CN104247140A - Method for manufacturing electricity storage device and electricity storage device obtained using said method - Google Patents
Method for manufacturing electricity storage device and electricity storage device obtained using said method Download PDFInfo
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- CN104247140A CN104247140A CN201380014715.6A CN201380014715A CN104247140A CN 104247140 A CN104247140 A CN 104247140A CN 201380014715 A CN201380014715 A CN 201380014715A CN 104247140 A CN104247140 A CN 104247140A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
In order to obtain a novel electricity storage device with sufficient battery performance without the need for cumbersome work of predoping an electrode with lithium ions, provided is a method for manufacturing an electricity storage device having an electrolyte layer (3) and a positive electrode (2) and a negative electrode (4) facing each other and sandwiching the electrolyte layer (3). The method is provided with a step in which the positive electrode (2) is formed by steps a through c described hereinafter and a step in which the negative electrode (4) is formed by step d described hereinafter. a. A step in which (X), described hereinafter, is put in a reduced dedoped state. b. A step in which the anions in (Y), described hereinafter, are compensated by counterions. c. A step in which the positive electrode (2) is formed using at least the (X) in a reduced dedoped state, obtained through the above-described step a, and the (Y) in a compensated state, obtained through the above-described step b. d. A step in which the negative electrode (4) is formed using (Z), described hereinafter, in an undoped state. (X) A positive electrode active material in a doped state, the conductivity of which changes according to the insertion and desorption of ions. (Y) An anionic material. (Z) A negative electrode active material capable of ion insertion and desorption.
Description
Technical field
The present invention relates to the manufacture method of electrical storage device and electrical storage device therefrom, specifically, relate to without the need to just there is the manufacture method of the novel electrical storage device of sufficient battery performance and electrical storage device therefrom with lithium ion to the troublesome operation that electrode carries out pre-doping.
Background technology
In recent years, along with progress, the development of the electronic technology of portable computer, mobile phone, portable information terminal (PDA) etc., as the electrical storage device of these electronic equipments, the secondary cell etc. that can repeat discharge and recharge is widely used.In the electrochemical accumulators such as this secondary cell, expect the high capacity of the material used as electrode.
The electrode of electrical storage device contains the active material with the function that can embed deintercalation ion.The embedding deintercalation of the ion of active material is also referred to as so-called doping (doping) and goes doping (dedoping) (or sometimes also referred to as " doping (dope) goes to adulterate (dedope) "), doping is gone to be called doping rate the doping of per unit specific molecular structure, the doping rate of material is higher, more can high capacity as battery.
In electrochemistry, use material that the embedding deintercalation amount of ion is many as electrode, thus as battery energy high capacity.More specifically, in the lithium secondary battery received publicity as electrical storage device, use the negative pole that can embed the graphite-like of deintercalate lithium ions, every 6 carbon atoms embed the lithium ion of deintercalation about 1, can obtain high capacity.
In the middle of this lithium secondary battery, positive pole uses the lithium-containing transition metal oxide of LiMn2O4, cobalt acid lithium and so on, negative pole uses the material with carbon element that can embed deintercalate lithium ions and make two electrodes in the electrolytic solution relatively and the lithium secondary battery obtained has high-energy-density, therefore as above-mentioned electronic equipment electrical storage device and widely used.
But above-mentioned lithium secondary battery is the secondary cell being obtained electric energy by electrochemical reaction, and the speed of above-mentioned electrochemical reaction is little, therefore there is the shortcoming that output density is low.And then, because the internal resistance of secondary cell is high, be therefore difficult to repid discharge, and be also difficult to quick charge.In addition, electrode, electrolyte can be deteriorated because of the electrochemical reaction with discharge and recharge, and therefore life-span, i.e. cycle characteristics are also bad usually.
Therefore, in order to improve the problems referred to above, also there will be a known the lithium secondary battery (see the patent documentation 1) electric conductive polymer of the polyaniline with alloy and so on being used for positive active material.
But, usually have electric conductive polymer as the secondary cell of positive active material be when charging anion doped in electric conductive polymer, this anion adulterates from polymer when discharging anion mobile model.Therefore, negative electrode active material uses when can embed the material with carbon element etc. of deintercalate lithium ions, the rocking chair type secondary cell of the cation mobile model of cation movement between two electrodes when cannot be formed in discharge and recharge.Even if rocking chair type secondary cell have electrolyte content less also can advantage, above-mentioned to have electric conductive polymer then not all right as the secondary cell of positive active material, also cannot make contributions to the miniaturization of electrical storage device.
In order to address this is that, also proposed the secondary cell of cation mobile model, it is without the need to a large amount of electrolyte, and object is the ion concentration in electrolyte is not changed in fact, and improves unit volume, the capacity density of weight, energy density thus.This secondary cell uses the electric conductive polymer with polymer anion of polyvinylsulfonic acid and so on as alloy to form positive pole, and negative pole uses lithium metal (see patent documentation 2).
