JP7121730B2 - Gas generation inhibitor for electricity storage device and electricity storage device using this gas generation inhibitor for electricity storage device - Google Patents
Gas generation inhibitor for electricity storage device and electricity storage device using this gas generation inhibitor for electricity storage device Download PDFInfo
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- JP7121730B2 JP7121730B2 JP2019515721A JP2019515721A JP7121730B2 JP 7121730 B2 JP7121730 B2 JP 7121730B2 JP 2019515721 A JP2019515721 A JP 2019515721A JP 2019515721 A JP2019515721 A JP 2019515721A JP 7121730 B2 JP7121730 B2 JP 7121730B2
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- 238000003860 storage Methods 0.000 title claims description 105
- 230000005611 electricity Effects 0.000 title claims description 57
- 239000003112 inhibitor Substances 0.000 title claims description 49
- -1 alkaline earth metal titanate Chemical class 0.000 claims description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 claims description 12
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 89
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- 239000001569 carbon dioxide Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002250 absorbent Substances 0.000 description 7
- 230000002745 absorbent Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000011358 absorbing material Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- WEUCVIBPSSMHJG-UHFFFAOYSA-N calcium titanate Chemical compound [O-2].[O-2].[O-2].[Ca+2].[Ti+4] WEUCVIBPSSMHJG-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229920006369 KF polymer Polymers 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 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
- 239000002131 composite material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910020264 Na2TiO3 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- DKKXQTSDXGEATA-UHFFFAOYSA-N dipotassium oxido-(oxido(oxo)titanio)oxy-oxotitanium Chemical compound [K+].[K+].[O-][Ti](=O)O[Ti]([O-])=O DKKXQTSDXGEATA-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- UJPWWRPNIRRCPJ-UHFFFAOYSA-L strontium;dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Sr+2] UJPWWRPNIRRCPJ-UHFFFAOYSA-L 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
- H01G11/20—Reformation or processes for removal of impurities, e.g. scavenging
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明はリチウムイオン電池や電気二重層キャパシタなどの蓄電デバイスに用いられるガス発生抑制剤に関するものである。 TECHNICAL FIELD The present invention relates to gas generation inhibitors used in electricity storage devices such as lithium ion batteries and electric double layer capacitors.
リチウムイオン電池や電気二重層キャパシタなどの蓄電デバイスは、それぞれが持つ高エネルギー密度、高出力密度という特徴を活用し、近年急速に実用化が行われている。 Electricity storage devices such as lithium ion batteries and electric double layer capacitors have been rapidly put to practical use in recent years, taking advantage of their respective characteristics of high energy density and high output density.
しかしながら、このような蓄電デバイスにおいては、蓄電デバイスの内に存在する不純物（例えば活物質内に残存している未反応の炭酸リチウムなど）や水分の混入、あるいは使用によって電解液や電極を構成する材料が酸化分解することなどが原因となって、蓄電デバイス内に炭酸ガス、水素ガス、フッ素ガスなどのガスが発生してしまうという課題がある。係るガスは蓄電デバイスの性能を低下させる原因となるものであり、またこのようなガスの発生が継続することになると蓄電デバイスからの液漏れや形状変化（膨張）を招き、最終的には炎上、爆発という重大事象を引き起こすことになるものとなる。
ここで、このようなガスの中には、未反応の炭酸リチウムが経時劣化（分解）したり、充放電を繰り返すことによって電解液が酸化分解したりすることによって発生するガス（炭酸ガス）といったものもあるが、このようなガスとは別に、水素ガス、フッ素ガスの原因となるプロトン（Ｈ＋）も発生する。具体的には、蓄電デバイス内に浸入した水分自体が電気分解することによって発生するプロトン（Ｈ＋）や、電解液に電解質としてヘキサフルオロリン酸リチウム（ＬｉＰＦ６）やホウフッ化リチウム（ＬｉＢＦ４）などを用いている場合に、係る電解質から分解したＢＦ４
－やＰＦ６
－などの陰イオンと蓄電デバイス内に浸入した水分とが反応して形成されたフッ化水素（ＨＦ）がさらに解離することによって発生するプロトン（Ｈ＋）などがある。そして、係るプロトン同士が結合することで水素ガスが発生したり、フッ化水素（ＨＦ）から解離したフッ素イオン同士が結合することでフッ素ガスが発生したりするのである。
また、電解質から分解したＢＦ４
－やＰＦ６
－などの陰イオンと未反応の炭酸リチウムとが反応することによって発生する炭酸ガスもある。However, in such an electric storage device, impurities present in the electric storage device (for example, unreacted lithium carbonate remaining in the active material) and moisture are mixed in, or the electrolyte and the electrodes are formed by use. There is a problem that gases such as carbon dioxide gas, hydrogen gas, and fluorine gas are generated in the electric storage device due to oxidative decomposition of the material. Such gas causes deterioration of the performance of the electricity storage device, and if such gas continues to be generated, it will lead to leakage of liquid from the electricity storage device, change in shape (expansion), and finally fire. , which will cause a serious event called an explosion.
