US20110129723A1 - All-solid-state lithium secondary battery - Google Patents
All-solid-state lithium secondary battery Download PDFInfo
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- US20110129723A1 US20110129723A1 US12/521,654 US52165408A US2011129723A1 US 20110129723 A1 US20110129723 A1 US 20110129723A1 US 52165408 A US52165408 A US 52165408A US 2011129723 A1 US2011129723 A1 US 2011129723A1
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- United States
- Prior art keywords
- sulfide
- metal salt
- lithium secondary
- solid electrolyte
- water
- Prior art date
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 92
- 239000002184 metal Substances 0.000 claims abstract description 92
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 69
- 150000003839 salts Chemical class 0.000 claims abstract description 66
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 150000001768 cations Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 125000000129 anionic group Chemical group 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 43
- 239000007789 gas Substances 0.000 abstract description 31
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 25
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 15
- 239000008188 pellet Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052976 metal sulfide Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000010494 dissociation reaction Methods 0.000 description 7
- 230000005593 dissociations Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- 229910010945 LiGe0.25P0.75S4 Inorganic materials 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- -1 sulfide ions Chemical class 0.000 description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000006182 cathode active material Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910009311 Li2S-SiS2 Inorganic materials 0.000 description 2
- 229910009433 Li2S—SiS2 Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910009294 Li2S-B2S3 Inorganic materials 0.000 description 1
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910007307 Li2S:P2S5 Inorganic materials 0.000 description 1
- 229910009346 Li2S—B2S3 Inorganic materials 0.000 description 1
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a safe and highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material which can restrain generation of hydrogen sulfide gas.
- all-solid-state lithium secondary batteries are produced, for example, by: forming a pellet of three-layer structure of cathode/solid electrolyte/anode by a powder-molding method, inserting the respective battery into a conventional coin-type battery case or a button type battery case, and sealing the periphery thereof.
- Such all-solid-state lithium secondary batteries tend to have a larger electrochemical resistance and a smaller output current compare to lithium secondary batteries using organic electrolyte solution, because their members constituting the batteries, which are cathode, anode and electrolyte, are all hard solid.
- a material having a high ion conductivity as an electrolyte in order to enhance an output current of an all-solid-state lithium secondary battery.
- Sulfide glasses such as Li 2 S—SiS 2 , Li 2 S—B 2 S 3 , Li 2 S—P 2 S 5 show a high ion conductivity over 10 ⁇ 4 S/cm.
- a material in which a substance such as LiI, Li 3 PO 4 added thereto also show a high ion conductivity of about 10 ⁇ 3 S/cm.
- a method of providing an adsorbent to inside or outside of a battery case to absorb the gas generated inside the battery is proposed.
- hydrogen sulfide gas is absorbed by using adsorbents such as zeolite, silica gel and activated carbon.
- adsorbents such as zeolite, silica gel and activated carbon.
- the adsorbent such as zeolite, silica gel and activated carbon absorb the gas using the surface adsorption, their adsorptive capacity are lost when the surface is covered by a large amount of water or the like.
- a main object of the present invention is to provide a safe and highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material which can restrain generation of hydrogen sulfide gas, in case a large amount of water is entered into a battery case by an accident such as submersion associated with a breakage of the container.
- the present invention provides an all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material, characterized in that the battery has a metal salt M-X comprising a metal element “M” and an anionic part “X” in a battery case thereof, and further characterized in that a metal cation of the metal salt M-X generated by disassociation caused with water can react with a sulfide ion generated by a reaction between the sulfide-based solid electrolyte material and the water.
- the metal cation of the metal salt M-X generated by disassociation caused with water can react with the sulfide ion generated by a reaction between the sulfide-based solid electrolyte material and the water. Accordingly, the present invention can provide a safe and highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material which can restrain generation of hydrogen sulfide gas, in case a large amount of water is entered into a battery case by an accident such as submersion associated with a breakage of the container.
- the metal element “M” of the metal salt M-X is at least one selected from the group consisting of Cd, Sn, Pb, Cu, Hg, Ag, Al, Mn, Zn, Fe and Ni, and that the anionic part “X” of the metal salt M-X is at least one selected from the group consisting of OH, SO 4 and NO 3 .
- the present invention attains an effect of providing a safe and highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material which can restrain generation of hydrogen sulfide gas, in case a large amount of water is entered into a battery case by an accident such as submersion associated with a breakage of the container.
- FIGS. 1A and 1B are a schematic sectional view showing one example of the structure of an all-solid-state lithium secondary battery of the present invention.
- the all-solid-state lithium secondary battery of the present invention uses a sulfide-based solid electrolyte material and is characterized in that the battery has a metal salt M-X comprising a metal element “M” and an anionic part “X” in a battery case thereof, and further characterized in that a metal cation of the metal salt M-X generated by disassociation caused with water can react with a sulfide ion generated by a reaction between the sulfide-based solid electrolyte material and the water.
- the metal cation of the metal salt M-X generated by disassociation caused with water can react with the sulfide ion generated by a reaction between the sulfide-based solid electrolyte material and the water.
- the sulfide-based solid electrolyte material generates hydrogen sulfide (H 2 S) gas when it is contacted to water.
- the hydrogen sulfide (H 2 S) gas firstly dissolves into the water and dissociates to H + and S 2 ⁇ in the water.
- the amount that H + and S 2 ⁇ respectively dissolves into water has a saturated amount, and when the dissolved amount reaches to the saturated amount, hydrogen sulfide (H 2 S) gas is generated into the atmosphere.
- the metal salt M-X is presented in a battery case.
- the metal salt M-X reacts with the water and dissociates therefrom to generate a metal cation.
- the metal cation reacts with the sulfide ion (S 2 ⁇ ).
- S 2 ⁇ sulfide ion
- an M-S metal sulfide
- S 2 ⁇ hydrogen sulfide
- the present invention can provide a safe and highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material which can restrain generation of hydrogen sulfide gas, in case a large amount of water is entered into a battery case by an accident such as submersion associated with a breakage of the container.
- FIG. 1A is a view showing one embodiment of a technical structure of a coin type all-solid-state lithium secondary battery of the present invention.