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 3-129679 publication
Patent documentation 2: Japanese Unexamined Patent Publication 1-132052 publication
Summary of the invention
the problem that invention will solve
But above-mentioned secondary cell is still insufficient at aspect of performance.That is, compared with the lithium secondary battery using the lithium-containing transition metal oxide of LiMn2O4, cobalt acid lithium and so on positive pole, capacity density, energy density are lower.
And positive pole use active carbon and negative pole use pre-doping (adulterated in advance) lithium ion carbon, the double electric layer capacitor that is called as lithium-ion capacitor due to ionic molecule accumulated charge, therefore, it is possible to carry out the discharge and recharge under big current.
But, in above-mentioned lithium-ion capacitor, need pre-doping lithium ion in the carbon of negative pole, this complex operation and expending time in.
The present invention makes in order to the problems referred to above solved in the electrical storage device of existing lithium secondary battery, double electric layer capacitor and so on, a kind of manufacture method of novel electrical storage device and electrical storage device therefrom are provided, described novel electrical storage device without the need to carrying out the troublesome operation of pre-doping to electrode with lithium ion, and has sufficient battery performance.
for the scheme of dealing with problems
First technical scheme of the present invention is a kind of manufacture method of electrical storage device, described electrical storage device has dielectric substrate and the positive pole being clamped and be oppositely arranged and negative pole, and the method is possessed and forms the operation of positive pole by following a ~ c and become the operation of negative pole by following D-shaped.
A. following (X) is made to be in the operation of reducing and going dopant states.
B. by the operation that the anion of counter ion counterionsl gegenions to following (Y) compensates.
C. the reduction obtained by above-mentioned a is at least used to go (X) of dopant states and (Y) of compensating coefficient that obtained by above-mentioned b to form the operation of positive pole.
D. following (Z) of non-dopant states is used to form the operation of negative pole.
(X) positive active material (hereinafter sometimes referred to " positive active material ") of dopant states of the conductivity change because of the embedding deintercalation of ion.
(Y) anionic property material.
(Z) negative electrode active material (hereinafter sometimes referred to " negative electrode active material ") of deintercalation ion can be embedded.
In addition, the second technical scheme of the present invention is the electrical storage device obtained by the manufacture method of above-mentioned electrical storage device.
That is, the present inventor etc. in order to obtain can manufacturing without the need to loaded down with trivial details operation, have high capacity density, high-energy-density novel electrical storage device and conduct in-depth research.In this process, even if be conceived to electrolyte content less also can cation mobile model and the electrical storage device mechanism of the electrical storage device mechanism of rocking chair type and the anion mobile model of output characteristic excellence and dispenser-type (reserve type), centered by the mechanism both them, carry out large quantity research further, and carry out various experiment.As a result, the present inventor etc. have found a kind of manufacture method of electrical storage device, and it can save the troublesome operation of pre-doping lithium ion in the negative poles such as carbon, can manufacture simple, convenient and rapidly, and can obtain the electrical storage device with sufficient battery behavior.
Infer that reason that electrical storage device of the present invention has a high power capacity is because it has the characteristic of above-mentioned rocking chair type and dispenser-type both sides concurrently.
the effect of invention
So, the present invention is the manufacture method of the electrical storage device with dielectric substrate and the positive pole being clamped and be oppositely arranged and negative pole, and the method has the operation of above-mentioned a ~ d.According to this manufacture method, the electrical storage device with sufficient battery performance can be obtained, and the troublesome operation of pre-doping lithium ion in the negative poles such as carbon can be saved, electrical storage device can be manufactured simple, convenient and rapidly.
In addition, if the reduction of above-mentioned a goes dopant states to be by via above-mentioned (X) being gone the operation of operation and the reduction of adulterating to obtain, then the high performance electrical storage device of capacity density excellence can be obtained.
And then, if the reduction of above-mentioned a goes dopant states to be by via being gone by above-mentioned (X) direct-reduction the operation of adulterating to obtain, then can obtain the high performance electrical storage device of capacity density excellence.
If be the electrical storage device obtained by the manufacture method of above-mentioned electrical storage device, then as mentioned above, the high performance electrical storage device that capacity density is more excellent can be obtained.
If be following electrical storage device, then capacity density is more excellent, the positive pole of described electrical storage device is at least formed by above-mentioned (X) and (Y) and negative pole contains above-mentioned (Z), (X) of positive pole goes dopant states for reduction, and the anion counter ion counterionsl gegenions being fixed on (Y) in positive pole compensate, (Z) of negative pole is the state of non-doping treatment.