Here, among such gases, unreacted lithium carbonate degrades (decomposes) over time, and the electrolyte is oxidized and decomposed by repeated charging and discharging (carbon dioxide gas). However, apart from such gases, protons (H + ) that cause hydrogen gas and fluorine gas are also generated. Specifically, protons (H + ) generated by the electrolysis of water itself that has entered the electricity storage device, and lithium hexafluorophosphate (LiPF 6 ) and lithium borofluoride (LiBF 4 ) as electrolytes in the electrolytic solution. etc., hydrogen fluoride (HF) formed by the reaction of anions such as BF 4 − and PF 6 − decomposed from the electrolyte and moisture that has entered the electricity storage device is further dissociated. protons (H + ) generated by Hydrogen gas is generated by combining protons, and fluorine gas is generated by combining fluorine ions dissociated from hydrogen fluoride (HF).
There is also carbon dioxide gas generated by reaction between anions such as BF 4 − and PF 6 − decomposed from the electrolyte and unreacted lithium carbonate.
そこで、従前から発生したガスを吸収するための様々なガス吸収材が開発されている（特許文献１～４）。具体的には、特許文献１には、炭酸ガスの吸収材として、リチウム複合酸化物やゼオライトを用いることが記載されている（特許文献１の請求項２、３および［００１２］～［００１４］参照）。特許文献２には、水酸化リチウムを炭酸ガスの吸収材として用いることが記載されている（特許文献２の請求項３および［０００９］、［００１０］参照）。特許文献３には、アルカリ金属の炭酸塩をフッ素ガスの吸収材として用いることが記載されている（特許文献３の請求項１、３、４および［００１４］参照）。特許文献４には、ＺｎＯ、ＮａＡｌＯ２、ケイ素をフッ素ガスの吸収材として用いることが記載されている（特許文献４の請求項１５、１６および［００６３］参照）。Therefore, various gas absorbents have been developed for absorbing generated gas (
さらに、特許文献５には、炭酸リチウム粉末と酸化リチウム粉末と二酸化チタン粉末を特定の比率で混合した炭酸ガス吸収材が記載されており（特許文献５の請求項１および［００２８］参照）、非特許文献１には、リチウム複合酸化物が炭酸ガスの吸収材料となり得ることが開示されている（非特許文献１の１２頁の「新しいＣＯ２吸収材料の特長」を参照）。Furthermore,
しかしながら、これらの文献はいずれも発生したガスを吸収することを目的とするものであり、ガスの発生自体を抑制すること、すなわちガス発生の源となるプロトン（Ｈ＋）自体を捕捉することを目的（技術的思想）とするものではない。
従って、これらの文献に記載されている各種の吸収材は、液漏れ、形状変化（膨張）、炎上、爆発という事象については防止することができるかもしれないが、ガスが発生している（電解液や電極を構成する材料の酸化分解などが発生している）ことには変わりがないことから、蓄電デバイス性能の低下を防止することはできないものとなっている。However, all of these documents aim to absorb the generated gas, and are intended to suppress the generation of the gas itself, that is, to capture the protons (H + ) themselves that are the source of the gas generation. It is not the purpose (technical idea).
Therefore, the various absorbents described in these documents may be able to prevent events such as liquid leakage, shape change (expansion), flames, and explosions, but gas is generated (electrolytic However, there is no change in the fact that oxidative decomposition of the liquid and the materials that make up the electrodes occurs), so it is impossible to prevent the deterioration of the performance of the electric storage device.
また、従前のガス吸収材としては、蓄電デバイスにおいて使用実績の多い元素であることから、特許文献１、２に記載されているようなリチウム化合物を用いることが一般的となっている。
In addition, lithium compounds as described in
今般、本願発明者らは鋭意検討を行った結果、一般的に用いられているリチウム化合物ではなく、ナトリウムのチタン酸塩、カリウムのチタン酸塩、アルカリ土類金属のチタン酸塩から選ばれる１種以上のチタン酸塩がガスの発生自体を抑制する効果を有する、具体的にはガス発生の源となるプロトン（Ｈ＋）自体を捕捉するという知見を得るに至った。As a result of intensive studies, the inventors of the present application have found that instead of the commonly used lithium compound, 1 selected from sodium titanate, potassium titanate, and alkaline earth metal titanate The present inventors have found that more than one kind of titanate has the effect of suppressing gas generation itself, specifically, captures protons (H + ) themselves that are the source of gas generation.