- an all-solid-state lithium secondary battery 1 comprises a solid electrolyte layer 2 sandwiched between a cathode layer 3 and an anode layer 4 , a spacer 5 is further provided on the outside of the anode layer, and those mentioned are covered by a battery case 6 as a whole and sealed by a resin packing 7 .
- a metal salt 8 is provided in a place inside the battery case 6 where no potential is applied.
- FIG. 1B is a view showing one embodiment of a technical structure of a laminate type all-solid-state lithium secondary battery of the present invention.
- the battery of the present invention when the battery of the present invention is a laminate type, it has a technical structure wherein an all-solid-state lithium secondary battery 1 comprises a solid electrolyte layer 2 sandwiched between a cathode layer 3 and an anode layer 4 , a current collector 9 is further provided on the outside thereof, and those mentioned are covered by a battery case 6 as a whole and sealed.
- a metal salt 8 is provided in a place inside the battery case 6 where no potential is applied.
- the metal salt used in the present invention comprises a metal element “M” and an anionic part “X”, wherein a metal cation of the metal salt M-X generated by dissociation caused with water can react with a sulfide ion generated by a reaction between water and a sulfide-based solid electrolyte material to be explained later.
- the sulfide-based solid electrolyte material is specifically a sulfide-based solid electrolyte material Li-A-S comprising Li, A (A is at least one selected from the group consisting of P, Ge, B, Si and I), and S.
- Li-A-S (sulfide-based solid electrolyte material)+H 2 O ⁇ Li-A-O+H 2 S (1)
- A is at least one selected from the group consisting of P, Ge, B, Si and I).
- the hydrogen sulfide (H 2 S) gas firstly dissolves into water and dissociates to H + and S 2 ⁇ in the water.
- the amount that H + and S 2 ⁇ respectively dissolves into water has a saturated amount, and when the dissolved amount reaches to the saturated amount, hydrogen sulfide (H 2 S) gas is generated into the atmosphere.
- the metal salt M-X is presented in a battery case, and a metal cation is generated by disassociation caused by a reaction between the metal salt M-X and water in case a large amount of water is entered into the battery case.
- a metal cation reacts with the sulfide ion (S 2 ⁇ )
- an M-S metal sulfide
- S 2 ⁇ sulfide ion
- A is at least one selected from the group consisting of P, Ge, B, Si and I. Therefore, the sulfide ion (S 2 ⁇ ) in the water is restrained from reaching to its saturated amount and further, generation of hydrogen sulfide (H 2 S) gas into the atmosphere can be restrained.
- the metal salt M-X is not particularly restricted as long as the metal salt reacts with water to generate a metal cation and the metal cation can react with the sulfide ion (S 2 ⁇ ). It is preferable that the generated substance thereby obtained is a stable solid substance less soluble in water and precipitates therein. By being precipitated as the solid substance mentioned above, the resultant does not disperse in the atmosphere and possible dangers such as a person inhaling the resultant can be strongly restrained. Therefore, a safer and more highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material can be obtained.
- Such metal element “M” of the metal salt M-X is preferably at least one selected from the group consisting of Cd, Sn, Pb, Cu, Hg, Ag, Al, Mn, Zn, Fe and Ni.
- Cd, Sn, Pb, Cu, Hg and Ag are more preferable and Ag, Cu and Sn are especially preferable because they have fast generating rate in generating the precipitate and being low in their environmental burden.
- the part is at least one selected from the group consisting of OH ⁇ , SO 4 2 ⁇ and NO 3 ⁇ .
- SO 4 2 ⁇ and NO 3 ⁇ is more preferable, and NO 3 ⁇ is especially preferable since they have a high dissociation degree.
- the anionic part “X” is preferably OH ⁇ .
- the state of the metal salt used in the present invention is not particularly limited as long as the metal salt has the above-mentioned functions as a metal salt. It is preferable that the metal state is in a state which reacts with water when the water enters into the battery case.
- a metal salt in solid state can be cited.
- a powder state, a pellet state obtained by molding and solidifying the powder or by other means, and a film state can be cited.
- a film state is preferable because it dissolves well into the entered water.
- a producing method of a metal salt in such a film state a method of dropping an aqueous solution of metal salt to a predetermined position and drying it can be cited.
- a position to provide the metal salt is preferably a position which does not contact to a part where potential of a terminal and an electrode such as a cathode or an anode is applied. This is to prevent the metal salt from changing caused with a reaction such as reduction by the potential to the metal salt.
- a position close to a sulfide-based solid electrolyte layer which has a risk of generating much hydrogen sulfide gas when water is entered into the battery case, a position close to the sealed part sealing the battery where the water is likely to enter, and the like are preferable.
- the metal salt can be dissociated no matter where of the battery case the water is entered, the metal cation generated by the dissociation can react with a sulfide ion to precipitate the metal sulfide and the sulfide ion can be fixed. As a result, generation of the hydrogen sulfide gas can be restricted more safely.
- the amount of the metal salt provided in the battery case is not particularly restricted as long as the above-mentioned functions as the metal salt can be retained.
- the amount varies depending on factors such as the amount of the sulfide ion (S 2 ⁇ ) generated when the sulfide-based solid electrolyte material reacts with water, or the state of the metal salt.
- the metal salt is preferably provided in large excess to the sulfur (S) contained in the sulfide-based solid electrolyte layer.
- the anionic part “X” of the metal salt is a monovalent anion, the amount needs to be double of the case when the anionic part “X” of the metal salt is divalent.
- the sulfide-based solid electrolyte layer used in the present invention uses a sulfide-based solid electrolyte material.
- a sulfide-based solid electrolyte material uniaxially-compressed and molded into a pellet form can be cited as an example.
- a solid electrolyte material (Li-A-S) made of Li, A, and S can be cited.
- the “A” of the sulfide-based solid electrolyte material Li-A-S is at least one selected from the group consisting of P, Ge, B, Si and I.
- 70Li 2 S-30P 2 S 5 , LiGe 0.25 P 0.75 S 4 , 80Li 2 S-20P 2 S 5 , and Li 2 S—SiS 2 can be cited.
- 70Li 2 S-30P 2 S 5 is particularly preferable because it has a high ion conductivity.
