CN100361331C - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte battery Download PDFInfo
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- CN100361331C CN100361331C CNB2003801026174A CN200380102617A CN100361331C CN 100361331 C CN100361331 C CN 100361331C CN B2003801026174 A CNB2003801026174 A CN B2003801026174A CN 200380102617 A CN200380102617 A CN 200380102617A CN 100361331 C CN100361331 C CN 100361331C
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- electrolyte battery
- electrolyte
- film
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 75
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 17
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 56
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 56
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 43
- 239000000758 substrate Substances 0.000 claims description 40
- 150000003624 transition metals Chemical class 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 229920001721 polyimide Polymers 0.000 claims description 19
- 150000004767 nitrides Chemical class 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 13
- 239000004642 Polyimide Substances 0.000 claims description 10
- 229910013872 LiPF Inorganic materials 0.000 claims description 9
- 101150058243 Lipf gene Proteins 0.000 claims description 9
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims 1
- 229910017464 nitrogen compound Inorganic materials 0.000 claims 1
- 150000002830 nitrogen compounds Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- -1 group III elements Inorganic materials 0.000 abstract description 5
- 229910021480 group 4 element Inorganic materials 0.000 abstract 1
- 229910021478 group 5 element Inorganic materials 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 description 59
- 230000003647 oxidation Effects 0.000 description 58
- 230000015572 biosynthetic process Effects 0.000 description 23
- 239000007789 gas Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 125000004122 cyclic group Chemical group 0.000 description 17
- 230000001351 cycling effect Effects 0.000 description 14
- 230000003252 repetitive effect Effects 0.000 description 14
- 238000002484 cyclic voltammetry Methods 0.000 description 12
- 238000000691 measurement method Methods 0.000 description 12
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 7
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 229910013075 LiBF Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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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
Landscapes
- Cell Electrode Carriers And Collectors (AREA)
Abstract
A nonaqueous electrolyte battery whose electrolyte can be selected from a wider range of materials is disclosed. The nonaqueous electrolyte battery comprises a positive electrode, a negative electrode and a nonaqueous electrolytic solution. At least one of the positive and negative electrodes has a collector which includes a compound containing at least one element selected from the group consisting of transition metal elements, group III elements, group IV elements, and group V elements.
Description
Technical field
The present invention relates to nonaqueous electrolyte battery, especially relate to nonaqueous electrolyte battery with collector body.
Background technology
In the past, carried out the research of relevant electrode active material, electrolyte, separator (separator) and collector body etc. as the research that relates to nonaqueous electrolyte battery.Wherein, many researchs have been carried out for electrode active material, electrolyte and separator.On the other hand, about collector body, the electricity that produces on what is called must be effectively to electrode carries out on the fundamental property of current collection, is limited to metal or semiconductor etc. owing to constitute the material of collector body, so only rest at most in the local research.
As everyone knows, the metal material as the fundamental property that satisfies this collector body necessity for example has Al etc.And, in the prior art, use known to the Al paper tinsel as collector body and the nonaqueous electrolyte battery that formed electrode active material layer on the Al paper tinsel also is.Non-hydrolyte battery is so for example opened in the flat 7-70327 communique open the spy.
The collector body that is made of the Al paper tinsel of above-mentioned prior art has good current collection performance, on the other hand, has so-called because used electrolyte kind and improper situation that characteristic changes.For example dissolved LiPF in use
6The situation of organic electrolyte under, can under the high potential of 6V, use.Yet dissolved LiPF in use
6Under the situation of the organic electrolyte of solute in addition,, be difficult so under high potential, use owing to before and after 3.5V, produce the stripping of collector body.Especially, dissolving LiN (CF
3SO
2)
2Or LiN (C
2F
5SO
2)
2Organic electrolyte in increase because constitute the stripping of the Al of element as collector body, so current collection self is difficult.Its result, under with the situation of Al as collector body, because a large amount of electrolyte that uses difficulty that exists is difficult so expand electrolytical range of choice, this is a problem.
Summary of the invention
An object of the present invention is to provide the nonaqueous electrolyte battery that to expand the electrolyte range of choice.
Another object of the present invention is the collector body that can easily obtain chemical stabilization in above-mentioned non-electrolyte battery.
In order to achieve the above object, found that of the wholwe-hearted research of the present application person contains transition metal by use; With the compound of at least a element in 3 families, 4 families and 5 families collector body, thereby can in multiple electrolyte, obtain good current collection performance as nonaqueous electrolyte battery.
That is, nonaqueous electrolyte battery according to an aspect of the present invention has positive pole, negative pole and nonaqueous electrolytic solution, and the either party's at least of described positive pole and described negative pole collector body comprises and contains transition metal; Compound with at least a element in 3 families, 4 families and 5 families.
In the nonaqueous electrolyte battery aspect this, as noted above, constitute by the collector body that constitutes at least one side who makes positive pole and negative pole and to comprise transition metal, compound with at least a element in 3 families, 4 families and 5 families, the compound that comprises at least a element in transition metal and 3 families, 4 families and 5 families is when having conductivity, because chemically be nonactive, in multiple electrolyte, can obtain having the collector body of stable good current collection performance in wide potential range.In addition, because can under high potential, use for example by (LiN (CF
3SO
2)
2Or LiN (C
2F
5SO
2)
2Use the electrolyte of difficulty in the collector body that constitutes etc. the Al paper tinsel of prior art, so can expand electrolytical range of choice.
Non-electrolyte battery according to an above-mentioned situation is preferably, and at least one element is nitrogen (N) in 3 families of containing in compound, 4 families and 5 families, and compound is an intrusion type nitride.According to constituting in this wise, because intrusion type nitride is chemically stable material, so can easily obtain chemically stable collector body.