本発明は、上記した従来の問題点に鑑みてなされたものであって、蓄電デバイス用ガス発生抑制剤の提供を目的とするものである。また、この蓄電デバイス用ガス発生抑制剤を用いた蓄電デバイスの提供を目的とするものである。 The present invention has been made in view of the conventional problems described above, and an object of the present invention is to provide a gas generation inhibitor for an electric storage device. Another object of the present invention is to provide an electricity storage device using this gas generation inhibitor for an electricity storage device.
上記目的を達成するために、本発明に係る蓄電デバイス用ガス発生抑制剤は、ナトリウムのチタン酸塩、カリウムのチタン酸塩、アルカリ土類金属のチタン酸塩から選ばれる１種以上のチタン酸塩を含有することを特徴とする。 In order to achieve the above object, the gas generation inhibitor for an electricity storage device according to the present invention comprises at least one titanate selected from sodium titanate, potassium titanate, and alkaline earth metal titanate. It is characterized by containing salt.
本発明に係る蓄電デバイス用ガス発生抑制剤は、アルカリ土類金属が、Ｍｇ、Ｃａ、Ｓｒ、Ｂａから選ばれる１種以上のものであることを特徴とする。 The gas generation inhibitor for electrical storage devices according to the present invention is characterized in that the alkaline earth metal is one or more selected from Mg, Ca, Sr and Ba.
本発明に係る蓄電デバイスは、本発明の蓄電デバイス用ガス発生抑制剤を含有することを特徴とする。 An electricity storage device according to the present invention is characterized by containing the gas generation inhibitor for an electricity storage device of the present invention.
（基本構造）
本発明の蓄電デバイス用ガス発生抑制剤は、ナトリウムのチタン酸塩、カリウムのチタン酸塩、アルカリ土類金属のチタン酸塩から選ばれる１種以上のチタン酸塩を含有することを基本構造とする。このように、本発明の蓄電デバイス用ガス発生抑制剤は、特定のアルカリ金属のチタン酸塩または／および特定のアルカリ土類金属のチタン酸塩を含有することによって、従前の蓄電デバイスにおいて問題となっていた使用時や経時変化における炭酸ガス、水素ガス、フッ素ガスなどの各種のガスの発生を抑制することができるのである。
具体的には、以下に例示（チタン酸ナトリウムを使用）する反応式に示すように、本発明の蓄電デバイス用ガス発生抑制剤のアルカリ金属イオンまたはアルカリ土類金属イオンと、蓄電デバイス内において発生するプロトンとがイオン交換反応をすることによって、ガス発生の源となるプロトン（Ｈ＋）自体を捕捉することができるのである。
また、本発明の蓄電デバイス用ガス発生抑制剤のチタン酸イオンと炭酸イオンとがイオン交換反応をすることによって、炭酸ガスも捕捉することができるのである。
Ｎａ２ＴｉＯ３ ＋ ２Ｈ＋ → Ｈ２ＴｉＯ３ ＋ ２Ｎａ＋（プロトン捕捉＝イオン交換反応）
Ｎａ２ＴｉＯ３ ＋ ＣＯ２ → Ｎａ２ＣＯ３ ＋ ＴｉＯ２（ＣＯ２吸収）(Basic structure)
The basic structure of the gas generation inhibitor for an electricity storage device of the present invention is that it contains at least one titanate selected from sodium titanate, potassium titanate, and alkaline earth metal titanate. do. As described above, the gas generation inhibitor for an electric storage device of the present invention contains a specific alkali metal titanate and/or a specific alkaline earth metal titanate, which causes problems in conventional electric storage devices. It is possible to suppress the generation of various gases such as carbon dioxide gas, hydrogen gas, and fluorine gas during use and aging.
Specifically, as shown in the reaction formula exemplified below (using sodium titanate), the alkali metal ion or alkaline earth metal ion of the gas generation inhibitor for an electricity storage device of the present invention and the The protons (H + ) themselves, which are the source of gas generation, can be captured by the ion exchange reaction with protons.
Carbon dioxide gas can also be captured by the ion exchange reaction between titanate ions and carbonate ions in the gas generation inhibitor for electrical storage devices of the present invention.
Na 2 TiO 3 + 2H + → H 2 TiO 3 + 2Na + (proton capture = ion exchange reaction)
Na2TiO3 + CO2 → Na2CO3 + TiO2 ( CO2 absorption)
（ナトリウムのチタン酸塩、カリウムのチタン酸塩）
本発明の蓄電デバイス用ガス発生抑制剤に用いられるアルカリ金属のチタン酸塩は、チタン酸ナトリウム、チタン酸カリウムである。このように特定のアルカリ金属のチタン酸塩を含有することによって、従前の蓄電デバイスにおいて主に使用されていたチタン酸リチウムなどのリチウム化合物にはない、ガス発生の抑制効果を発現させることができるのである。なお、これらアルカリ金属のチタン酸塩については、単独で用いても良いし、併用することもできる。(sodium titanate, potassium titanate)
Alkali metal titanates used in the gas generation inhibitor for electrical storage devices of the present invention are sodium titanate and potassium titanate. By containing a specific alkali metal titanate in this way, it is possible to exhibit an effect of suppressing gas generation, which is not found in lithium compounds such as lithium titanate that have been mainly used in conventional electric storage devices. of. These alkali metal titanates may be used alone or in combination.