- a method to produce a sulfide-based solid electrolyte material used in the present invention it is not particularly restricted as long as a desired sulfide-based solid electrolyte material can be obtained.
- a method of vitrifying a material such as a material containing Li and S by a planetary ball mill and heat treating the same can be cited.
- the cathode layer used in the present invention is not particularly limited as long as the layer has a function as a cathode layer.
- Materials used for general all-solid-state lithium secondary batteries can be applied as cathode materials used for the cathode layer.
- a material wherein a cathode active material LiCoO 2 and a solid electrolyte LiGe 0.25 P 0.75 S 4 are mixed and made to a cathode mix can be cited.
- a conductivity auxiliary agent such as an acetylene black, a Ketjen Black and carbon fiber may be contained in the cathode layer in order to improve conductivity.
- a layer thickness of the cathode layer used in the present invention is not particularly restricted.
- a cathode layer having a thickness same to a thickness of a solid electrolyte film used for a general all-solid-state lithium secondary battery may be used.
- the anode layer used in the present invention is not particularly limited as long as the layer has a function as an anode layer.
- Materials used for general all-solid-state lithium secondary batteries can be applied as an anode layer material used for the anode layer.
- an indium foil can be cited.
- a conductivity auxiliary agent such as an acetylene black, a Ketjen Black and carbon fiber may be contained in the anode layer in order to improve conductivity.
- a layer thickness of the anode layer used in the present invention is not particularly restricted.
- An anode layer having a thickness same to a thickness of a solid electrolyte film used for a general all-solid-state lithium secondary battery may be used.
- constituents other than the above-mentioned metal salt, sulfide-based solid electrolyte layer, cathode layer, anode layer, i.e., such as a spacer, a resin packing, a battery case, and a current collector are not particularly restricted and those used in general all-solid-state lithium secondary batteries can be used.
- a spacer a material same as the battery case is preferable and a spacer made of materials such as stainless and aluminum can be cited as examples.
- a resin packing a resin having a low water absorption rate is preferable and an epoxy resin can be cited as an example.
- a metal made is generally used and a battery case made of stainless can be cited as an example.
- a current collector has a function to transmit an electron caused by a reaction.
- the current collector it is not particularly restricted as long as it has conductivity.
- a metal foil of Al, Ni, Ti, or a carbon paper can be cited as an example.
- the current collector used in the present invention may be the one combining the function of the battery case. Specifically, a case of preparing a battery case made of a SUS (stainless steel) and using a part thereof as a current collector can be cited as an example.
- a material such as zeolite, silica gel and activated carbon may be provided inside or outside of the battery case.
- a material such as zeolite, silica gel and activated carbon
- H 2 S hydrogen sulfide
- the generated hydrogen sulfide (H 2 S) gas can be adsorbed. Therefore, a safer and more highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material can be obtained.
- a method for producing an all-solid-state lithium secondary battery of the present invention is not particularly restricted as long as the above-mentioned all-solid-state lithium secondary battery can be obtained.
- the following method of producing a battery cell can be cited: the cathode material, the sulfide-based solid electrolyte material, and the anode material are placed in a molding holder and uniaxial compressed and molded into a pellet form to obtain an all-solid-state lithium secondary battery pellet in pellet state; and next, after an aqueous solution of a metal salt is provided to the predetermined position in the battery case, the all-solid-state lithium secondary battery pellet is provided in the battery case.
- the application of the all-solid-state lithium secondary battery obtained by the present invention is not particularly limited.
- the battery can be used as an all-solid-state lithium secondary battery for an automobile.
- a coin type, a laminate type, a cylindrical type, and a square type can be cited.
- a coin type, a laminate type and a square type is preferable.
- the present invention is not limited to the embodiments described above.
- the embodiments described above are mere illustrative, and those having substantially the same constitution and the same working effect as in the technical idea described in the claims of the present invention are included in the technical scope of the present invention.
- a cathode active material (LiCoO 2 ) and a solid electrolyte material (LiGe 0.25 P 0.75 S 4 ) were mixed by a mass ratio of 7:3 and a cathode mix was prepared.
- This cathode mix of 15 mg and the solid electrolyte material of 200 mg, and an indium foil of 60 mg (thickness 0.2 mm) as an anode were placed in a molding holder and pressed by 5 t/cm 2 to produce an electrode pellet having a diameter of about 10 mm and a thickness of about 1.5 mm.
- cupric nitrate metal salt
- the above-mentioned electrode pellet was placed inside of the coin case and the coin case was sealed by a resin (PP (polypropylene)) to produce a coin cell.
- a resin PP (polypropylene)
- a cathode active material (LiCoO 2 ) and a solid electrolyte material (LiGe 0.25 P 0.75 S 4 ) were mixed by a mass ratio of 7:3 and a cathode mix was prepared.
- This cathode mix of 15 mg and the solid electrolyte material of 200 mg, and an indium foil of 60 mg (thickness 0.2 mm) as an anode were placed in a molding holder and pressed by 5 t/cm 2 to produce an electrode pellet having a diameter of about 10 mm and a thickness of about 1.5 mm.
- cupric nitrate was dropped onto an upper cover for a battery case of laminate case type (made of aluminum) provided with a current collector made of SUS and a part of the inside of a lower cover thereof where no current collector is provided, that is the part where no potential is applied, and dried to precipitate cupric nitrate (metal salt) of about 0.5 g. Further, as the Example was supposed to create a submersion of the battery case at the time of case breakage, a hole of ⁇ 1 mm was made to the upper cover of the laminate case.
- the laminate case was sealed so as the current collector was derived to outside of the battery case. Thereby, a laminate cell was produced.
- a laminate cell was produced in the same manner as in the Example 3 except that the metal salt used in the Example 3 was changed into lead nitrate and its amount precipitated was 1.5 g.
- a coin cell is produced in the same manner as in the Example 1 except that the metal salt used in the Example 1 was not used.
- a laminate cell is produced in the same manner as in the Example 3 except that the metal salt used in the Example 3 was not used.