In the nonaqueous electrolyte battery aspect above-mentioned one, be preferably, the transition metal that contains in compound is titanium (Ti).According to constituting in this wise, can obtain the chemically stable collector body that constitutes by as intrusion type nitride TiN.Because TiN is as the material that stops metal (barrier metal) to use, so in order to obtain chemically stable collector body, it is unusual preferable material.
In this case, in non-hydrolysis electrolyte, be preferably dissolving (LiN (CF
3SO
2)
2And LiN (C
2F
5SO
2)
2In at least a kind of solute.In such nonaqueous electrolytic solution,, be used so can be used as chemically more stable collector body because the collector body that is made of TiN obtains chemically stable especially performance.
In the nonaqueous electrolyte battery aspect above-mentioned one, be preferably, the transition metal that contains in compound is zirconium (Zr).According to such formation, can obtain the chemically stable collector body that constitutes by ZrN as intrusion type nitride.ZrN can be used as the material that stops metal to use, and in order to obtain chemically stable collector body, it is extraordinary material.
In this case, in nonaqueous electrolytic solution, be preferably dissolving (LiN (CF
5SO
2)
2, LiPF
6And LiBF
4In at least a solute.In such nonaqueous electrolyte,, be used so can be used as chemically more stable collector body because the collector body that is made of ZrN obtains chemically stable especially performance.
In the nonaqueous electrolyte battery aspect above-mentioned one, be preferably, the transition metal that contains in compound is tantalum (Ta).According to such formation, can obtain the chemically stable collector body that constitutes by TaN as intrusion type nitride.Because TaN is that in order to obtain chemically stable collector body, it is extraordinary material as the material that stops metal to use.
In this case, be preferably, nonaqueous electrolytic solution comprises the LiPF of dissolving as solute
6Nonaqueous electrolytic solution.In such nonaqueous electrolytic solution,, be used so can be used as chemically more stable collector body because the collector body that is made of TaN obtains chemically stable especially performance.
In these cases, nonaqueous electrolytic solution also can comprise as the ethylene carbonate of solvent and the mixed solvent of diethyl carbonate.
In above-mentioned nonaqueous electrolyte battery, be preferably, the compound that contains at least a element in transition metal and 3 families, 4 families and 5 families is membranaceous formation.So, be membranaceous formation if contain common compound as at least a element in pulverous transition metal and 3 families, 4 families and 5 families, then because can form, so can be to contain transition metal with metal forming same thickness ground as the collector body that always uses; Be used as collector body with the compound of at least a element in 3 families, 4 families and 5 families.
In this case, be preferably, the compound that contains at least a element in transition metal and 3 families, 4 families and 5 families forms by sputtering method and is membranaceous.Can easily make the compound that contains at least a element in transition metal and 3 families, 4 families and 5 families form membranaceous according to such formation.
In the formation that forms above-claimed cpd membranaceously, be preferably, the compound that contains at least a element in transition metal and 3 families, 4 families and 5 families forms on the film like substrate.According to such formation, because the film like substrate is rich in flexibility, so the collector body that forms on the film like substrate also is rich in flexibility.Can form distortion in view of the above and be easy to electrode for cell.
In this case, the film like substrate is preferably formed by polyimides.According to such formation, can obtain not only flexibility, and the substrate of the also good film like of thermal endurance.
In above-mentioned nonaqueous electrolyte battery, collector body also can be anodal collector body.
In the nonaqueous electrolyte battery aspect above-mentioned one, be preferably, the compound that contains at least a element in transition metal and 3 families, 4 families and 5 families is to be selected from a kind of among TiN, ZrN and the TaN.According to such formation, can obtain as TiN, the ZrN of intrusion type nitride or the chemically stable collector body of TaN formation.Because TiN, ZrN or TaN are as the material that stops metal to use, so in order to obtain chemically stable collector body, it is extraordinary material.
Description of drawings
Fig. 1 is the skeleton diagram that the sputter equipment that uses in the positive electrode collector making shared in the nonaqueous electrolyte battery of embodiment of the invention 1-1～1-5 is shown.
Fig. 2 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of embodiment of the invention 1-1 and the oxidation current.
Fig. 3 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of embodiment of the invention 1-2 and the oxidation current.
Fig. 4 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of embodiment of the invention 1-3 and the oxidation current.
Fig. 5 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of embodiment of the invention 1-4 and the oxidation current.
Fig. 6 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of embodiment of the invention 1-5 and the oxidation current.
Fig. 7 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of comparative example 1-1 and the oxidation current.
Fig. 8 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of comparative example 1-2 and the oxidation current.
Fig. 9 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of comparative example 1-3 and the oxidation current.
Figure 10 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of embodiment of the invention 2-1 and the oxidation current.
Figure 11 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of embodiment of the invention 2-2 and the oxidation current.
Figure 12 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of embodiment of the invention 2-3 and the oxidation current.
Figure 13 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of embodiment of the invention 2-4 and the oxidation current.
Figure 14 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of embodiment of the invention 2-5 and the oxidation current.
Figure 15 illustrates the cyclic voltammetric characteristic curve that concerns between the scanning current potential of the embodiment of the invention 3 and the oxidation current.
Embodiment
Below, specify embodiments of the invention.
(embodiment 1-1～embodiment 1-5)
The making of collector body (positive pole)
At first, with reference to Fig. 1, the formation of the sputter equipment that uses among embodiment 1-1～1-5 is illustrated.The target 3 that this sputter equipment is equipped with vacuum tank 1, the water-cooled rotating cylinder of can be in vacuum tank 1 supporting (drum) 2 with being rotated, is provided with opposed to each other with water-cooled rotating cylinder 2, be used for high frequency power supply with the high frequency electric source 4 of target 3, the Ar conductance that is used for importing Ar gas to vacuum tank 1 in is gone into valve 5a, is used for importing N in vacuum tank 1
2The N of gas
2The vacuum gas discharge valve 6 that conductance is gone into valve 5b and is used to control the vacuum degree of vacuum tank 1.