（アルカリ土類金属のチタン酸塩）
本発明の蓄電デバイス用ガス発生抑制剤に用いられるアルカリ土類金属のチタン酸塩は、具体的にはチタン酸マグネシウム、チタン酸カルシウム、チタン酸ストロンチウム、チタン酸バリウム、チタン酸ラジウムが挙げられるが、その中でもチタン酸マグネシウム、チタン酸カルシウム、チタン酸ストロンチウム、チタン酸バリウムを用いることが好ましい。また、アルカリ土類金属のチタン酸塩についても、上記したアルカリ金属のチタン酸塩と同様に単独で用いても良いし、併用することもできる。(alkaline earth metal titanate)
Examples of the alkaline earth metal titanate used in the gas generation inhibitor for an electricity storage device of the present invention include magnesium titanate, calcium titanate, strontium titanate, barium titanate, and radium titanate. Among them, it is preferable to use magnesium titanate, calcium titanate, strontium titanate, and barium titanate. Also, the alkaline earth metal titanate may be used alone or in combination in the same manner as the alkali metal titanate described above.
なお、これらチタン酸塩の配合量については特に限定されるものではないが、正極活物質に対して、５～７０ｗｔ％とすることが好ましく、その中でも１０～５０ｗｔ％であることが好ましい。 Although the amount of these titanates to be added is not particularly limited, it is preferably 5 to 70 wt %, more preferably 10 to 50 wt %, relative to the positive electrode active material.
また、本発明の蓄電デバイス用ガス発生抑制剤は、ガス発生の抑制効果をより高めるために、後述する方法によって測定される粉体ｐＨが１０．５以上であることが好ましい。そしてその中でも１１．０以上であることがより好ましく、１１．５以上であることが更に好ましい。その理由としては、粉体ｐＨが高いほど、本発明の蓄電デバイス用ガス発生抑制剤（チタン酸塩）から、ナトリウムイオン、カリウムイオン、アルカリ土類金属イオンなどのカチオンが解離しやすくなり、それに伴って段落［００１５］に示す反応式のイオン交換反応が促進され、その結果、プロトン（Ｈ＋）を取り込みやすくなるためと考えられる。つまり、ガス発生の源となるプロトン（Ｈ＋）をより捕捉しやすくなることで、ガス発生の抑制効果もより高くなるものと考えられる。In order to further enhance the effect of suppressing gas generation, the gas generation inhibitor for an electricity storage device of the present invention preferably has a powder pH of 10.5 or more as measured by the method described later. Among them, 11.0 or more is more preferable, and 11.5 or more is even more preferable. The reason for this is that the higher the powder pH, the easier it is for cations such as sodium ions, potassium ions, and alkaline earth metal ions to dissociate from the gas generation inhibitor (titanate) for power storage devices of the present invention. Concomitantly, the ion exchange reaction of the reaction formula shown in paragraph [0015] is promoted, and as a result, protons (H + ) are taken in easily. In other words, it is considered that protons (H + ), which are the source of gas generation, are more likely to be captured, and the effect of suppressing gas generation is further enhanced.
（蓄電デバイス）
本発明の蓄電デバイスは、本発明の蓄電デバイス用ガス発生抑制剤を含有するものであるが、その中でも正極またはセパレータの材料に含有することが好ましい。(storage device)
The electricity storage device of the present invention contains the gas generation inhibitor for an electricity storage device of the present invention, and among these, it is preferable to contain it in the material of the positive electrode or the separator.
本発明に係る蓄電デバイス用ガス発生抑制剤によれば、従前の蓄電デバイスにおいて問題となっていた使用時や経時変化における炭酸ガス、水素ガス、フッ素ガスなどの各種のガスの発生を抑制することができる。 According to the gas generation inhibitor for electricity storage devices according to the present invention, it is possible to suppress the generation of various gases such as carbon dioxide gas, hydrogen gas, and fluorine gas during use and over time, which has been a problem in conventional electricity storage devices. can be done.
本発明に係る蓄電デバイス用ガス発生抑制剤によれば、特定のアルカリ土類金属を用いたチタン酸塩とすることによって、上記の効果をより向上させることができる。 According to the gas generation inhibitor for an electric storage device according to the present invention, the above effect can be further improved by using a titanate using a specific alkaline earth metal.