- the respective all-solid-state lithium secondary battery cells obtained in the Examples 1-4 and the Comparative Examples 1-2 were submersed into water of 30 ml in a 100 ml beaker placed inside of sealed plastic bag.
- the respective hydrogen sulfide level in the plastic bag after one minute from the submersion was subsequently measured with a hydrogen sulfide gas sensor (GBL-HS® manufactured by JIKCO Ltd.) set in the plastic bag. Measured results of the hydrogen sulfide level are shown in Table 1.
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Abstract
A safe and highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material which can restrain generation of hydrogen sulfide gas, in case a large amount of water is entered into a battery case by an accident such as submersion associated with a breakage of the container. An all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material, wherein the battery has a metal salt M-X comprising a metal element “M” and an anionic part “X” in a battery case thereof, and further wherein a metal cation of the metal salt M-X generated by disassociation caused with water can react with a sulfide ion generated by a reaction between the sulfide-based solid electrolyte material and the water.
Description
- The present invention relates to a safe and highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material which can restrain generation of hydrogen sulfide gas.
- With the recent rapid spread of information-related devices and communication devices such as personal computers, video cameras and cellular phones, developments of good secondary batteries, such as lithium secondary batteries, as electric power supply for those devices have been gaining recognition. Further, apart from the technical fields of information-related devices and communication devices, developments of high output and high capacity lithium secondary batteries for electric vehicles and hybrid-power cars as low-emission vehicles have been progressed in other fields such as an automobile industry.
- However, since current lithium secondary batteries commercially-supplied use organic electrolyte solutions which have combustible organic media as solvents, attaching of safety systems to prevent temperature rising against short circuit and improvements in their technical structures and materials to prevent short circuit are required.
- In contrast, since all-solid-state lithium secondary batteries having their batteries made to an all-solid-state by changing liquid electrolytes to solid electrolytes do not use combustible organic solvents therein, their safety systems are simplified. Accordingly, it is thought that such batteries are good in reducing production costs and in enhancing productivity.
- The above-mentioned all-solid-state lithium secondary batteries are produced, for example, by: forming a pellet of three-layer structure of cathode/solid electrolyte/anode by a powder-molding method, inserting the respective battery into a conventional coin-type battery case or a button type battery case, and sealing the periphery thereof. Such all-solid-state lithium secondary batteries tend to have a larger electrochemical resistance and a smaller output current compare to lithium secondary batteries using organic electrolyte solution, because their members constituting the batteries, which are cathode, anode and electrolyte, are all hard solid.
- In light of this, it is preferable to use a material having a high ion conductivity as an electrolyte in order to enhance an output current of an all-solid-state lithium secondary battery. Sulfide glasses such as Li2S—SiS2, Li2S—B2S3, Li2S—P2S5 show a high ion conductivity over 10−4 S/cm. Further, a material in which a substance such as LiI, Li3PO4 added thereto also show a high ion conductivity of about 10−3 S/cm. It is thought that these glasses having sulfide as their main constituent show higher ion conductivities compare to those of oxide glasses because sulfide ions are ions having larger polarization compare to oxide ions and sulfide ions have small electrostatic attractive force with lithium ions.
- However, with batteries using solid electrolyte materials (sulfide-based solid electrolyte materials) which have the above-mentioned sulfide as their main constituent, there is a risk of leaking hydrogen sulfide gas to the outside of their battery cases when water is entered into the battery cases and the gas is generated. As hydrogen sulfide gas has pungent odor, prevention of the gas leakage to the outside of the battery case is desired.
- To respond such desire, a method of providing an adsorbent to inside or outside of a battery case to absorb the gas generated inside the battery is proposed. For example, in the
Patent Document 1, hydrogen sulfide gas is absorbed by using adsorbents such as zeolite, silica gel and activated carbon. However, since the adsorbent such as zeolite, silica gel and activated carbon absorb the gas using the surface adsorption, their adsorptive capacity are lost when the surface is covered by a large amount of water or the like. Therefore, there has been a problem of being incapable in preventing the leakage of hydrogen sulfide gas generated because their adsorptive capacity is lowered when a large amount of water is entered into a battery by an accident such as submersion caused by breakage of the container or being exposed to buckets of rain. - Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 2004-087152
- Patent Document 2: JP-A No. 2004-227818
- Patent Document 3: JP-A No. 2003-151558
- Patent Document 4: JP-A No. 2001-052733
- Patent Document 5: JP-A No. 11-219722
- Patent Document 6: JP-A No. 2001-155790
- The present invention was achieved in view of the above-mentioned problems. A main object of the present invention is to provide a safe and highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material which can restrain generation of hydrogen sulfide gas, in case a large amount of water is entered into a battery case by an accident such as submersion associated with a breakage of the container.
- To attain the above-mentioned object, the present invention provides an all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material, characterized in that the battery has a metal salt M-X comprising a metal element “M” and an anionic part “X” in a battery case thereof, and further characterized in that a metal cation of the metal salt M-X generated by disassociation caused with water can react with a sulfide ion generated by a reaction between the sulfide-based solid electrolyte material and the water.
- According to the present invention, the metal cation of the metal salt M-X generated by disassociation caused with water can react with the sulfide ion generated by a reaction between the sulfide-based solid electrolyte material and the water. Accordingly, the present invention can provide a safe and highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material which can restrain generation of hydrogen sulfide gas, in case a large amount of water is entered into a battery case by an accident such as submersion associated with a breakage of the container.
- In the above-mentioned invention, it is preferable that the metal element “M” of the metal salt M-X is at least one selected from the group consisting of Cd, Sn, Pb, Cu, Hg, Ag, Al, Mn, Zn, Fe and Ni, and that the anionic part “X” of the metal salt M-X is at least one selected from the group consisting of OH, SO4 and NO3. This is because, such “M” and “X” as mentioned above allow a reaction between: the metal cation generated by dissociation of the metal salt M-X in water, and the sulfide ion generated by a reaction between the sulfide-based solid electrolyte material and the water, and the resultant can precipitate as a stable solid substance less likely to be dissolved in water. Further, by being precipitated as the solid substance mentioned above, the resultant does not disperse in the atmosphere and possible dangers such as a person inhaling the resultant can be strongly restrained. Therefore, a safer and more highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material can be obtained.