Here, in the non-electrolyte battery of making embodiment 1-1～1-5 when the shared collector body, as shown in Figure 1, in water-cooled rotating cylinder 2, be provided with in the substrate that constitutes by polyimide film (eastern レ デ ユ Port Application corporate system カ プ ト Application 70V), under the condition shown in the following table 1, on substrate 7, form the TiN film.
Table 1
| The working gas flow | Ar：50(sccm)，N 2：5(sccm) |
| Air pressure | 0.18(Pa) |
| High frequency power | 200(W) |
| Formation time | 180(min) |
With reference to above-mentioned table 1, the formation condition of shared TiN film is working gas (ambiance gas) flow among embodiment 1-1～1-5: Ar gas (50sccm) and the N that constitutes as the N (nitrogen) of 5 family's elements
2Gas (5sccm), air pressure: 0.18Pa, target drops into high frequency power: 200W, formation time: 180min.N (nitrogen) is an example of " at least a elements in 3 families, 4 families and 5 families " of the present invention.
When making the shared collector body of present embodiment 1-1～1-5, make the Ti metal forming person of containing 99.9% the Ti as transition metal (titanium) as target 3, simultaneously, between target 3 and the substrate 7 apart from getting 6cm.Ti (titanium) is an example of " transition metal " of the present invention.The thickness of the substrate 7 that is made of polyimides is got 17.5 μ m, and simultaneously, the TiN thickness that forms on substrate 7 is got 0.3 μ m.
As concrete manufacturing process, at first open in 6 pairs of vacuum tanks shown in Figure 11 of vacuum gas discharge valve and carry out vacuum exhaust.When reaching arrival vacuum degree, go into valve 5a and N by the Ar conductance
2Conductance is gone into valve 5b and is imported Ar gas (50sccm) and N
2Gas (5sccm) is then adjusted the degree of opening of vacuum gas discharge valve 6, obtains the pressure of 0.18Pa.And, by the high frequency power (200W) from high frequency electric source 4 is supplied to target 3 (Ti metal), produce plasma 8.In view of the above, because the atom (Ti) that constitutes target 3 is ejected on the surface of the bombardment by ions target 3 in the plasma 8.Under this state, vow the rotation of A direction by making the water-cooled rotating cylinder 2 that is provided with the substrate 7 that constitutes by polyimide film along arrow, on substrate 7, form TiN film (not shown) with 0.3 μ m thickness.TiN is that " compound " of the present invention reaches an example of " intrusion type thing ".And, substrate 7 and TiN film cut out have the portion of terminal of gathering electricity and 2cm square the flag-shaped of square portion after, by 110 ℃ of following 2 hours dryings in a vacuum, make shared positive electrode collector in the nonaqueous electrolyte battery of implementing 1-1～1-5.
(comparative example 1-1～comparative example 1-3)
The making of collector body (positive pole)
By forming the Al paper tinsel, shared positive electrode collector in the nonaqueous electrolyte battery of making comparative example 1-1～1-3.
(embodiment 1-1～embodiment 1-5, comparative example 1-1～comparative example 1-3)
Secondly, different for the performance of the collector body of embodiment 1-1～1-5 of investigating making as noted above and comparative example 1-1～1-3 and electrolyte combination are carried out cyclic voltammetry measurement method as follows and are measured.
The cyclic voltammetry measurement method is measured
In this cyclic voltammetry measurement method is measured, with the collector body made by the foregoing description 1-1～1-5 and comparative example 1-1～1-3 as the effect utmost point, simultaneously, with to Li metal forming person as to the utmost point (negative pole) and with reference to the utmost point.
As electrolyte, in embodiment 1-1 and comparative example 1-1, use dissolving LiN (CF in ethylene carbonate (EC) and diethyl carbonate (DEC) equal-volume mixed solvent (EC/DEC (1/1))
3SO
2)
2, be modulated into the solution of concentration with 1 mol.
At embodiment 1-2 and comparative example 1-2,, use dissolving LiN (C in EC/DEC (1/1) as electrolyte
2F
5SO
2)
2, be modulated into the solution of concentration with 1 mol.
At embodiment 1-3 and comparative example 1-3,, use dissolving LiPF in EC/DEC (1/1) as electrolyte
6, be modulated into the solution of concentration with 1 mol.
In embodiment 1-4,, use dissolving LiCF in EC/DEC (1/1) as electrolyte
3SO
3, be modulated into the solution of concentration with 1 mol.
At embodiment 1-5,, use dissolving LiBF in EC/DEC (1/1) as electrolyte
4, be modulated into the solution of concentration with 1 mol.
And, by Li constitute with reference to the utmost point as reference electrode (Vvs.Li/Li
+) during to electric potential scanning,, measure the effect utmost point that constitutes by TiN or Al and the oxidation current that constitutes by Li to flowing through between the utmost point by the oxidation reaction that the effect utmost point that is made of TiN or Al causes.In addition, as the electric potential scanning scope, in embodiment 1-1,1-2,1-4,1-5 and comparative example 1-2, take from right current potential～6Vvs.Li/Li
+At embodiment 1-3, take from right current potential～5Vvs.Li/Li
+At comparative example 1-1, take from right current potential～4.7Vvs.Li/Li
+At comparative example 1-3, get 3Vvs.Li/Li
+～6Vvs.Li/Li
+It during the scanning beginning oxidation direction (increasing the direction of current potential).Thereafter along reducing direction (reducing the direction of current potential) to electric potential scanning.The result that this cyclic voltammetry measurement method is measured illustrates in Fig. 2～Fig. 9.