次に、本発明に係る蓄電デバイス用ガス発生抑制剤を実施例および比較例に基づいて詳しく説明する。なお、本発明は以下の実施例に限定されるものではない。 Next, the gas generation inhibitor for electrical storage devices according to the present invention will be described in detail based on examples and comparative examples. In addition, the present invention is not limited to the following examples.
（実施例１）
アナタース型酸化チタン（テイカ社製ＡＭＴ－１００）３００ｇと水酸化ナトリウム（シグマアルドリッチ社製）３９９ｇを湿式混合したのち、大気中において７５０℃で２ｈｒ焼成することによって、実施例１の蓄電デバイス用ガス発生抑制剤（チタン酸ナトリウム（Ｎａ２ＴｉＯ３））を作製した。(Example 1)
After wet-mixing 300 g of anatase-type titanium oxide (AMT-100 manufactured by Tayka) and 399 g of sodium hydroxide (manufactured by Sigma-Aldrich), the electricity storage device gas of Example 1 was obtained by firing at 750 ° C. for 2 hours in the air. A generation inhibitor (sodium titanate (Na 2 TiO 3 )) was prepared.
（実施例２）
水酸化ナトリウムの量を１３３ｇとした以外は実施例１と同様にして実施例２の蓄電デバイス用ガス発生抑制剤（チタン酸ナトリウム（Ｎａ４Ｔｉ５Ｏ１２））を作製した。(Example 2)
A gas generation inhibitor for an electricity storage device (sodium titanate (Na 4 Ti 5 O 12 )) of Example 2 was produced in the same manner as in Example 1, except that the amount of sodium hydroxide was changed to 133 g.
（実施例３）
水酸化ナトリウムの量を１１１ｇとした以外は実施例１と同様にして実施例３の蓄電デバイス用ガス発生抑制剤（チタン酸ナトリウム（Ｎａ２Ｔｉ３Ｏ７））を作製した。(Example 3)
A gas generation inhibitor for an electricity storage device (sodium titanate (Na 2 Ti 3 O 7 )) of Example 3 was prepared in the same manner as in Example 1, except that the amount of sodium hydroxide was changed to 111 g.
（実施例４）
水酸化ナトリウムを水酸化カリウム（シグマアルドリッチ社製）２４９ｇとした以外は実施例１と同様にして実施例４の蓄電デバイス用ガス発生抑制剤（チタン酸カリウム（Ｋ２Ｔｉ２Ｏ５））を作製した。(Example 4)
In the same manner as in Example 1 except that 249 g of potassium hydroxide (manufactured by Sigma-Aldrich) was used instead of sodium hydroxide, the gas generation inhibitor for an electricity storage device of Example 4 (potassium titanate (K 2 Ti 2 O 5 )) was added. made.
（実施例５）
水酸化カリウムの量を１０８ｇとした以外は実施例４と同様にして実施例５の蓄電デバイス用ガス発生抑制剤（チタン酸カリウム（Ｋ２Ｔｉ６Ｏ１３））を作製した。(Example 5)
A gas generation inhibitor for an electricity storage device (potassium titanate (K 2 Ti 6 O 13 )) of Example 5 was prepared in the same manner as in Example 4, except that the amount of potassium hydroxide was changed to 108 g.
（実施例６）
水酸化カリウムの量を１４４ｇとした以外は実施例４と同様にして実施例６の蓄電デバイス用ガス発生抑制剤（チタン酸カリウム（Ｋ２Ｔｉ４Ｏ９））を作製した。(Example 6)
A gas generation inhibitor for an electricity storage device (potassium titanate (K 2 Ti 4 O 9 )) of Example 6 was prepared in the same manner as in Example 4, except that the amount of potassium hydroxide was changed to 144 g.
（実施例７）
水酸化ナトリウムを水酸化マグネシウム（シグマアルドリッチ社製）４３８ｇとした以外は実施例１と同様にして実施例７の蓄電デバイス用ガス発生抑制剤（チタン酸マグネシウム（ＭｇＴｉＯ３））を作製した。(Example 7)
A gas generation inhibitor for an electricity storage device (magnesium titanate (MgTiO 3 )) of Example 7 was prepared in the same manner as in Example 1 except that 438 g of magnesium hydroxide (manufactured by Sigma-Aldrich) was used instead of sodium hydroxide.
（実施例８）
水酸化ナトリウムを水酸化カルシウム（シグマアルドリッチ社製）５６４ｇとした以外は実施例１と同様にして実施例８の蓄電デバイス用ガス発生抑制剤（チタン酸カルシウム（ＣａＴｉＯ３））を作製した。(Example 8)
A gas generation inhibitor for an electricity storage device (calcium titanate (CaTiO 3 )) of Example 8 was prepared in the same manner as in Example 1 except that 564 g of calcium hydroxide (manufactured by Sigma-Aldrich) was used instead of sodium hydroxide.