- The present invention attains an effect of providing a safe and highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material which can restrain generation of hydrogen sulfide gas, in case a large amount of water is entered into a battery case by an accident such as submersion associated with a breakage of the container.
-
FIGS. 1A and 1B are a schematic sectional view showing one example of the structure of an all-solid-state lithium secondary battery of the present invention. -
- 1 All-solid-state lithium secondary battery
- 2 Solid electrolyte layer
- 3 Cathode layer
- 4 Anode layer
- 5 Spacer
- 6 Battery case
- 7 Resin packing
- 8 Metal salt
- 9 Current collector
- Hereinafter, an all-solid-state lithium secondary battery of the present invention will be explained in detail.
- The all-solid-state lithium secondary battery of the present invention uses a sulfide-based solid electrolyte material and is characterized in that the battery has a metal salt M-X comprising a metal element “M” and an anionic part “X” in a battery case thereof, and further characterized in that a metal cation of the metal salt M-X generated by disassociation caused with water can react with a sulfide ion generated by a reaction between the sulfide-based solid electrolyte material and the water.
- According to the present invention, the metal cation of the metal salt M-X generated by disassociation caused with water can react with the sulfide ion generated by a reaction between the sulfide-based solid electrolyte material and the water. The sulfide-based solid electrolyte material generates hydrogen sulfide (H2S) gas when it is contacted to water. The hydrogen sulfide (H2S) gas firstly dissolves into the water and dissociates to H+ and S2− in the water. The amount that H+ and S2− respectively dissolves into water has a saturated amount, and when the dissolved amount reaches to the saturated amount, hydrogen sulfide (H2S) gas is generated into the atmosphere.
- In the present invention, the metal salt M-X is presented in a battery case. When a large amount of water is entered into the battery case, the metal salt M-X reacts with the water and dissociates therefrom to generate a metal cation. The metal cation reacts with the sulfide ion (S2−). As a result, an M-S (metal sulfide) is generated and become a precipitate to fix the sulfide ion (S2−). Therefore, it is possible to restrain the sulfide ion (S2−) in the water from reaching to the saturated amount and to further restrain the generation of the hydrogen sulfide (H2S) gas into the atmosphere. Accordingly, the present invention can provide a safe and highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material which can restrain generation of hydrogen sulfide gas, in case a large amount of water is entered into a battery case by an accident such as submersion associated with a breakage of the container.
- Hereinafter, the all-solid-state lithium secondary battery of the present invention will be explained with a reference to the drawings.
-
FIG. 1A is a view showing one embodiment of a technical structure of a coin type all-solid-state lithium secondary battery of the present invention. As shown inFIG. 1A , when the battery of the present invention is a coin type, it has a technical structure wherein an all-solid-state lithiumsecondary battery 1 comprises asolid electrolyte layer 2 sandwiched between acathode layer 3 and ananode layer 4, aspacer 5 is further provided on the outside of the anode layer, and those mentioned are covered by abattery case 6 as a whole and sealed by aresin packing 7. Ametal salt 8 is provided in a place inside thebattery case 6 where no potential is applied.FIG. 1B is a view showing one embodiment of a technical structure of a laminate type all-solid-state lithium secondary battery of the present invention. As shown inFIG. 1B , when the battery of the present invention is a laminate type, it has a technical structure wherein an all-solid-state lithiumsecondary battery 1 comprises asolid electrolyte layer 2 sandwiched between acathode layer 3 and ananode layer 4, acurrent collector 9 is further provided on the outside thereof, and those mentioned are covered by abattery case 6 as a whole and sealed. Similar to the coin type battery, ametal salt 8 is provided in a place inside thebattery case 6 where no potential is applied. - Hereinafter, the all-solid-state lithium secondary battery will be explained by each structure.
- The metal salt used in the present invention comprises a metal element “M” and an anionic part “X”, wherein a metal cation of the metal salt M-X generated by dissociation caused with water can react with a sulfide ion generated by a reaction between water and a sulfide-based solid electrolyte material to be explained later. The sulfide-based solid electrolyte material is specifically a sulfide-based solid electrolyte material Li-A-S comprising Li, A (A is at least one selected from the group consisting of P, Ge, B, Si and I), and S. Accordingly, generation of hydrogen sulfide gas can be restrained, in case a large amount of water is entered into the battery case by an accident such as submersion associated with a breakage of the container. This is because of the following reasons. Generally, when the sulfide-based solid electrolyte material is in contact with water, a reaction shown in the below formula (1) is caused and hydrogen sulfide (H2S) gas is generated:
-
Li-A-S (sulfide-based solid electrolyte material)+H2O→Li-A-O+H2S (1) - (in the formula, A is at least one selected from the group consisting of P, Ge, B, Si and I).
- In the above-mentioned formula (1), the hydrogen sulfide (H2S) gas firstly dissolves into water and dissociates to H+ and S2− in the water. The amount that H+ and S2− respectively dissolves into water has a saturated amount, and when the dissolved amount reaches to the saturated amount, hydrogen sulfide (H2S) gas is generated into the atmosphere.
- In the present invention, the metal salt M-X is presented in a battery case, and a metal cation is generated by disassociation caused by a reaction between the metal salt M-X and water in case a large amount of water is entered into the battery case. As the metal cation reacts with the sulfide ion (S2−), an M-S (metal sulfide) is generated, become a precipitate and fixes the sulfide ion (S2−) as shown in the below formula (2):
-
Li-A-S (sulfide-based solid electrolyte material)+M-X+H2O→Li-A-O+M-S (metal sulfide)+2H—X (2) - (in the formula, A is at least one selected from the group consisting of P, Ge, B, Si and I). Therefore, the sulfide ion (S2−) in the water is restrained from reaching to its saturated amount and further, generation of hydrogen sulfide (H2S) gas into the atmosphere can be restrained.