Accompanying drawing explanation
Fig. 1 illustrates the cutaway view of the structure of the electrical storage device obtained by the manufacture of electrical storage device, and the state at assembling initial stage is shown especially.
Embodiment
Be described in detail to embodiments of the present invention below, but the following explanation recorded is an example of embodiments of the present invention, the present invention is not limited to following content.
The manufacture method of electrical storage device of the present invention as previously mentioned, for having the manufacture method of the electrical storage device of dielectric substrate and the positive pole being clamped and be oppositely arranged and negative pole, the method is possessed and forms the operation of positive pole by following a ~ c and become the operation of negative pole by following D-shaped.
A. following (X) is made to be in the operation of reducing and going dopant states.
B. by the operation that the anion of counter ion counterionsl gegenions to following (Y) compensates.
C. the reduction obtained by above-mentioned a is at least used to go (X) of dopant states and (Y) of compensating coefficient that obtained by above-mentioned b to form the operation of positive pole.
D. following (Z) of non-dopant states is used to form the operation of negative pole.
(X) positive active material of dopant states of the conductivity change because of the embedding deintercalation of ion.
(Y) anionic property material.
(Z) negative electrode active material of deintercalation ion can be embedded.
Then, the feature of the electrical storage device obtained by above-mentioned manufacture method is, as shown in Figure 1, it has dielectric substrate 3 and the positive pole 2 being clamped and be oppositely arranged and negative pole 4, positive pole 2 is at least formed by above-mentioned (X) and (Y), negative pole 4 is containing above-mentioned (Z), (X) of positive pole 2 goes dopant states for reduction, and the anion counter ion counterionsl gegenions being fixed on (Y) in positive pole 2 compensate, (Z) of negative pole 4 is the state of non-doping treatment.
For (X) ~ (Z), next coming in order are described.
In addition, in FIG, positive pole 2 and dielectric substrate 3 represent containing ion (grey parts).
< is about positive active material (X) >
The positive active material of dopant states that above-mentioned (X) is the embedding deintercalation because of ion and conductivity change, include, for example out: polyacetylene, polypyrrole, polyaniline, polythiophene, poly-furans, poly-selenophen, polyisothianaphthene, polyphenylene sulfide, polyphenylene oxide, poly-Azulene, poly-(3,4-ethyldioxythiophene) etc. electric conductive polymer class material, or the carbon-based material such as coalescence benzene, graphite, carbon nano-tube, carbon nano-fiber, Graphene.Particularly preferably use the polyaniline that electrochemistry capacitance is large or polyaniline derivative.Usually, electric conductive polymer class material is in dopant states.
As the derivative of above-mentioned polyaniline, include, for example out: the position beyond 4 of aniline has the substituent material such as alkyl, alkenyl, alkoxyl, aryl, aryloxy group, alkylaryl, aryl alkyl, alkoxyalkyl of at least 1.Wherein preferably use: the O-substituted aniline such as o-toluidine, o ethyl aniline, adjacent phenylaniline, o-aminoanisole, O-ethoxyl amine, position substituted aniline between m-toluidine, m-ethyl aniline, m-anisidine, m-oxethyl aniline, a phenylaniline etc.These can be used alone or combine two or more and use.
Manufacture method of the present invention has makes above-mentioned (X) be in the operation of reducing and going dopant states.Going dopant states to obtain this reduction, following 2 kinds of methods can be listed: (i) method by obtaining via the operation making above-mentioned (X) be the operation and reduction of going dopant states; (ii) method by obtaining via above-mentioned (X) direct-reduction being gone the operation of doping.Next coming in order are described.
[method about (i)]
First, the method for above-mentioned (i) has makes (X) for going the operation of dopant states, and this goes dopant states to pass through neutralize (X) alloy of having and obtain.Such as, in and above-mentioned (X) alloy solution in stir, then carry out washing and filtering, can obtain thus (X) of dopant states.Specifically, in order to using tetrafluoro boric acid as the polyaniline of alloy go doping, can enumerate by sodium hydrate aqueous solution stir and in carrying out and method.
Then, the method for (i) has and makes (X) of dopant states be that the operation of dopant states is gone in reduction.Reduction goes dopant states pass through going (X) of dopant states to reduce and obtain.Such as, stirring in the solution going (X) of dopant states to reduce, then carrying out washing and filtering, can obtain thus reducing (X) of dopant states.Specifically can enumerate the method for reducing by being carried out stirring in the methanol aqueous solution of phenylhydrazine by the polyaniline becoming dopant states.
[method about (ii)]
The method of above-mentioned (ii) is by going the operation of dopant states via directly making (X) to be in reduction and obtain reducing the method for doping.Such as, stir in the reductant solution that polypyrrole is reduced, then carry out washing and filtering, can obtain reducing the polypyrrole of dopant states thus.