（実施例９）
水酸化ナトリウムを水酸化ストロンチウム・８水和物（シグマアルドリッチ社製）９９７ｇとした以外は実施例１と同様にして実施例９の蓄電デバイス用ガス発生抑制剤（チタン酸ストロンチウム（ＳｒＴｉＯ３））を作製した。(Example 9)
Gas generation inhibitor for electricity storage device (strontium titanate (SrTiO 3 )) of Example 9 was prepared in the same manner as in Example 1 except that 997 g of strontium hydroxide octahydrate (manufactured by Sigma-Aldrich) was used as sodium hydroxide. was made.
（実施例１０）
水酸化ナトリウムを水酸化バリウム ・８水和物（シグマアルドリッチ社製）１１９４ｇとした以外は実施例１と同様にして実施例１０の蓄電デバイス用ガス発生抑制剤（チタン酸バリウム（ＢａＴｉＯ３））を作製した。(Example 10)
Gas generation inhibitor for electricity storage device (barium titanate (BaTiO 3 )) of Example 10 in the same manner as in Example 1 except that 1194 g of barium hydroxide octahydrate (manufactured by Sigma-Aldrich) was used instead of sodium hydroxide. was made.
（蓄電デバイス用ガス発生抑制剤の粉体ｐＨの測定）
作製した各蓄電デバイス用ガス発生抑制剤１０ｇを純水１００ｍｌ中に加え、攪拌しながら加熱し、沸騰した状態で５分間保持したのちに室温まで冷却した。その後、得られた懸濁液のｐＨを、ｐＨメーター（堀場製作所製）を用いて測定し、その値を蓄電デバイス用ガス発生抑制剤の粉体ｐＨとした。(Measurement of powder pH of gas generation inhibitor for electricity storage device)
10 g of each prepared gas generation inhibitor for electric storage devices was added to 100 ml of pure water, heated with stirring, kept in a boiling state for 5 minutes, and then cooled to room temperature. Thereafter, the pH of the obtained suspension was measured using a pH meter (manufactured by Horiba, Ltd.), and the value was taken as the powder pH of the gas generation inhibitor for electricity storage devices.
次に、作製した各蓄電デバイス用ガス発生抑制剤を用いて蓄電デバイス用正極を作製するとともに、係る正極を用いた蓄電デバイスを作製し、ガス発生の抑制効果、蓄電デバイス性能（サイクル特性）の評価を行った。 Next, a positive electrode for an electric storage device was produced using each produced gas generation inhibitor for an electric storage device, an electric storage device was produced using the positive electrode, and the effect of suppressing gas generation and the performance (cycle characteristics) of the electric storage device were evaluated. made an evaluation.
（蓄電デバイス用正極の作製）
まず、実施例１～１０の各蓄電デバイス用ガス発生抑制剤２．３ｇを活性炭（ＡＴエレクトロード社製ベルファインＡＰ２０－０００１）４．９ｇおよびアセチレンブラック（電気化学工業社製デンカブラック）０．９ｇと乾式混合した。次に、ポリフッ化ビニリデン（クレハ社製ＫＦポリマー）０．９ｇを加え、プラネタリーミキサーを用いて混練した。次に、Ｎ－メチル－２－ピロリドン（キシダ化学社製）３６ｇを加えて粘度調整をすることによって各正極用塗料を作製した。(Preparation of positive electrode for electricity storage device)
First, 4.9 g of activated carbon (BELLFINE AP20-0001 manufactured by AT Electrode Co., Ltd.) and 0.3 g of acetylene black (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.) were added to 2.3 g of the gas generation inhibitor for each power storage device of Examples 1 to 10. 9 g and dry blended. Next, 0.9 g of polyvinylidene fluoride (KF polymer manufactured by Kureha Co., Ltd.) was added and kneaded using a planetary mixer. Next, 36 g of N-methyl-2-pyrrolidone (manufactured by Kishida Kagaku Co., Ltd.) was added to adjust the viscosity to prepare each positive electrode paint.
次に、上記にて作製した各正極用塗料をアルミ箔に塗付、乾燥することによって、各蓄電デバイス用正極を作製した。なお、このときの蓄電デバイス内に存在する実施例の各蓄電デバイス用ガス発生抑制剤の重量は１６．５ｍｇであり、実施例の各蓄電デバイス用ガス発生抑制剤と活性炭の重量比は３２：６８であった。 Next, each positive electrode for an electric storage device was produced by applying each positive electrode paint prepared above to an aluminum foil and drying it. At this time, the weight of each gas generation inhibitor for power storage devices in the power storage device present in the power storage device was 16.5 mg. was 68.