- In the present invention, the metal salt M-X is not particularly restricted as long as the metal salt reacts with water to generate a metal cation and the metal cation can react with the sulfide ion (S2−). It is preferable that the generated substance thereby obtained is a stable solid substance less soluble in water and precipitates therein. By being precipitated as the solid substance mentioned above, the resultant does not disperse in the atmosphere and possible dangers such as a person inhaling the resultant can be strongly restrained. Therefore, a safer and more highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material can be obtained. Such metal element “M” of the metal salt M-X is preferably at least one selected from the group consisting of Cd, Sn, Pb, Cu, Hg, Ag, Al, Mn, Zn, Fe and Ni. Among them, Cd, Sn, Pb, Cu, Hg and Ag are more preferable and Ag, Cu and Sn are especially preferable because they have fast generating rate in generating the precipitate and being low in their environmental burden.
- Further, as the anionic part “X” of the metal salt M-X, it is preferable that the part is at least one selected from the group consisting of OH−, SO4 2− and NO3 −. Among them, SO4 2− and NO3 − is more preferable, and NO3 − is especially preferable since they have a high dissociation degree.
- When the metal element “M” is Al, the anionic part “X” is preferably OH−.
- The state of the metal salt used in the present invention is not particularly limited as long as the metal salt has the above-mentioned functions as a metal salt. It is preferable that the metal state is in a state which reacts with water when the water enters into the battery case. For example, a metal salt in solid state can be cited. As the example of the solid state, a powder state, a pellet state obtained by molding and solidifying the powder or by other means, and a film state can be cited. Among them, a film state is preferable because it dissolves well into the entered water. As an example of a producing method of a metal salt in such a film state, a method of dropping an aqueous solution of metal salt to a predetermined position and drying it can be cited.
- A position to provide the metal salt is preferably a position which does not contact to a part where potential of a terminal and an electrode such as a cathode or an anode is applied. This is to prevent the metal salt from changing caused with a reaction such as reduction by the potential to the metal salt.
- Further, a position close to a sulfide-based solid electrolyte layer which has a risk of generating much hydrogen sulfide gas when water is entered into the battery case, a position close to the sealed part sealing the battery where the water is likely to enter, and the like are preferable.
- Still further, it is preferable to provide the metal salt over parts as wide as possible within the battery case. This is to respond to a damage caused to every part of the battery case. Thereby, the metal salt can be dissociated no matter where of the battery case the water is entered, the metal cation generated by the dissociation can react with a sulfide ion to precipitate the metal sulfide and the sulfide ion can be fixed. As a result, generation of the hydrogen sulfide gas can be restricted more safely.
- The amount of the metal salt provided in the battery case is not particularly restricted as long as the above-mentioned functions as the metal salt can be retained. The amount varies depending on factors such as the amount of the sulfide ion (S2−) generated when the sulfide-based solid electrolyte material reacts with water, or the state of the metal salt. Generally, the metal salt is preferably provided in large excess to the sulfur (S) contained in the sulfide-based solid electrolyte layer. Specifically, when the anionic part “X” of the metal salt is a divalent anion in mol ratio to 1 mol, for example, it is preferable to be within the range of: sulfur (S): metal salt=1:1 to 100, more preferable to be within the range of: sulfur (S): metal salt=1:1 to 10, and particularly preferable to be within the range of: sulfur (S): metal salt=1:1 to 5. When the anionic part “X” of the metal salt is a monovalent anion, the amount needs to be double of the case when the anionic part “X” of the metal salt is divalent.
- When the mol ration between the sulfur (S) and the metal salt remains the above-mentioned ranges, it is sufficient for the metal cation generated by dissociation of the metal salt caused with water to fix, as the metal sulfide, the sulfide ion (S2−) generated when the sulfide-based solid electrolyte material reacts with water and dissolves therein. Accordingly, sulfur (S) can be fixed better and generation of the hydrogen sulfide gas can be restrained more safely.
- A sulfide-based solid electrolyte layer used in the present invention will be explained. The sulfide-based solid electrolyte layer used in the present invention uses a sulfide-based solid electrolyte material. Specifically, a sulfide-based solid electrolyte material uniaxially-compressed and molded into a pellet form can be cited as an example.
- In the present invention, as the sulfide-based solid electrolyte material used for the sulfide-based solid electrolyte layer, a solid electrolyte material (Li-A-S) made of Li, A, and S can be cited. The “A” of the sulfide-based solid electrolyte material Li-A-S is at least one selected from the group consisting of P, Ge, B, Si and I. As the specific examples of such sulfide-based solid electrolyte material Li-A-S, 70Li2S-30P2S5, LiGe0.25P0.75S4, 80Li2S-20P2S5, and Li2S—SiS2 can be cited. Among them, 70Li2S-30P2S5 is particularly preferable because it has a high ion conductivity.
- As a method to produce a sulfide-based solid electrolyte material used in the present invention, it is not particularly restricted as long as a desired sulfide-based solid electrolyte material can be obtained. For example, a method of vitrifying a material such as a material containing Li and S by a planetary ball mill and heat treating the same can be cited.
- A cathode layer used in the present invention will be explained. The cathode layer used in the present invention is not particularly limited as long as the layer has a function as a cathode layer. Materials used for general all-solid-state lithium secondary batteries can be applied as cathode materials used for the cathode layer. For example, a material wherein a cathode active material LiCoO2 and a solid electrolyte LiGe0.25P0.75S4 are mixed and made to a cathode mix can be cited. Further, a conductivity auxiliary agent such as an acetylene black, a Ketjen Black and carbon fiber may be contained in the cathode layer in order to improve conductivity.
- A layer thickness of the cathode layer used in the present invention is not particularly restricted. A cathode layer having a thickness same to a thickness of a solid electrolyte film used for a general all-solid-state lithium secondary battery may be used.
- An anode layer used in the present invention will be explained. The anode layer used in the present invention is not particularly limited as long as the layer has a function as an anode layer. Materials used for general all-solid-state lithium secondary batteries can be applied as an anode layer material used for the anode layer. For example, an indium foil can be cited. Further, a conductivity auxiliary agent such as an acetylene black, a Ketjen Black and carbon fiber may be contained in the anode layer in order to improve conductivity.
- A layer thickness of the anode layer used in the present invention is not particularly restricted. An anode layer having a thickness same to a thickness of a solid electrolyte film used for a general all-solid-state lithium secondary battery may be used.