Carry out as mentioned above, can obtain reducing (X) of dopant states.Then, remove (X) of dopant states by containing this reduction and form positive pole with the material of counter ion counterionsl gegenions to the anionic property material (Y) that anion compensates.
< is about anionic property material (Y) >
Here, as anionic property material (Y), include, for example out: the anionic compound that polymer anion, molecular weight are larger, the anionic compound etc. low to electrolyte dissolubility.Further specifically, preferably use the compound in molecule with carboxyl, particularly as the polycarboxylic acids of polymer due to can also binding agent be doubled as, therefore use preferably.
As polycarboxylic acids, include, for example out: polyacrylic acid, polymethylacrylic acid, polyvinyl benzoic acid, polyallyl benzoic acid, poly-methallyl yl benzoic acid, poly, poly-fumaric acid, polyglutamic acid and poly-aspartate etc., particularly preferably use polyacrylic acid and polymethylacrylic acid.These can be used alone or combine two or more and use.
In electrical storage device of the present invention, when using the polymer such as above-mentioned polycarboxylic acids, think due to this polymer have as binding agent effect and play the effect of alloy, therefore there is the mechanism of rocking chair type, the characteristic improving electrical storage device of the present invention also contributed to some extent.
In manufacture method of the present invention, there is the operation compensating (formation electric neutrality) with the anion of counter ion counterionsl gegenions to anionic property material (Y).Can enumerate and make the carboxylic acid of the compound in molecule with carboxyl be the material of lithium type.Exchange rate to lithium type is preferably 100%, and according to circumstances, exchange rate also can be lower, is preferably 40% ~ 100%.
Relative to 100 weight portion positive active materials (X), above-mentioned anionic property material (Y) is usually with 1 ~ 100 weight portion, preferably 2 ~ 70 weight portions, the scope use most preferably being 5 ~ 40 weight portions.When anionic property material (Y) is very few relative to the amount of above-mentioned (X), existence cannot obtain the tendency of the electrical storage device of energy density excellence, even and if anionic property material (Y) is too much relative to the amount of above-mentioned (X), also there is the tendency that cannot obtain the high electrical storage device of energy density.
< is about positive pole >
The positive pole of manufacture method of the present invention is formed as follows.Such as, the aqueous solution is made by water-soluble for above-mentioned anionic property material (Y), add the binding agent of the conductive auxiliary agent or vinylidene fluoride and so on of positive active material (X) and the conductive carbon black that depends on the needs and so on wherein, make it fully disperse to prepare paste.After being coated with on the current collector, evaporate the water, pellet electrode can be obtained with the form of the complex on the current collector with the layer of the mixture of X composition and Y composition (with the conductive auxiliary agent depended on the needs and binding agent) thus.
In the positive pole formed as mentioned above, anionic property material (Y) configures with the form of the layer of the mixture with X composition, is therefore fixed in positive pole.
Above-mentioned positive pole is made up of the complex at least being formed by (X) and (Y), is preferably formed to the sheet of Porous.The thickness of usual positive pole is preferably 1 ~ 500 μm, more preferably 10 ~ 300 μm.
The thickness of above-mentioned positive pole can obtain as follows: use the dial gauge (the rugged making of tail is manufactured) that front end geometry is the flat board of diameter 5mm to measure positive pole, electrode surface is obtained to the average of the measured value of 10, obtain thus.When arranging positive pole (porous layer) on the current collector and carried out Composite, measure the thickness of this compound compound as described above, obtain the average of measured value, the thickness deducting collector body calculates, and can obtain the thickness of positive pole thus.
< is about dielectric substrate >
The dielectric substrate of manufacture method of the present invention is made up of electrolyte, such as, preferably make the sheet material that electrolyte is impregnated into sheet material in slider, is formed by solid electrolyte.The sheet material formed by solid electrolyte itself can double as slider.
Above-mentioned electrolyte is made up of the material containing solute and the solvent depended on the needs and various additive.As this solute, such as, preferably use metal ions such as lithium ions and be the material that counter ion counterionsl gegenions, sulfonate ion, perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, hexafluoro arsenic ion, two (trifluoromethane sulfonyl group) imide ionic, two (pentafluoroethane sulfonyl) imide ionic, the halogen ion be suitable for is formed by combining to it.Therefore, as this electrolytical object lesson, LiCF can be listed
3sO
3, LiClO
4, LiBF
4, LiPF
6, LiAsF
6, LiN (SO
2cF
3)
2, LiN (SO
2c
2f
5)
2, LiCl etc.
