capacity of electrical storage device (D-1)～(D-7) is 0.08mAh.Use has the negative pole with respect to the reversible capacity of the abundant excess quantity of positive electrode capacity, and capacity of negative plates is abundant bigger than positive electrode capacity.Therefore, the theoretical charge/discharge capacity of these electrical storage devices is 0.08mAh.
The evaluation of charge/discharge capacity is following to be carried out, and, carries out constant current charge-discharge with the current value of 4mA that is, and the charging upper voltage limit is that 3.75V, discharge lower voltage limit are 2.75V, and charging off time and discharge off time were respectively 1 minute.The charging off time is to the time of discharging and beginning next time behind the charging termination.The discharge off time is to the time of charging and beginning next time behind the discharge off.Carry out repeatedly 3 times this discharge and recharge, with the 3rd discharge capacity as charge/discharge capacity.Its evaluation result is as shown in table 7 below.In addition, in table 7, also show the characteristic of the negative electrode collector of each electrical storage device, the rising height of negative electrode collector or the ratio (rising height/cathode film formation thickness, perforation aperture/cathode film formation thickness) of through hole and cathode film formation thickness (4.5 μ m).
[table 7]
Using the surface to have in the electrical storage device (D-1)～(D-4) of the negative electrode collector of projection, up to 44～55%, can keep electrolyte on the negative electrode collector surface with respect to the V/V of the electrolyte maintaining part of the possessive volume of negative electrode collector.Therefore, electrical storage device (D-1)～(D-4) can access the discharge capacity of the high power capacity of design load.
In the electrical storage device (D-5) that uses the negative electrode collector of making by the multiple aperture plasma membrane that has through hole along thickness direction (D-5), can give full play to the electrolyte maintenance effect that negative electrode collector produces, can access high power capacity.In negative electrode collector (D-5) each negative electrode collector in table 7, being 80% with respect to the V/V (porosity) of the electrolyte maintaining part of the possessive volume of negative electrode collector, is the highest, and the electrolyte retention performance is the most excellent.
Have in the electrical storage device (D-6) of atresia matter Copper Foil as negative electrode collector of smooth surface in use, the electrolyte that negative electrode collector produced keeps effect to be almost 0, and discharge capacity is low, is 0.05mAh.
Negative electrode collector (D-7) and negative electrode collector (D-1)～(D-4) compare, V/V with respect to the electrolyte maintaining part of the possessive volume of negative electrode collector is low, be 27%, because rising height deficiency ((rising height/cathode film formation thickness)=1.8) therefore can not obtain sufficient electrolyte and keep effect.Therefore, (D-6) compares with electrical storage device, though the generate output of electrical storage device (D-7) make moderate progress,, low discharge capacity obtains comparing with electrical storage device (D-1)～(D-4).
As shown in the above, in order to improve the charge-discharge characteristic of electrical storage device, the V/V of preferred electrolyte maintaining part is more than 30%.
Except using with positive active material uses the identical anodal duplexer of the embodiment 3 of above-mentioned pi-conjugated polymer, the same with the electrical storage device (D-1) of embodiment 10, making electrical storage device (D-8).
In addition, the same except using with the electrical storage device (D-1) of embodiment 10 with positive active material uses the identical anodal duplexer of the embodiment 4 of above-mentioned free radical polyalcohol, making electrical storage device (D-9).
At electrical storage device (D-8) and (D-9), carry out the charge/discharge capacity evaluation.The evaluation of charge/discharge capacity is to carry out under charging and discharging currents value 4mA, charging upper voltage limit 4.2V and discharge lower voltage limit 2.75V, charging off time and discharge off time are respectively 1 minute condition.The charging off time is to the time of discharging till beginning next time behind the charging termination.Carry out repeatedly 3 times this discharge and recharge, with the 3rd discharge capacity as charge/discharge capacity.
Resulting charge/discharge capacity is 0.14mAh in electrical storage device (D-8), is 0.08mAh in electrical storage device (D-9), can access the high power capacity of design capacity.In any case,, electrolyte can be remained in the negative electrode collector up to 55% with respect to the V/V of the electrolyte maintaining part of the possessive volume of negative electrode collector.
The industry utilizability
Electrical storage device of the present invention has high output, high power capacity and excellent repeated charge characteristic, therefore, is suitable for the power supply, uninterrupted power source of transporting equipment, electric/electronic apparatus etc. etc. In transporting equipment, can list such as hybrid vehicle etc. In electric/electronic apparatus, can list such as mobile communicating equipment, portable equipment etc.