Promptly, Fig. 2～Fig. 6 illustrates the cyclic voltammetric performance diagram that concerns between the scanning current potential of embodiments of the invention 1-1～1-5 and the oxidation current respectively, and Fig. 7～Fig. 9 illustrates the cyclic voltammetric performance diagram that concerns between the scanning current potential of comparative example 1-1～1-3 and the oxidation current.
With reference to Fig. 2 and Fig. 3, as the combination by having dissolved LiN (CF
3SO
2)
2The electrolyte that constitutes of EC/DEC and the embodiment 1-1 of the collector body that constitutes by the TiN film, and as combination by having dissolved LiN (C
2F
5SO
2)
2The electrolyte that constitutes of EC/DEC and the embodiment 1-2 of the collector body that constitutes by the TiN film in, distinguish that the oxidation current value reduces in each repetitive cycling.Think that this is because the collector body surface is topped by inert matter in the 1st circulation, is difficult to the cause that oxidation current is flow through in the later mensuration of the 2nd circulation.According to this result, think constitute collector body the TiN film hardly stripping to by having dissolved LiN (CF
3SO
2)
2Or LiN (C
2F
5SO
2)
2The electrolyte that constitutes of EC/DEC in.Distinguish in view of the above, if combination is as the TiN film of collector body with dissolved LiN (CF
3SO
2)
2Or LiN (C
2F
5SO
2)
2The electrolyte that constitutes of EC/DEC, then can under the high potential of 6V, use.
With reference to Fig. 4 as can be known, as the combination by having dissolved LiPF
6The EC/DEC electrolyte and embodiment 1-3 that constitute by the film formed collector body of TiN in, each repetitive cycling, oxidation current increases.Think that this is that each repetitive cycling, the oxidized reacted surface of collector body are amassed and increased owing to pass through the collector body stripping in electrolyte, so the oxidation current that flows through increases.According to this result, can think that the TiN film stripping that constitutes collector body is to by having dissolved LiPF
6The electrolyte that constitutes of EC/DEC in.Wherein, scanning current potential at 4Vvs.Li/Li
+Under the following situation, almost there is not oxidation current to flow through.Think in view of the above by combination as the TiN film of collector body with by having dissolved LiPF
6The electrolyte that constitutes of EC/DEC, can below 4V, use.
With reference to Fig. 5 as can be known, as the combination by having dissolved LiCF
3SO
3The electrolyte that constitutes of EC/DEC and the embodiment 1-4 of the collector body that constitutes by the TiN film in, each repetitive cycling, the oxidation current value reduces, and on the other hand, the oxidation current value of reduction direction (along the direction that reduces current potential) exceeds the oxidation current value of oxidation direction (along the direction that increases current potential).Think this be since by the collector body stripping in electrolyte, and compare during to electric potential scanning in the oxidation direction, become big at the side of reduction direction during the oxidized surface area of collector body, so this flows through oxidation current easily to electric potential scanning.According to this result, think that the TiN film stripping that constitutes collector body is to by having dissolved LiCF
3SO
3The electrolyte that constitutes of EC/DEC in.But, scanning current potential at 4Vvs.Li/Li
+Under the following situation, flow through oxidation current hardly.Think in view of the above, by making up as the TiN film of collector body with by having dissolved LiCF
3SO
3The electrolyte that constitutes of EC/DEC, can below 4V, use.
With reference to Fig. 6 as can be known, as the combination by having dissolved LiBF
4The electrolyte that forms of EC/DEC and the embodiment 1-5 of the collector body that constitutes by the TiN film in, each repetitive cycling, the oxidation current value reduces, yet, if the scanning current potential exceeds 4.5Vvs.Li/Li
+, then when the oxidation current value became the mA magnitude, maximum became greatly 3.4mA.According to this result, think if current potential exceeds 4.5Vvs.Li/Li
+, the easy stripping of TiN film that then constitutes collector body is in the electrolyte that is made of the EC/DEC that has dissolved LiBF4.But, scanning current potential at 4.5Vvs.Li/Li
+Under the following situation, almost there is not oxidation current to flow through.Think in view of the above, by making up as the TiN film of collector body with by having dissolved LiBF
4The electrolyte that constitutes of EC/DEC, can below 4.5V, use.
Secondly, with reference to Fig. 7 as can be known, as combination by having dissolved LiN (CF
3SO
2)
2The electrolyte that constitutes of EC/DEC and the comparative example 1-1 of the collector body that constitutes by the Al paper tinsel in, each repetitive cycling, when the oxidation current value increased, the oxidation current value of reduction direction exceeded the oxidation current value of oxidation direction, and if surpass 3.5Vvs.Li/Li
+, then oxidation current value maximum becomes 18mA, and is very big.According to this result, think that the Al paper tinsel stripping easily that constitutes collector body is to by having dissolved LiN (CF
3SO
2)
2The electrolyte that constitutes of EC/DEC in.Thereby, in combination by as the Al paper tinsel of collector body with by having dissolved LiN (CF
3SO
2)
2The electrolyte that constitutes of EC/DEC in, using more than 3.5V is difficulty.
With reference to Fig. 8 as can be known, as making up by having dissolved LiN (C
2F
5SO
2)
2The electrolyte that constitutes of EC/DEC and the comparative example 1-2 of the collector body that constitutes by the Al paper tinsel in, the oxidation current value of reduction direction exceeds the oxidation current value of oxidation direction.Think that according to this result the Al paper tinsel that constitutes collector body is very easy to stripping to by having dissolved LiN (C
2F
5SO
2)
2The electrolyte that constitutes of EC/DEC in.Because by the stripping collector body, make the surface area of oxidation collector body become big, so each repetitive cycling, the stripping of collector body increases.Thereby think, as the Al paper tinsel of collector body with by having dissolved LiN (C
2F
5SO
2)
2The electrolyte that constitutes of EC/DEC, use is difficult.