As the solvent used as required, such as, can use at least a kind of nonaqueous solvents in carbonates, nitrile, amide-type, ethers etc., i.e. organic solvent.As the object lesson of this organic solvent, can list: ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, acetonitrile, propionitrile, N, N '-dimethylacetylamide, METHYLPYRROLIDONE, dimethoxy-ethane, diethoxyethane, gamma-butyrolacton etc.These can be used alone or combine two or more and use.In addition, sometimes the material being dissolved with solute is in a solvent called " electrolyte ".
In addition, in the present invention, as mentioned above, slider can be used in a variety of manners.As above-mentioned slider, as long as can prevent from being clamped and electrical short between the positive pole of provided opposite and negative pole and then electrochemical stability, ion permeability are large, the porous chips with the insulating properties of mechanical strength to a certain degree.Therefore, as the material of above-mentioned slider, the porous film such as preferably make paper using, nonwoven fabrics, being formed by resins such as polypropylene, polyethylene, polyimides.These can be used alone or combine two or more and use.
< is about negative pole >
As the negative pole in electrical storage device of the present invention, the negative electrode active material (Z) that can embed deintercalation ion is used to be formed.As above-mentioned negative electrode active material (Z), the material with carbon element, transition metal oxide, silicon, tin etc. of deintercalate lithium ions when being preferably used in redox, can be embedded.In addition, in the present invention, " use " refer to except comprise only use this formation material situation except, also comprise the situation this formation material and other being formed combination of materials and use, usually, other usage rates forming material are set smaller than 50 % by weight of this formation material.
In addition, the thickness of negative pole is preferably as the criterion with the thickness of positive pole.
< is about the making > of electrical storage device
Use above-mentioned material, based on Fig. 1, the making of electrical storage device is described.In addition, the assembling of battery is preferably carried out in glove box, under the non-active gas atmosphere such as ultra-high purity argon gas.
In FIG, as the collector body (1,5 of Fig. 1) of positive pole 2 and negative pole 4, metal forming, the wire netting of nickel, aluminium, stainless steel, copper etc. is suitably used.Then, on this collector body 1,5, connect the electric current taking-up splicing ear (ear electrode, not shown) of positive pole and negative pole with spot welding machine and use.
Then, vacuumize is carried out to positive pole 2 and collector body 1.Afterwards, in the glove box of-100 DEG C, the hard carbon electrode of non-dopant states is pressed on stainless steel wire mesh, make the complex of negative pole 4 and collector body 5.
In glove box, clamp slider (not shown) between this positive pole 2 and negative pole 4, in the laminated cell of they threes through sealing, the position of adjustment slider, makes positive pole 2 correct relative with negative pole 4 and is not short-circuited.
After positive pole and negative pole are with ear's configuration sealant, reserve electrolyte inlet a little, carry out the heat-sealing of ear electrode part.Then, draw the battery electrolyte of ormal weight with micropipettor, inject ormal weight from the electrolyte inlet of laminated cell.Finally with heat-sealing, frit seal is carried out to the electrolyte inlet on laminated cell top, complete electrical storage device of the present invention (laminated cell).
As electrical storage device of the present invention, except above-mentioned laminated cell, also can be formed as the various shapes such as film-type, sheet type, square, cylinder type, buttonhole type.In addition, as the anode electrode size of electrical storage device, if laminated cell, then 1 limit is preferably 1 ~ 300mm, is particularly preferably 10 ~ 50mm, and the electrode size of negative pole is preferably 1 ~ 400mm, is particularly preferably 10 ~ 60mm.The electrode size of negative pole is preferably slightly larger than anode electrode size.
According to the manufacture method of electrical storage device of the present invention, the negative pole of the pre-doping process not needing lithium can be used, can the high performance electrical storage device of the capacity density of manufacturer's active material weight, the capacity density excellence of unit anode volume easily.
As the discharge and recharge mechanism of electrical storage device of the present invention, can imagine as follows: the anionic property material (Y) belonging to polymer is used as binding agent, and this binding agent self also plays the effect of alloy, there is rocking chair type mechanism in local.That is, though not yet accurately understand, can imagine and there is following rocking chair type mechanism: when discharging, the cations such as lithium ion move from negative pole to positive pole, when charging, cation moves from positive pole to negative pole.
Embodiment
Below embodiment is described.But the present invention is not limited to these embodiments.
First, before making the electrical storage device as embodiment, prepare following shown each composition.
The preparation of positive active material (X) of the dopant states of conductivity change [because of the embedding deintercalation of ion]
As positive active material (X), prepare the conductive polyaniline powder using tetrafluoro boric acid as alloy as follows.
To be equipped with ion exchange water 138g 300mL capacity glass beaker in add tetrafluoroborate solution (Wako Pure Chemical Industries, Ltd. manufacture, the special grade chemical) 84.0g (0.402 mole) of 42 % by weight concentration, while add aniline 10.0g (0.107 mole) wherein with magnetic stirrer limit.When just adding aniline in tetrafluoroborate solution, aniline disperses with the form of oily drop in tetrafluoroborate solution, then, water-soluble within several minutes, forms even and transparent aniline-water solution.Use low temperature thermostat bath that the aniline-water solution so obtained is cooled to less than-4 DEG C.