Claims (25)
1. electrical storage device, it comprises:
Positive electrode collector,
Be disposed on the above-mentioned positive electrode collector and contain can reversibly adsorb at least with the positive pole of the anionic positive active material of desorb,
Negative electrode collector and
Be disposed on the above-mentioned negative electrode collector and, it is characterized in that in fact by occlusion reversibly with emit the negative pole that the negative electrode active material of lithium ion forms,
Above-mentioned negative electrode active material is to be selected from least a in the alloy of silicon, siliceous alloy, silicon compound, tin, stanniferous and the tin compound,
Above-mentioned negative pole is that thickness is the following films of 10 μ m.
2. electrical storage device according to claim 1, the capacity of the unit are of above-mentioned negative pole are 0.2～2.0mAh/cm
2
3. electrical storage device according to claim 1, the thickness of above-mentioned positive pole are more than 5 times of thickness of above-mentioned negative pole.
4. electrical storage device according to claim 1, the specific area of above-mentioned negative pole are more than 5.
5. electrical storage device according to claim 1, the specific area of above-mentioned negative electrode collector are more than 5.
6. electrical storage device according to claim 1, the value of the surface roughness Ra of above-mentioned negative electrode collector are that the thickness with above-mentioned negative pole is identical or than its big value.
7. electrical storage device according to claim 1, occlusion in advance has lithium in above-mentioned negative electrode active material.
8. electrical storage device according to claim 1, the occlusion lithium carries out mechanically in above-mentioned negative electrode active material.
9. electrical storage device according to claim 1, when above-mentioned electrical storage device discharged and recharged, the SOC of above-mentioned negative pole was 20%～95%.
10. electrical storage device according to claim 1, above-mentioned negative electrode active material are silicon.
11. electrical storage device according to claim 1, above-mentioned negative electrode active material are silicon nitride or silicon-oxygen nitride.
12. electrical storage device according to claim 1, above-mentioned silicon compound are by formula SiO
xThe Si oxide of expression, wherein 0＜x＜2.
13. electrical storage device according to claim 1, above-mentioned positive active material are active carbon.
14. electrical storage device according to claim 1, above-mentioned positive active material are the organic compound of oxidable reduction.
15. electrical storage device according to claim 14, above-mentioned organic compound has free radical in molecule.
16. electrical storage device according to claim 14, above-mentioned organic compound has pi-conjugated electron cloud in molecule.
17. electrical storage device according to claim 1,
Above-mentioned negative electrode collector has the electrolyte maintaining part, and the volume of above-mentioned electrolyte maintaining part is more than 30% of possessive volume of above-mentioned negative electrode collector.
18. electrical storage device according to claim 1,
Above-mentioned negative electrode collector has the electrolyte maintaining part, and the volume of above-mentioned electrolyte maintaining part is more than 50% of possessive volume of above-mentioned negative electrode collector.
19. electrical storage device according to claim 1, above-mentioned negative electrode collector are the multiple aperture plasma membranes that has along a plurality of through holes of thickness direction perforation.
20. electrical storage device according to claim 1,
Above-mentioned negative electrode collector does not have the through hole that connects along thickness direction, and has a plurality of projections on the surface,
The cross sectional shape along the thickness direction of above-mentioned negative electrode collector of above-mentioned projection is trapezoidal or accurate trapezoidal.
21. electrical storage device according to claim 20, the height of above-mentioned projection are more than 2 times of thickness of above-mentioned negative pole.
22. electrical storage device according to claim 20 is formed with the coating that contains negative electrode active material at least a portion of the top ends of above-mentioned projection.
23. a notebook computer, it has the described electrical storage device of claim 1.
24. a hybrid vehicle, it has the described electrical storage device of claim 1.