- In the all-solid-state lithium secondary battery of the present invention, constituents other than the above-mentioned metal salt, sulfide-based solid electrolyte layer, cathode layer, anode layer, i.e., such as a spacer, a resin packing, a battery case, and a current collector, are not particularly restricted and those used in general all-solid-state lithium secondary batteries can be used. Specifically, as a spacer, a material same as the battery case is preferable and a spacer made of materials such as stainless and aluminum can be cited as examples. As a resin packing, a resin having a low water absorption rate is preferable and an epoxy resin can be cited as an example. Further, as a battery case, a metal made is generally used and a battery case made of stainless can be cited as an example. Moreover, a current collector has a function to transmit an electron caused by a reaction. As the current collector, it is not particularly restricted as long as it has conductivity. For example, a metal foil of Al, Ni, Ti, or a carbon paper can be cited as an example. Further, the current collector used in the present invention may be the one combining the function of the battery case. Specifically, a case of preparing a battery case made of a SUS (stainless steel) and using a part thereof as a current collector can be cited as an example.
- In the present invention, as an adsorbent, a material such as zeolite, silica gel and activated carbon may be provided inside or outside of the battery case. Thereby, when hydrogen sulfide (H2S) gas is generated by a small amount of water, small to the extent that dissociation of the metal salt of the present invention would not be caused, such as in a case when the battery is placed under a highly-humid environment and moisture presented in the atmosphere enters into the battery case, the generated hydrogen sulfide (H2S) gas can be adsorbed. Therefore, a safer and more highly-reliable all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material can be obtained.
- A method for producing an all-solid-state lithium secondary battery of the present invention is not particularly restricted as long as the above-mentioned all-solid-state lithium secondary battery can be obtained. For example, the following method of producing a battery cell can be cited: the cathode material, the sulfide-based solid electrolyte material, and the anode material are placed in a molding holder and uniaxial compressed and molded into a pellet form to obtain an all-solid-state lithium secondary battery pellet in pellet state; and next, after an aqueous solution of a metal salt is provided to the predetermined position in the battery case, the all-solid-state lithium secondary battery pellet is provided in the battery case.
- The application of the all-solid-state lithium secondary battery obtained by the present invention is not particularly limited. For example, the battery can be used as an all-solid-state lithium secondary battery for an automobile.
- As an example of the all-solid-state lithium secondary battery obtained in the present invention, a coin type, a laminate type, a cylindrical type, and a square type can be cited. Among them, a coin type, a laminate type and a square type is preferable.
- The present invention is not limited to the embodiments described above. The embodiments described above are mere illustrative, and those having substantially the same constitution and the same working effect as in the technical idea described in the claims of the present invention are included in the technical scope of the present invention.
- Hereinafter, the present invention is explained in more detail by reference to the Examples.
- A cathode active material (LiCoO2) and a solid electrolyte material (LiGe0.25P0.75S4) were mixed by a mass ratio of 7:3 and a cathode mix was prepared. This cathode mix of 15 mg and the solid electrolyte material of 200 mg, and an indium foil of 60 mg (thickness 0.2 mm) as an anode were placed in a molding holder and pressed by 5 t/cm2 to produce an electrode pellet having a diameter of about 10 mm and a thickness of about 1.5 mm.
- Next, an aqueous solution of cupric nitrate was dropped onto the end part of the inner side of an upper cover for a battery case of coin case type (made of SUS) and dried to precipitate cupric nitrate (metal salt) of about 0.5 g. Further, as the Example was supposed to create a submersion of the battery case at the time of case breakage, a hole of
φ 1 mm was made to the upper cover of the coin case. - The above-mentioned electrode pellet was placed inside of the coin case and the coin case was sealed by a resin (PP (polypropylene)) to produce a coin cell.
- A cathode active material (LiCoO2) and a solid electrolyte material (LiGe0.25P0.75S4) were mixed by a mass ratio of 7:3 and a cathode mix was prepared. This cathode mix of 15 mg and the solid electrolyte material of 200 mg, and an indium foil of 60 mg (thickness 0.2 mm) as an anode were placed in a molding holder and pressed by 5 t/cm2 to produce an electrode pellet having a diameter of about 10 mm and a thickness of about 1.5 mm.
- Next, an aqueous solution of cupric nitrate was dropped onto an upper cover for a battery case of laminate case type (made of aluminum) provided with a current collector made of SUS and a part of the inside of a lower cover thereof where no current collector is provided, that is the part where no potential is applied, and dried to precipitate cupric nitrate (metal salt) of about 0.5 g. Further, as the Example was supposed to create a submersion of the battery case at the time of case breakage, a hole of
φ 1 mm was made to the upper cover of the laminate case. - After the above-mentioned electrode pellet was placed inside of the laminate case, the laminate case was sealed so as the current collector was derived to outside of the battery case. Thereby, a laminate cell was produced.
- A laminate cell was produced in the same manner as in the Example 2 except that a solid electrolyte material was changed to 70Li2S-30P2S5 (obtained by following to the method disclosed in JP-A No. 2005-228570, wherein Li2 and P2S5 were vitrified by a planetary ball mill with a mole ratio of Li2S:P2S5=70:30 and then by heat treated) and an amount of cupric nitrate precipitated was made to 1.0 g.
- A laminate cell was produced in the same manner as in the Example 3 except that the metal salt used in the Example 3 was changed into lead nitrate and its amount precipitated was 1.5 g.
- A coin cell is produced in the same manner as in the Example 1 except that the metal salt used in the Example 1 was not used.
- A laminate cell is produced in the same manner as in the Example 3 except that the metal salt used in the Example 3 was not used.
- The respective all-solid-state lithium secondary battery cells obtained in the Examples 1-4 and the Comparative Examples 1-2 were submersed into water of 30 ml in a 100 ml beaker placed inside of sealed plastic bag. The respective hydrogen sulfide level in the plastic bag after one minute from the submersion was subsequently measured with a hydrogen sulfide gas sensor (GBL-HS® manufactured by JIKCO Ltd.) set in the plastic bag. Measured results of the hydrogen sulfide level are shown in Table 1.