Then, manganese dioxide powder (Wako Pure Chemical Industries, Ltd.'s manufacture, 1 grade of reagent) 11.63g (0.134 mole) as oxidant is repeatedly joined in above-mentioned aniline-water solution on a small quantity, makes the temperature of the mixture in beaker be no more than-1 DEG C.By so adding oxidant in aniline-water solution, aniline-water solution is changed to immediately blackish green.Then, when continuing to stir a moment, start to generate cyan solid.
Operation like this, after adding oxidant with 80 minutes, limit cooling is containing the reactant mixture of the product generated to some extent, and limit stirs 100 minutes further.Then, use Buchner funnel and inhale bottle, with No.2 (manufacture of ADVANTEC company) filter paper, suction filtration being carried out to gained solid, obtain powder.In the tetrafluoroborate solution of about 2 moles/L, used by this powder magnetic stirring apparatus to carry out stirring, washing.Then, stir in acetone, wash for several times, filtration under diminished pressure is carried out to it.By the vacuumize 10 hours under room temperature (25 DEG C) of gained powder, obtain conductive polyaniline (hereinafter referred to as " the conductive polyaniline ") 12.5g using tetrafluoro boric acid as alloy thus.This conductive polyaniline is bright-coloured green powder.
[conductivity of conductive polyaniline powder]
After being pulverized above-mentioned conductive polyaniline powder 130mg with agate mortar, use infrared spectrum measurement KBr tablet former, at the vacuum under pressure press molding 10 minutes of 75MPa, obtain the disk of the conductive polyaniline of thickness 720 μm.The conductivity of the above-mentioned disk recorded in based on 4 terminal method conductance measurements of Van der Pauw is 19.5S/cm.
[preparation of anionic property material (Y)]
As the anionic property material (Y) of anion with counter-ions compensate, use polyacrylic acid (Wako Pure Chemical Industries, Ltd.'s manufacture, weight average molecular weight 2.5 ten thousand), add the lithium hydroxide of carboxylate equivalent in aqueous, prepare the even of 4.4 % by weight concentration and the polyacrylic acid aqueous solution of thickness.
[preparation of the negative electrode active material (Z) of deintercalation ion can be embedded]
As negative electrode active material (Z), prepare hard carbon (AIR WATER INC. manufacture, Bellfine LN-0010).
[embodiment 1] (Fig. 1)
< makes conductive polyaniline powder be in the operation > of dopant states
Conductive polyaniline powder by dopant states obtained above is dropped in 2 moles/L sodium hydrate aqueous solution, stir 30 minutes in the removable flask of 3L, go doping by the tetrafluoro boric acid of neutralization reaction to alloy.After being washed by the polyaniline carrying out adulterating till filtrate is neutrality, agitator treating in acetone, uses Buchner funnel and inhales bottle and carry out filtration under diminished pressure, No.2 filter paper obtains the polyaniline powder adulterated.By its at room temperature vacuumize 10 hours, obtain the polyaniline powder going dopant states of brown.
< makes the polyaniline powder of dopant states be in the operation > reducing and go dopant states
Then, in the methanol aqueous solution of phenylhydrazine, drop into the polyaniline powder that this goes dopant states, under agitation carry out reduction treatment in 30 minutes.The color of polyaniline powder becomes grey because of reduction from brown.After reaction, carry out methanol wash, acetone washing, after leaching, at room temperature carry out vacuumize, obtain reducing the polyaniline of dopant states.
[conductivity of the polyaniline powder of dopant states is gone in reduction]
Above-mentioned reduction gone after the polyaniline powder 130mg of dopant states pulverizes with agate mortar, use infrared spectrum measurement KBr tablet former, at the vacuum under pressure press molding 10 minutes of 75MPa, the disk of the polyaniline of dopant states is removed in the reduction obtaining thickness 720 μm.The conductivity of the above-mentioned disk recorded in based on 4 terminal method conductance measurements of Van der Pauw is 5.8 × 10
-3s/cm.
< uses reduction to go (X) of dopant states and above-mentioned (Y) to form the operation > of positive pole
Prepare the polyacrylic acid aqueous solution 21.0g through lithiumation prepared as above-mentioned Y composition.
The reduction of above-mentioned preparation is gone after the polyaniline powder 4g of dopant states and conductive carbon black (Deuki Kagaku Kogyo Co., Ltd manufactures, DENKA BLACK) powder 0.5g mixes, joined in the polyacrylic acid aqueous solution 21.0g of above-mentioned 4.4 % by weight concentration, fully stirred with spatula.With ultrasonic type homogenizer, ultrasonic wave process in 1 minute is implemented to it, obtain the paste with mobility.Further use vacuum suction filter bell-jar (vacuum suction bell) and rotary pump carry out deaeration to this paste.