また、実施例４の蓄電デバイス用ガス発生抑制剤と活性炭の量をそれぞれ１．４ｇと５．８ｇ、３．５ｇと３．７ｇ、５．０ｇと２．２ｇに変更したもの（すなわち、後記する蓄電デバイス内に存在する蓄電デバイス用ガス発生抑制剤の重量を３．９ｍｇ 、３３．６ｍｇ、７７．９ｍｇとしたもの）も作製した。なお、このときの実施例３の蓄電デバイス用ガス発生抑制剤と活性炭の重量比はそれぞれ１９：８１、４９：５１、６９：３１であった。 Further, the amounts of gas generation inhibitor for electric storage device and activated carbon in Example 4 were changed to 1.4 g and 5.8 g, 3.5 g and 3.7 g, 5.0 g and 2.2 g, respectively (that is, 3.9 mg, 33.6 mg, and 77.9 mg) were also produced. At this time, the weight ratios of the gas generation inhibitor for electric storage devices and the activated carbon of Example 3 were 19:81, 49:51 and 69:31, respectively.
（蓄電デバイス用負極の作製）
まず、オルソチタン酸（テイカ社製）５２０ｇと水酸化リチウム・１水和物（ＦＭＣ社製）２１８ｇを湿式混合したのち、大気中６５０℃で２ｈｒ焼成することによって、比表面積７０ｍ２／ｇの微粒子Ｌｉ４Ｔｉ５Ｏ１２を得た。
次に、上記の微粒子Ｌｉ４Ｔｉ５Ｏ１２、７．２ｇおよびアセチレンブラック（電気化学工業社製デンカブラック）０．９ｇを乾式混合した。次に、ポリフッ化ビニリデン（クレハ社製ＫＦポリマー）０．９ｇを加え、プラネタリーミキサーを用いて混練した。次に、Ｎ－メチル－２－ピロリドン（キシダ化学社製）３６ｇを加えて粘度調整をすることによって負極用塗料を作製した。
次に、上記にて作製した負極用塗料をアルミ箔に塗付、乾燥することによって、蓄電デバイス用負極を作製した。(Preparation of negative electrode for electricity storage device)
First, 520 g of orthotitanic acid (manufactured by Tayka) and 218 g of lithium hydroxide monohydrate (manufactured by FMC) were wet-mixed and then fired at 650° C. in the air for 2 hours to obtain a specific surface area of 70 m 2 /g. Fine particles of Li 4 Ti 5 O 12 were obtained.
Next, 7.2 g of the fine particles Li 4 Ti 5 O 12 and 0.9 g of acetylene black (Denka black manufactured by Denki Kagaku Kogyo Co., Ltd.) were dry mixed. Next, 0.9 g of polyvinylidene fluoride (KF polymer manufactured by Kureha Co., Ltd.) was added and kneaded using a planetary mixer. Next, 36 g of N-methyl-2-pyrrolidone (manufactured by Kishida Chemical Co., Ltd.) was added to adjust the viscosity, thereby preparing a negative electrode paint.
Next, the negative electrode for an electric storage device was produced by applying the negative electrode paint prepared above to an aluminum foil and drying it.
（蓄電デバイスの作製）
次に、上記にて作製した各蓄電デバイス用正極、負極、セパレータ（日本高度紙工業社製）、タブリードを準備し、図１のように配置（積層）した後、ケースに納め、さらに電解液として１ＭのＬｉＢＦ４／ＰＣ（キシダ化学社製）を注液した後、封止することによって、表１に記載の実施例１１～２３の各蓄電デバイスを作製した。なお、このときの電気容量は６００μＡｈであった。
また、比較例として、活性炭７．２ｇ、アセチレンブラック０．９ｇ、ポリフッ化ビニリデン０．９ｇ、Ｎ－メチル－２－ピロリドン３６ｇのみで作製した正極用塗料を用いた比較例１の蓄電デバイスと、実施例の蓄電デバイス用ガス発生抑制剤２．３ｇの代わりにアナタース型酸化チタン（テイカ社製ＡＭＴ－１００）２．３ｇを用いた以外は上記と同様にして作製した正極用塗料を用いた比較例２の蓄電デバイスについても作製した。(Production of power storage device)
Next, prepare the positive electrode, negative electrode, separator (manufactured by Nippon Kodo Paper Industry Co., Ltd.), and tab leads for each storage device prepared above, arrange (laminate) as shown in FIG. 1M of LiBF 4 /PC (manufactured by Kishida Chemical Co., Ltd.) was injected as a liquid, and then sealed, whereby each of the power storage devices of Examples 11 to 23 shown in Table 1 was produced. The electric capacity at this time was 600 μAh.