Distinguish with reference to Fig. 9, dissolved LiPF as combination
6The electrolyte that constitutes of EC/DEC and the comparative example 1-3 of the collector body that constitutes by the Al paper tinsel in, each repetitive cycling, the oxidation current value reduces.Think that according to this result the Al paper tinsel of formation collector body almost completely not stripping arrives by dissolving LiPF
6The electrolyte that constitutes of EC/DEC in.
Result according to comparative example 1-1～1-3 of Fig. 7～shown in Figure 9 thinks, as the Al paper tinsel of collector body with by having dissolved LiPF
6The electrolyte combination that constitutes of EC/DEC be operable, on the other hand, as the A1 paper tinsel of collector body and dissolved LiN (CF
3SO
2)
2Or LiN (C
2F
5SO
2)
2The electrolyte combination that constitutes of EC/DEC, use is difficult.
In embodiment 1-1～1-5, as noted above, by constitute anodal collector body by the TiN film, when containing Ti (titanium) and having conductivity as the TiN of the N (nitrogen) of 5 family's elements as transition metal, because chemically be nonactive, so in multiple electrolyte, can obtain having the collector body of stable good current collection performance in wide potential range.Because can under high potential, use LiN (CF
3SO
2)
2Or LiN (C
2F
5SO
2)
2Use difficult electrolyte Deng the collector body that constitutes at traditional Al paper tinsel, so can expand electrolytical range of choice.In addition, because TiN is chemically stable intrusion type nitride, can easily obtain chemically stable collector body.
In the shared collector body manufacturing process of the nonaqueous electrolyte battery of embodiment 1-1～1-5, as noted above, use sputter equipment, usually because by form the Ti (titanium) that contains as Powdered transition metal and membranaceously as N (nitrogen) compound of the N (nitrogen) of 5 family's elements, can with as the same thickness ground formation of the metal forming of the collector body that always uses, so can easily use as collector body with the compound that contains transition metal Ti and the 5 element N of family.In addition,, compare, can reduce the impurity level that contains at collector body, and can improve the close property between substrate 7 and the collector body with the situation that on substrate, forms collector body by rubbing method by using sputtering method.In addition, on by the substrate 7 that forms by polyimide film, form collector body, because polyimide film is rich in flexibility, so the collector body that forms also should be rich in flexibility on the substrate 7 that is formed by polyimide film.In view of the above, can form distortion and be easy to positive electrode for nonaqueous electrolyte battery.Because the polyimide film excellent heat resistance, so, also can suppress variation by the substrate 7 of polyimides structure even forming time substrate temperature at the TiN film rises.
(embodiment 2-1～embodiment 2-5)
The making of collector body (positive pole)
In embodiment 2-1～2-5, use the sputtering method same with the foregoing description 1-1～1-5, make the shared positive electrode collector of nonaqueous electrolyte battery of embodiment 2-1～2-5., in embodiment 2-1～2-5, on the substrate 7 (with reference to Fig. 1) that constitutes by polyimide film, under the condition shown in the following table 2, form ZrN film with 0.3 μ m thickness.ZrN is that " compound " of the present invention reaches an example of " intrusion type nitride ".
Table 2
| The working gas flow | Ar：50(sccm)，N 2：3(sccm) |
| Air pressure | 0.18(Pa) |
| High frequency power | 200(W) |
| Formation time | 120(min) |
With reference to above-mentioned table 2, the formation condition of shared ZrN film is working gas (ambiance gas) flow among embodiment 2-1～2-5: by Ar gas (50sccm) and the N that constitutes as the N (nitrogen) of 5 family's elements
2Gas (3sccm), operating pressure: 0.18Pa, target drops into high frequency power 200W, formation time: 120min.In making embodiment 2-1～2-5 when the shared collector body, make the Zr metal forming thing that contains 99.9% the Zr as transition metal (zirconium) as target 3 (with reference to Fig. 1).Zr (zirconium) is " transition metal " of the present invention example.
Secondly, different for the performance of the collector body of embodiment 2-1～2-5 of investigating combination making as noted above and electrolyte, the cyclic voltammetry measurement method of carrying out is as shown below measured.
The cyclic voltammetry measurement method is measured
In present embodiment 2-1～2-5, carry out the cyclic voltammetry measurement method measurement same with the foregoing description 1-1～1-5.That is, by the collector body (positive pole) made with the foregoing description 2-1～2-5 as when acting on the utmost point, with to Li metal forming thing as using to the utmost point (negative pole) and with reference to the utmost point.
As electrolyte, in embodiment 2-1,1-1 is same with the foregoing description, uses dissolving LiN (CF in the equal-volume mixed solvent (EC/DEC (1/1)) of ethylene carbonate (EC) and diethyl carbonate (DEC)
3SO
2)
2, be modulated into and have 1 mole/solution of 1 liter concentration.
At embodiment 2-2,1-2 is same with the foregoing description, dissolves LiN (C as used for electrolyte in EC/DEC (1/1)
2F
5SO
2)
2, be modulated into and have 1 mole/solution of 1 liter concentration.
At embodiment 2-3,1-3 is same with the foregoing description, dissolves LiPF as used for electrolyte in EC/DEC (1/1)
6, be modulated into and have 1 mole/solution of 1 liter concentration.
At embodiment 2-4,1-4 is same with the foregoing description, dissolves LiCF as used for electrolyte in EC/DEC (1/1)
3SO
3, be modulated into and have 1 mole/solution of 1 liter concentration.
At embodiment 2-5,1-5 is same with the foregoing description, dissolves LiBF as used for electrolyte in EC/DEC (1/1)
4, be modulated into and have 1 mole/solution of 1 liter concentration.
In power taking bit scan scope is natural potential～6Vvs.Li/Li
+The time, measure the effect utmost point that constitutes by ZrN and constitute by Li to the utmost point between the oxidation current that flows through.This cyclic voltammetry measurement method measurement result illustrates at Figure 10～Figure 14.