Use desk-top automatic coating device (TESTER SANGYO CO., LTD. manufacture), utilize the scraper type spreader of band micrometer, solution coating thickness is adjusted to 360 μm, above-mentioned deaeration paste is coated on double electric layer capacitor etching aluminium foil (precious Izumi Ltd. manufactures, 30CB) with the coating speed of 10mm/ second.Then, after at room temperature placing 45 minutes, dry on the hot plate of temperature 100 DEG C.Afterwards, use vacuum press (Kitagawaseiki Co., Ltd.'s manufacture, KVHC), be clamped between the square corrosion resistant plate of 15cm, suppress 5 minutes under temperature 140 DEG C, pressure 1.5MPa, make the polyaniline plate electrode of porous, obtain the complex of positive pole and collector body.
The making > of the material of < electrical storage device
First, at the following material of assembling electrical storage device (lithium secondary battery) front preparation.
As positive pole, use by polyaniline plate electrode obtained above, and as negative pole, use the hard carbon electrode of non-pre-doping lithium ion.In addition, (void content: 55%), these electrodes and slider be vacuumize 5 hours at 100 DEG C in vacuum drier before battery assembling to use as slider the nonwoven fabrics TF40-50 buied from precious Izumi Ltd..Electrolyte uses 1 mole/dm
3liBF4 (the LiBF of concentration
4) ethylene carbonate/dimethyl carbonate solution (manufacture of KISHIDA CHEMICAL Co., Ltd.).
Use the above-mentioned material prepared, the assembling of the laminated cell as electrical storage device (lithium secondary battery) is below shown.In addition, being assembled in glove box, under ultra-high purity argon gas atmosphere of battery is carried out (dew point in glove box :-100 DEG C).
The electrode size of laminated cell positive pole is set to 27mm × 27mm, and negative pole size is set to 29mm × 29mm, slightly larger than anode electrode size.
As the electric current taking-up ear electrode of negative pole, connect the nickel metal forming of thickness 50 μm with spot welding machine and use.As the electric current taking-up ear electrode of positive pole, with spot welding machine, the aluminum metallic foil of thickness 50 μm be connected to the aluminium foil of positive electrode collector and use.Positive pole complex, hard carbon, stainless steel wire mesh and slider as negative pole are put into the glove box of dew point-100 DEG C, hard carbon electrode is pressed on the stainless steel wire mesh of collector body in glove box, make the complex of negative pole and collector body.
In addition, in glove box, slider is clamped between this positive pole and negative pole, they being arranged on has sealed in the laminated cell of this three, and adjust the position of slider, make positive pole and negative pole correct relative and be not short-circuited, after positive pole and negative pole are with ear's configuration sealant, reserve electrolyte inlet a little, carry out the heat-sealing of ear electrode part.Then, draw the battery electrolyte of ormal weight with micropipettor, inject ormal weight from the electrolyte inlet of laminated cell, finally frit seal is carried out to the electrolyte inlet on laminated cell top, complete layer piezoelectric battery with heat-sealing.
For the characteristic of so assembling the lithium secondary battery obtained, battery charging and discharging device (manufacture of Big Dipper electrician Co., Ltd., SD8) is used to carry out with constant current-constant-potential charge/constant current discharge mode.End of charge voltage is set to 3.8V, makes after voltage reaches 3.8V, to carry out the 3.8V constant-potential charge of 2 minutes, afterwards, carry out constant current electric discharge until reach final discharging voltage 2.0V by constant current charge.Charging and discharging currents carries out with 0.18mA.In 15th circulation, gravimetric energy density is 225Wh/kg.
Although give the specific embodiment of the present invention in the above-described embodiments, above-described embodiment is only illustrate, and should not do limited explanation.Can expect those skilled in the art variation clearly of the present invention be included in protection scope of the present invention.
utilizability in industry
The manufacture method of electrical storage device of the present invention can be used as the manufacture method of the electrical storage devices such as lithium secondary battery aptly.In addition, electrical storage device of the present invention can be used in the purposes same with existing secondary cell, such as, can be widely used in the driving power of mobile electronic apparatus, hybrid-electric car, electric automobile, the fuel cell cars etc. such as portable computer, mobile phone, portable information terminal (PDA).