25. a portable phone, it has the described electrical storage device of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510424822.7A CN105098223A (en) | 2006-11-16 | 2007-11-13 | Electricity storage device |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006310003 | 2006-11-16 | ||
| JP310003/2006 | 2006-11-16 | ||
| JP026245/2007 | 2007-02-06 | ||
| JP043154/2007 | 2007-02-23 | ||
| JP066385/2007 | 2007-03-15 | ||
| JP123275/2007 | 2007-05-08 |
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|---|---|---|---|
| CN201510424822.7A Division CN105098223A (en) | 2006-11-16 | 2007-11-13 | Electricity storage device |
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| CN101536243A true CN101536243A (en) | 2009-09-16 |
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| CNA2007800424844A Pending CN101536243A (en) | 2006-11-16 | 2007-11-13 | Electricity storage device |
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| CN102738515A (en) * | 2011-03-31 | 2012-10-17 | 富士重工业株式会社 | Method of manufacturing lithium ion storage device |
| CN103633361A (en) * | 2012-08-24 | 2014-03-12 | 太阳诱电株式会社 | Electrochemical device |
| CN104412438A (en) * | 2012-06-26 | 2015-03-11 | 三菱自动车工业株式会社 | Secondary cell |
| CN104769692A (en) * | 2012-10-08 | 2015-07-08 | 麦克斯威科技公司 | Electrolyte for three-volt ultracapacitor |
| CN110521040A (en) * | 2017-11-16 | 2019-11-29 | 松下知识产权经营株式会社 | Air cell anode and air cell |
| CN112151795A (en) * | 2020-09-07 | 2020-12-29 | 中国科学院深圳先进技术研究院 | Positive electrode active material, positive electrode, and secondary battery |
| CN114068945A (en) * | 2021-11-17 | 2022-02-18 | 鄂尔多斯市紫荆创新研究院 | Tin alloy cathode target material for preparing thin film lithium battery and preparation method thereof |
| CN114361606A (en) * | 2020-09-28 | 2022-04-15 | 比亚迪股份有限公司 | Pole core, battery and battery module |
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- 2007-11-13 CN CNA2007800424844A patent/CN101536243A/en active Pending
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| CN102738515A (en) * | 2011-03-31 | 2012-10-17 | 富士重工业株式会社 | Method of manufacturing lithium ion storage device |
| CN104412438A (en) * | 2012-06-26 | 2015-03-11 | 三菱自动车工业株式会社 | Secondary cell |
| CN103633361B (en) * | 2012-08-24 | 2016-01-20 | 太阳诱电株式会社 | Electrochemical appliance |
| CN103633361A (en) * | 2012-08-24 | 2014-03-12 | 太阳诱电株式会社 | Electrochemical device |
| CN104769692B (en) * | 2012-10-08 | 2018-02-16 | 麦克斯威科技公司 | Electrolyte for dog days' ultracapacitor |
| US11302488B2 (en) | 2012-10-08 | 2022-04-12 | Ucap Power, Inc. | Carbon surface modification for three-volt ultracapacitor |
| US9715970B2 (en) | 2012-10-08 | 2017-07-25 | Maxwell Technologies, Inc. | Electrolyte for three-volt ultracapacitor |
| US9728342B2 (en) | 2012-10-08 | 2017-08-08 | Maxwell Technologies, Inc. | Coated housing for ultracapacitor |
| CN104769692A (en) * | 2012-10-08 | 2015-07-08 | 麦克斯威科技公司 | Electrolyte for three-volt ultracapacitor |
| US10043615B2 (en) | 2012-10-08 | 2018-08-07 | Maxwell Technologies, Inc. | Electrode porosity for three-volt ultracapacitor |
| US10249448B2 (en) | 2012-10-08 | 2019-04-02 | Maxwell Technologies, Inc. | Carbon surface modification for three-volt ultracapacitor |
| US9679703B2 (en) | 2012-10-08 | 2017-06-13 | Maxwell Technologies, Inc. | Carbon surface modification for three-volt ultracapacitor |
| US10763051B2 (en) | 2012-10-08 | 2020-09-01 | Maxwell Technologies, Inc. | Carbon surface modification for three-volt ultracapacitor |
| CN110521040A (en) * | 2017-11-16 | 2019-11-29 | 松下知识产权经营株式会社 | Air cell anode and air cell |
| CN112151795A (en) * | 2020-09-07 | 2020-12-29 | 中国科学院深圳先进技术研究院 | Positive electrode active material, positive electrode, and secondary battery |
| CN114361606A (en) * | 2020-09-28 | 2022-04-15 | 比亚迪股份有限公司 | Pole core, battery and battery module |
| CN114361606B (en) * | 2020-09-28 | 2023-08-08 | 比亚迪股份有限公司 | Pole core, battery and battery module |
| CN114068945A (en) * | 2021-11-17 | 2022-02-18 | 鄂尔多斯市紫荆创新研究院 | Tin alloy cathode target material for preparing thin film lithium battery and preparation method thereof |
| CN114068945B (en) * | 2021-11-17 | 2023-08-29 | 鄂尔多斯市紫荆创新研究院 | Tin alloy negative electrode target material for preparing thin film lithium battery and preparation method thereof |
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