That is, the cyclic voltammetric performance diagram that concerns between the scanning current potential of embodiments of the invention 2-1～2-5 and the oxidation current is shown respectively at Figure 10～Figure 14.
Distinguish with reference to Figure 10, as the combination by having dissolved LiN (CF
3SO
2)
2The electrolyte that constitutes of EC/DEC and the embodiment 2-1 of the collector body that constitutes by the ZrN film in, different with the foregoing description 1-1 (with reference to Fig. 2) that uses the collector body that constitutes by the TiN film, under electronegative potential, use only.That is, in embodiment 2-1, distinguish each repetitive cycling, oxidation current reduces, and on the other hand, is scanning current potential at 4.8Vvs.Li/Li
+Under the above situation, the oxidation current value of reduction direction exceeds the value of the oxidation current of oxidation direction.According to this result, think that the ZrN film stripping that constitutes collector body is to by having dissolved LiN (CF
3SO
2)
2The electrolyte that constitutes of EC/DEC in., scanning current potential at 3.4Vvs.Li/Li
+Under the following situation, almost there is not oxidation current to flow through.Can think that in view of the above combination is as the ZrN film of collector body with by having dissolved LiN (CF
3SO
2)
2The electrolyte that constitutes of EC/DEC, can below 3.4V, use.
Distinguish with reference to Figure 11, as by having dissolved LiN (C
2F
5SO
2)
2The electrolyte that constitutes of EC/DEC and the embodiment 2-2 of the collector body that constitutes by the ZrN film, the collector body the foregoing description 1-2 (with reference to Fig. 3) that is made of the TiN film is same with using, and can use under the high potential of 6V.That is, distinguish in embodiment 2-2, each repetitive cycling, oxidation current reduces.Think according to this result, the ZrN film that constitutes collector body hardly stripping to by being dissolved with LiN (C
2F
5SO
2)
2The electrolyte that constitutes of EC/DEC in.
Distinguish with reference to Figure 12, as the combination by being dissolved with LiPF
6The electrolyte of EC/DEC and the embodiment 2-3 of the collector body that constitutes by the ZrN film different with the foregoing description 1-3 (with reference to Fig. 4) that uses the collector body that constitutes by the TiN film, can under the high potential of 6V, use.That is, distinguish in embodiment 2-3 that each repetitive cycling reduces oxidation current.Think according to this result, the ZrN film that constitutes collector body hardly stripping to being dissolved with LiPF
6The electrolyte that constitutes of EC/DEC in.
Distinguish with reference to Figure 13, making up by being dissolved with LiCF
3SO
3The electrolyte that constitutes of EC/DEC and the embodiment 2-4 of the collector body that constitutes by ZrN in, same with the foregoing description 1-4 (with reference to Fig. 5) that uses the collector body that constitutes by the TiN film, under electronegative potential, use only.That is, distinguish in embodiment 2-4, each repetitive cycling, the oxidation current value reduces, and if scanning voltage surpasses 4.2Vvs.Li/Li
+, when then the oxidation current value became the mA magnitude, maximum reached 1.2mA.Think according to this result, surpass 4.2Vvs.Li/Li if constitute the ZrN film scanning current potential of collector body
+, then easily stripping to by being dissolved with LiCF
3SO
3The electrolyte that constitutes of EC/DEC.But, scanning current potential at 4.2Vvs.Li/Li
+Under the following situation, flow through oxidation current hardly.Think in view of the above, by making up as the Zr film of collector body with by having dissolved LiCF
3SO
3The electrolyte that constitutes of EC/DEC, can below 4.2V, use.
Distinguish with reference to Figure 14, as the combination by being dissolved with LiBF
4The electrolyte that constitutes of EC/DEC and the embodiment 2-5 of the collector body that constitutes by the ZrN film in, different with the embodiment 1-5 (with reference to Fig. 6) that uses the collector body that constitutes by the TiN film, can under the high potential of 6V, use.That is, distinguish 2-5 at embodiment, each repetitive cycling, oxidation current reduces.Think according to this result, the ZrN film that constitutes collector body hardly stripping to being dissolved with LiBF
4The electrolyte that constitutes of EC/DEC in.
In embodiment 2-1～2-5, as noted above, by constitute anodal collector body by the ZrN film, contain as transition metal Zr (zirconium) and as the ZrN of the N (nitrogen) of 5 family's elements when having conductivity, because chemically be not active, so 1-1～1-5 is same with the foregoing description, in the electrolyte of multiple class, can obtain under the scope of broadcasting and TV position, having the collector body of stable good current collection ability.Make the electrolyte LiN (C that uses difficulty in the collector body that constitutes by always Al paper tinsel
2F
5SO
2)
2Under high potential, use and become possibility.In addition, LiPF
6Or LiBF
4Deng the collector body that constitutes by the TiN film using the electrolyte of difficulty also can under high potential, use under the high potential.In view of the above, even under the situation of using the collector body that constitutes by the ZrN film, also can expand electrolytical range of choice.Because ZrN is chemically stable intrusion type nitride, thus can be same with the foregoing description 1-1～1-5, easily obtain chemically stable collector body.
Effect in embodiment 2-1～2-5 manufacturing process is same with the foregoing description 1-1～1-5.That is,, can form and the metal forming same thickness of the collector body of use always, so can easily use ZrN as collector body because by forming the ZrN film by sputtering method.Can reduce the impurity level that contains at collector body, and, the close property between substrate 7 and the collector body can be improved.By forming collector body on the substrate 7 that constitutes by polyimide film, because polyimides is imbued with flexibility, and excellent heat resistance, so can form the positive electrode for nonaqueous electrolyte battery of easy deformation, the variation of the substrate 7 that the substrate temperature rising in the time of simultaneously, can being suppressed at the formation of ZrN film causes.