description of reference numerals
1 collector body (positive pole is used)
2 positive poles
3 dielectric substrates
4 negative poles
5 collector bodies (negative pole is used)
Claims (5)
1. the manufacture method of an electrical storage device, it is characterized in that, described electrical storage device has dielectric substrate and the positive pole being clamped and be oppositely arranged and negative pole, and the method is possessed and forms the operation of positive pole by following a ~ c and become the operation of negative pole by following D-shaped:
A. following (X) is made to be in the operation of reducing and going dopant states;
B. by the operation that the anion of counter ion counterionsl gegenions to following (Y) compensates;
C. the reduction obtained by described a is at least used to go (X) of dopant states and (Y) of compensating coefficient that obtained by described b to form the operation of positive pole;
D. following (Z) of non-dopant states is used to form the operation of negative pole;
(X) positive active material of dopant states of the conductivity change because of the embedding deintercalation of ion,
(Y) anionic property material,
(Z) negative electrode active material of deintercalation ion can be embedded.
2. the manufacture method of electrical storage device according to claim 1, wherein, the reduction of described a goes dopant states pass through via described (X) being gone the operation of operation and the reduction of adulterating and obtain.
3. the manufacture method of electrical storage device according to claim 1, wherein, the reduction of described a goes dopant states by obtaining via the operation of being gone by described (X) direct-reduction to adulterate.
4. an electrical storage device, its manufacture method by the electrical storage device according to any one of claims 1 to 3 and obtaining.
5. electrical storage device according to claim 4, it is characterized in that, its positive pole is at least formed by described (X) and (Y) and negative pole contains described (Z), (X) of positive pole goes dopant states for reduction, and the anion counter ion counterionsl gegenions being fixed on (Y) in positive pole compensate, (Z) of negative pole is non-doping treatment state.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012110778A JP2013239304A (en) | 2012-05-14 | 2012-05-14 | Method for manufacturing electricity storage device and electricity storage device obtained by the method |
| JP2012-110778 | 2012-05-14 | ||
| PCT/JP2013/062883 WO2013172221A1 (en) | 2012-05-14 | 2013-05-08 | Method for manufacturing electricity storage device and electricity storage device obtained using said method |
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| CN104247140A true CN104247140A (en) | 2014-12-24 |
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| CN201380014715.6A Pending CN104247140A (en) | 2012-05-14 | 2013-05-08 | Method for manufacturing electricity storage device and electricity storage device obtained using said method |
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| JP (1) | JP2013239304A (en) |
| CN (1) | CN104247140A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702962A (en) * | 2016-01-24 | 2016-06-22 | 北京化工大学 | Positive pole plate of lithium-sulfur battery and preparation method of positive pole plate |
Citations (5)
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|---|---|---|---|---|
| JP2002329495A (en) * | 2001-05-01 | 2002-11-15 | Matsushita Electric Ind Co Ltd | Lithium secondary battery and production process thereof |
| JP2003168436A (en) * | 2001-11-29 | 2003-06-13 | Denso Corp | Positive electrode for lithium battery and lithium battery |
| JP2003297362A (en) * | 2002-03-29 | 2003-10-17 | Asahi Glass Co Ltd | Hybrid type secondary power supply |
| JP2009245921A (en) * | 2008-03-13 | 2009-10-22 | Denso Corp | Electrode for secondary battery, method of manufacturing the same, and secondary battery employing the same |
| CN103765657A (en) * | 2011-06-29 | 2014-04-30 | 日东电工株式会社 | Nonaqueous-electrolyte secondary battery and positive-electrode sheet therefor |
-
2012
- 2012-05-14 JP JP2012110778A patent/JP2013239304A/en active Pending
-
2013
- 2013-05-08 WO PCT/JP2013/062883 patent/WO2013172221A1/en active Application Filing
- 2013-05-08 CN CN201380014715.6A patent/CN104247140A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002329495A (en) * | 2001-05-01 | 2002-11-15 | Matsushita Electric Ind Co Ltd | Lithium secondary battery and production process thereof |
| JP2003168436A (en) * | 2001-11-29 | 2003-06-13 | Denso Corp | Positive electrode for lithium battery and lithium battery |
| JP2003297362A (en) * | 2002-03-29 | 2003-10-17 | Asahi Glass Co Ltd | Hybrid type secondary power supply |
| JP2009245921A (en) * | 2008-03-13 | 2009-10-22 | Denso Corp | Electrode for secondary battery, method of manufacturing the same, and secondary battery employing the same |
| CN103765657A (en) * | 2011-06-29 | 2014-04-30 | 日东电工株式会社 | Nonaqueous-electrolyte secondary battery and positive-electrode sheet therefor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702962A (en) * | 2016-01-24 | 2016-06-22 | 北京化工大学 | Positive pole plate of lithium-sulfur battery and preparation method of positive pole plate |
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| Publication number | Publication date |
|---|---|
| WO2013172221A1 (en) | 2013-11-21 |
| JP2013239304A (en) | 2013-11-28 |
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