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TABLE 1 Hydrogen Sulfide Level Hydrogen Sulfide Level ppm Example 1 0 Example 2 0 Example 3 0 Example 4 0 Comparative Example 1 7 Comparative Example 2 16 - As shown in Table 1, the respective hydrogen sulfide levels obtained in Examples 1-4 were 0 ppm. On the other hand, hydrogen sulfide of 7 ppm and that of 16 ppm were detected in the Comparative Examples 1 and 2, respectively. The reason of this is assumed to be as follows. As no metal salt was presented in the respective cases when submersed, sulfide ions generated by a reaction between the sulfide-based solid electrolyte materials and water were unable to fix themselves so that hydrogen sulfide gas was generated in each cases.
- In view of the above-mentioned results, it was ascertained that, in the respective all-solid-state lithium secondary batteries obtained in the Examples, by comprising the metal salt in the battery case, the metal cation of the metal salt generated by dissociation caused with water reacted with the sulfide ion generated by a reaction between the sulfide-based solid electrolyte material and the water, the precipitate is generated, and thereby the sulfide ion is fixed as the metal sulfide. It was ascertained thereby that the all-solid-state lithium secondary battery of the present invention has an effect of restricting generation of hydrogen sulfide gas.
Claims (2)
1. An all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material,
wherein the battery has a metal salt M-X comprising a metal element “M” and an anionic part “X” in a battery case thereof, and further
wherein a metal cation of the metal salt M-X generated by disassociation caused with water can react with a sulfide ion generated by a reaction between the sulfide-based solid electrolyte material and the water.
2. The all-solid-state lithium secondary battery according to claim 1 , wherein the metal element “M” of the metal salt M-X is at least one selected from the group consisting of Cd, Sn, Pb, Cu, Hg, Ag, Al, Mn, Zn, Fe and Ni, and further
wherein the anionic part “X” of the metal salt M-X is at least one selected from the group consisting of OH, SO4 and NO3.
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JP2007-032561 | 2007-02-13 | ||
JP2007032561A JP4779988B2 (en) | 2007-02-13 | 2007-02-13 | All-solid lithium secondary battery |
PCT/JP2008/051055 WO2008099656A1 (en) | 2007-02-13 | 2008-01-25 | All-solid lithium secondary battery |
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PCT/JP2008/051055 A-371-Of-International WO2008099656A1 (en) | 2007-02-13 | 2008-01-25 | All-solid lithium secondary battery |
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US13/307,702 Continuation US8293389B2 (en) | 2007-02-13 | 2011-11-30 | All-solid state lithium secondary battery |
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US20110129723A1 true US20110129723A1 (en) | 2011-06-02 |
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US12/521,654 Abandoned US20110129723A1 (en) | 2007-02-13 | 2008-01-25 | All-solid-state lithium secondary battery |
US13/307,702 Active US8293389B2 (en) | 2007-02-13 | 2011-11-30 | All-solid state lithium secondary battery |
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US13/307,702 Active US8293389B2 (en) | 2007-02-13 | 2011-11-30 | All-solid state lithium secondary battery |
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US (2) | US20110129723A1 (en) |
JP (1) | JP4779988B2 (en) |
KR (1) | KR101027898B1 (en) |
CN (1) | CN101595590B (en) |
WO (1) | WO2008099656A1 (en) |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060073388A1 (en) * | 2004-10-01 | 2006-04-06 | Kabushiki Kaisha Toshiba | Rechargeable battery and method for fabricating the same |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11219722A (en) * | 1998-02-03 | 1999-08-10 | Matsushita Electric Ind Co Ltd | Lithium secondary battery |
JP4391609B2 (en) * | 1998-09-30 | 2009-12-24 | 株式会社ジーエス・ユアサコーポレーション | Non-aqueous electrolyte secondary battery for battery pack |
JP2001052733A (en) * | 1999-08-05 | 2001-02-23 | Matsushita Electric Ind Co Ltd | Entirely solid lithium secondary battery |
JP4529207B2 (en) | 1999-11-30 | 2010-08-25 | ソニー株式会社 | Non-aqueous electrolyte battery |
JP3890185B2 (en) * | 2000-07-27 | 2007-03-07 | 松下電器産業株式会社 | Positive electrode active material and non-aqueous electrolyte secondary battery including the same |
JP2003151558A (en) | 2001-11-14 | 2003-05-23 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery |
JP2004087152A (en) * | 2002-08-23 | 2004-03-18 | Hitachi Ltd | Sodium sulfur cell system |
JP3975923B2 (en) | 2003-01-20 | 2007-09-12 | ソニー株式会社 | Non-aqueous electrolyte battery |
WO2007004590A1 (en) * | 2005-07-01 | 2007-01-11 | National Institute For Materials Science | All-solid lithium battery |
JP2008103288A (en) * | 2006-10-20 | 2008-05-01 | Idemitsu Kosan Co Ltd | All-solid battery |
-
2007
- 2007-02-13 JP JP2007032561A patent/JP4779988B2/en active Active
-
2008
- 2008-01-25 WO PCT/JP2008/051055 patent/WO2008099656A1/en active Application Filing
- 2008-01-25 CN CN2008800023985A patent/CN101595590B/en not_active Expired - Fee Related
- 2008-01-25 US US12/521,654 patent/US20110129723A1/en not_active Abandoned
- 2008-01-25 KR KR1020097013833A patent/KR101027898B1/en active IP Right Grant
-
2011
- 2011-11-30 US US13/307,702 patent/US8293389B2/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060073388A1 (en) * | 2004-10-01 | 2006-04-06 | Kabushiki Kaisha Toshiba | Rechargeable battery and method for fabricating the same |
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Also Published As
Publication number | Publication date |
---|---|
WO2008099656A1 (en) | 2008-08-21 |
JP2008198489A (en) | 2008-08-28 |
US8293389B2 (en) | 2012-10-23 |
KR20090086462A (en) | 2009-08-12 |
US20120077078A1 (en) | 2012-03-29 |
JP4779988B2 (en) | 2011-09-28 |
CN101595590A (en) | 2009-12-02 |
CN101595590B (en) | 2011-08-31 |
KR101027898B1 (en) | 2011-04-07 |
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