(embodiment 3)
The making of collector body (positive pole)
At present embodiment 3, use the sputtering method same with the foregoing description 1-1～1-5, make the collector body of the positive pole of using in the nonaqueous electrolyte battery of embodiment 3., at embodiment 3, on the substrate 7 (with reference to Fig. 1) that constitutes by polyimides, under the condition shown in the following table 3, form TaN film with 0.3 μ m thickness.TaN is that " compound " of the present invention reaches an example of " intrusion type nitride ".
Table 3
| The working gas flow | Ar：50(sccm)，N 2：50(sccm) |
| Air pressure | 2.6×10 -1(Pa) |
| High frequency power | 200(W) |
| Formation time | 120(min) |
With reference to above-mentioned table 3, the TaN film formation condition of in embodiment 3, using, working gas (environmental gas) flow: Ar gas (50sccm) and the N that constitutes as the N (nitrogen) of 5 families
2Gas (50sccm), air pressure: 2.6 * 10
-1Pa, target drops into high frequency power: 200W, formation time: 120min.In addition, when the collector body of in making embodiment 3, using, as target 3 (with reference to Fig. 1) with the Ta metal forming thing that contains 99.9% the Ta as transition metal (tantalum).Ta (tantalum) is an example of " transition metal " of the present invention.
Secondly, different for the collector body of investigating the embodiment 3 by making up making as noted above and electrolyte property, the cyclic voltammetry measurement method of carrying out is as shown below measured.
The cyclic voltammetry measurement method is measured
At present embodiment 3, carry out the cyclic voltammetry measurement method measurement same with the foregoing description 1-1～1-5.That is, when the collector body (positive pole) that passes through to make with the foregoing description 3 is as the effect utmost point, use the conduct of Li metal forming thing to the utmost point (negative pole) and with reference to the utmost point.
In embodiment 3, same with the foregoing description 1-3 and embodiment 2-3, use the equal-volume mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (to dissolve LiPF in the EC/DEC (1/1) as electrolyte
6, be modulated into and have 1 mole/solution of 1 liter concentration.
In power taking bit scan scope is natural potential～6Vvs.Li/Li
+The time, measure the effect utmost point that constitutes by TaN and the oxidation current that constitutes by Li to flowing through between the utmost point.The result that this cyclic voltammetry measurement method is measured as shown in figure 15.
Distinguish with reference to Figure 15, as by being dissolved with LiPF
6The electrolyte that constitutes of EC/DEC and the embodiment 3 of the collector body that constitutes by the TaN film in, different with the foregoing description 1-3 (with reference to Fig. 4) that uses the collector body that constitutes by the TiN film, can under the high potential of 6V, use.That is, distinguish in embodiment 3, same with the foregoing description 2-3 (with reference to Figure 12) that uses the collector body that constitutes by the ZrN film, each repetitive cycling, oxidation current reduces.Think according to this result, the TaN film that constitutes collector body hardly stripping to by being dissolved with LiPF
6The electrolyte that constitutes of EC/DEC in.
In embodiment 3, as noted above, by constitute anodal collector body by the TaN film, contain Ta (tantalum) and have conductivity as the TaN of the N (nitrogen) of 5 family's elements as transition metal, simultaneously, because chemically be nonactive, so with being dissolved with LiPF
6Electrolytical situation under, can obtain having the collector body of stable good current collection performance in wide potential range.That is,, make the LiPF that has dissolved high potential use difficulty down by the collector body that constitutes by the TiN film
6Electrolyte under high potential, use and become possibility.Because TaN is chemically stable intrusion type nitride, thus same with the foregoing description 1-1～1-5 and embodiment 2-1～2-5, can easily obtain chemically stable collector body.
The effect of the manufacturing process of embodiment 3 and the foregoing description 1-1～1-5 and embodiment 2-1～2-5 are same.That is, because, can form with the metal forming same thickness ground of the collector body that always uses, so can easily use the TaN film as collector body by forming the TaN film by sputtering method.In addition, can reduce the impurity level that contains at collector body, and, the close property between substrate 7 and the collector body can be improved.By on the substrate 7 that constitutes by polyimides, forming collector body, because polyimide film is rich in flexibility and excellent heat resistance, be easy to positive electrode for nonaqueous electrolyte battery so can form distortion, simultaneously, can be suppressed at the TaN film and form substrate 7 variation that time substrate temperature rises and causes.
Current disclosed embodiment can think that all each points all are illustrations, and without limits.Scope of the present invention is not to illustrate by the scope in the above embodiments but by claim, in addition, also comprises and the scope equivalence of claim and all changes in the scope.
For example, in the foregoing description 1-1～1-5, embodiment 2-1～2-5 and embodiment 3 with contain Ti (titanium), Zr (zirconium) as transition metal, Ta (tantalum) and as TiN film, ZrN film or the TaN film of the N (nitrogen) of 5 family's elements as collector body, yet, the invention is not restricted to this, also can contain at least a element in transition metal and 3 families, 4 families and 5 families.
In the foregoing description 1-1～1-5, embodiment 2-1～2-5 and embodiment 3, the TiN film, ZrN film or the TaN film that use intrusion type thing are as collector body, yet, the invention is not restricted to this, also can use the collector body that constitutes by other intrusion type nitride beyond TiN, ZrN and the TaN.For example enumerate the nitride that contains rare earth element or HfN, VN, NbN, CrN, UN, ThN
2, WN
2, Mo
2N, W
2N, Fe
2N, Mn
3N
2, Co
3N
2And Ni
3N
2Deng as TiN, the intrusion type nitride beyond ZrN and the TaN.
In the foregoing description 1-1～1-5, embodiment 2-1～2-5 and embodiment 3, on the film substrate that constitutes by polyimides, form collector body as film like substrate one example, yet, the invention is not restricted to this, beyond polyimides, also can form collector body on other film substrate.The substrate of the film like that constitutes such as polyethylene, polypropylene, polyethylene terephthalate, polychlorostyrene second diene, polyvinyl chloride, Merlon for example.Wherein, because the film like substrate that is made of polyimides is a flexibility, and the substrate of excellent heat resistance, so preferred especially.
In the foregoing description 1-1～1-5, embodiment 2-1～2-5 and embodiment 3, with the collector body of collector body of the present invention as positive pole, yet, the invention is not restricted to this, also can be used as negative pole and use.Can use collector body of the present invention to positive pole and negative pole both sides.
In the foregoing description 1-1～1-5, embodiment 2-1～2-5 and embodiment 3, on substrate, form collector body with sputtering method, yet, the invention is not restricted to this, if from gas phase the method for base feed, also can use other method.For example, CVD method that can act on the PVD method of vapour deposition method etc. or plasma CVD method etc. etc. forms collector body on substrate.
In the foregoing description 1-1～1-5, embodiment 2-1～2-5 and embodiment 3, with the person that only forms the collector body on the substrate as positive pole, yet, the invention is not restricted to this, under situation about using, preferably on collector body, form positive electrode active material layer as nonaqueous electrolyte battery.Here, in lithium secondary battery (storage battery), use when of the present invention, but the material that can use occlusion and emit lithium is as positive active material.Can be used as the material that positive active material uses, enumerate for example Li of inorganic compound
2FeO
3, TiO
2And V
2O
5Deng the oxide with tunnel-like hole or have TiS
2And MoS
2Metal chalcogenide compound etc. bedded structure.Preferably use as positive active material and to have by Li
xMO
2(0≤x≤1) or Li
yM
2O
4The composite oxides of the composition that (0≤y≤2) illustrate.M in the composition formula is a transition metal.Enumerate LiCoO as composite oxides with above-mentioned composition formula
2, LiMnO
2, LiNiO
2, LiCrO
2And LiMn
2O
4Deng.In addition, also can use a part of replacement of Li side and a part of replacement of transition metal.
Claims (10)
1, a kind of nonaqueous electrolyte battery is characterized in that, has
Anodal,
Negative pole and
Nonaqueous electrolytic solution,
The collector body of described positive pole is made up of the compound that transition metal and nitrogen constituted, and described compound is to form membranaceous intrusion type nitride.
2, nonaqueous electrolyte battery according to claim 1 is characterized in that,
The transition metal that contains in the described compound is a titanium.
3, nonaqueous electrolyte battery according to claim 2 is characterized in that,
Described nonaqueous electrolytic solution comprises and is dissolved with LiN (CF
3SO
2)
2Or LiN (C
2F
5SO
2)
2In the nonaqueous electrolytic solution of at least a solute.
4, a kind of nonaqueous electrolyte battery is characterized in that, has
Anodal,
Negative pole and
Nonaqueous electrolytic solution,
Described positive pole and described negative pole either party's collector body at least comprise and contain zirconium and nitrogen compound, and described compound is an intrusion type nitride.
5, nonaqueous electrolyte battery according to claim 4 is characterized in that,
Described nonaqueous electrolytic solution comprises and is dissolved with LiN (C
2F
5SO
2)
2, LiPF
6, and LiBF
4In the nonaqueous electrolytic solution of at least a solute.
6, a kind of nonaqueous electrolyte battery is characterized in that, has
Anodal,
Negative pole and
Nonaqueous electrolytic solution,
Described positive pole and described negative pole either party's collector body at least are made up of the compound that tantalum and nitrogen constituted, and described compound is an intrusion type nitride.
7, nonaqueous electrolyte battery according to claim 6 is characterized in that,
Described nonaqueous electrolytic solution comprises the LiPF that is dissolved with as solute
6Nonaqueous electrolytic solution.
8, according to each described non-electrolyte battery among the claim 3,5 and 7, it is characterized in that,
Described liquid nonaqueous electrolyte comprises as the ethylene carbonate of solvent and the mixed solvent of diethyl carbonate.
9, according to each described non-electrolyte battery of claim 1～7, it is characterized in that,
Described collector body forms on the film like substrate,
Described film like substrate is made of polyimides.
10, non-electrolyte battery according to claim 1 is characterized in that,
The compound that is made of described transition metal and described nitrogen is to be selected from a kind of among TiN, ZrN and the TaN.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002325507 | 2002-11-08 | ||
| JP325507/2002 | 2002-11-08 | ||
| JP131138/2003 | 2003-05-09 | ||
| JP365386/2003 | 2003-10-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1708868A CN1708868A (en) | 2005-12-14 |
| CN100361331C true CN100361331C (en) | 2008-01-09 |
Family
ID=35581892
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|---|---|---|---|
| CNB2003801026174A Expired - Lifetime CN100361331C (en) | 2002-11-08 | 2003-11-05 | Nonaqueous electrolyte battery |
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| CN (1) | CN100361331C (en) |
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| CN109712820B (en) * | 2019-01-22 | 2020-02-18 | 大连理工大学 | All-transition metal nitride current collector/electrode super capacitor and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547782A (en) * | 1994-03-02 | 1996-08-20 | Dasgupta; Sankar | Current collector for lithium ion battery |
| US6168884B1 (en) * | 1999-04-02 | 2001-01-02 | Lockheed Martin Energy Research Corporation | Battery with an in-situ activation plated lithium anode |
-
2003
- 2003-11-05 CN CNB2003801026174A patent/CN100361331C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547782A (en) * | 1994-03-02 | 1996-08-20 | Dasgupta; Sankar | Current collector for lithium ion battery |
| US6168884B1 (en) * | 1999-04-02 | 2001-01-02 | Lockheed Martin Energy Research Corporation | Battery with an in-situ activation plated lithium anode |
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