Further, as a comparative example, the electricity storage device of Comparative Example 1 using a positive electrode paint made only from 7.2 g of activated carbon, 0.9 g of acetylene black, 0.9 g of polyvinylidene fluoride, and 36 g of N-methyl-2-pyrrolidone, Comparison using a positive electrode paint prepared in the same manner as above, except that 2.3 g of the gas generation inhibitor for electricity storage devices in the example was replaced with 2.3 g of anatase type titanium oxide (AMT-100 manufactured by Tayca). An electricity storage device of Example 2 was also produced.
（ガス発生量の測定）
まず、作製した実施例１１～２３および比較例１、２の各蓄電デバイスの初期体積を、アルキメデスの原理に基づいて測定した。具体的には、２５℃の水を張った水槽に蓄電デバイスを沈め、そのときの重量変化から各蓄電デバイスの初期体積を算出した。
次に、各蓄電デバイスを６０℃の条件下において、１．５～２．９Ｖの電圧範囲、１Ｃの充放電速度の条件の下で３サイクル充放電を行った。その後、上記測定方法と同様にして、充放電後の各蓄電デバイスの体積を算出し、初期体積との差から充放電前後の各蓄電デバイスの体積変化を求めることによって、各蓄電デバイスからのガス発生量を測定した。また、以下の計算式から、各蓄電デバイスの体積変化率も求めた。
体積変化率（％）＝体積変化（ｍｌ）÷初期体積（ｍｌ）×１００(Measurement of gas generation amount)
First, the initial volume of each of the produced electricity storage devices of Examples 11 to 23 and Comparative Examples 1 and 2 was measured based on Archimedes' principle. Specifically, the power storage device was submerged in a water tank filled with water at 25° C., and the initial volume of each power storage device was calculated from the weight change at that time.
Next, each electric storage device was subjected to 3 cycles of charge/discharge under conditions of 60° C., voltage range of 1.5 to 2.9 V, and charge/discharge rate of 1C. After that, in the same manner as the above measurement method, the volume of each electricity storage device after charging and discharging is calculated, and the volume change of each electricity storage device before and after charging and discharging is obtained from the difference from the initial volume. The amount generated was measured. Also, the volume change rate of each electricity storage device was obtained from the following formula.
Volume change rate (%) = volume change (ml) / initial volume (ml) x 100
（容量維持率（サイクル特性）の測定）
次に、作製した各蓄電デバイスを６０℃の条件下において１．５～２．８Ｖの電圧範囲で、３００Ｃの充放電速度で１０００サイクル充放電を行った後、以下の計算式にて容量維持率（サイクル特性）の算出を行った。
１０００サイクル目の放電容量÷２サイクル目の放電容量×１００＝容量維持率（％）(Measurement of capacity retention rate (cycle characteristics))
Next, after performing 1000 cycles of charging and discharging at a charging and discharging rate of 300 C in a voltage range of 1.5 to 2.8 V under conditions of 60 ° C., the capacity is maintained according to the following calculation formula. A rate (cycle characteristic) was calculated.
Discharge capacity at 1000th cycle/discharge capacity at 2nd cycle x 100 = capacity retention rate (%)
（ＩＲドロップの測定）
次に、作製した各蓄電デバイスを６０℃の条件下において２．９Ｖ（つまり、２９００ｍＶ）の一定電圧で放電を開始し、１０００時間保持した。その後、放電開始０．５秒後の電圧を測定し、以下の計算式からＩＲドロップを算出した。なお、ＩＲドロップとは蓄電デバイスの内部抵抗を表す値であり、値が小さいほど好ましいものとなる。
ＩＲドロップ（ｍＶ）＝２９００（ｍＶ）－放電開始０．５秒後の電圧（ｍＶ）(Measurement of IR drop)
Next, each of the produced electricity storage devices was discharged at a constant voltage of 2.9 V (that is, 2900 mV) under the condition of 60° C. and held for 1000 hours. After that, the voltage was measured 0.5 seconds after the start of discharge, and the IR drop was calculated from the following formula. Note that the IR drop is a value representing the internal resistance of an electricity storage device, and the smaller the value, the better.
IR drop (mV) = 2900 (mV) - voltage (mV) 0.5 seconds after the start of discharge
結果を表１および図２に示す。その結果、実施例１１～２３の蓄電デバイスについては正極にナトリウムのチタン酸塩、カリウムのチタン酸塩、アルカリ土類金属のチタン酸塩から選ばれる１種以上のチタン酸塩を含有した材料を用いていることから、比較例１、２の蓄電デバイスに比べてガスの発生量（絶対量）が少なく、体積変化率も小さい（より具体的には、体積変化率が１０％以下）という結果となった。 Results are shown in Table 1 and FIG. As a result, in the power storage devices of Examples 11 to 23, the positive electrode contained a material containing one or more titanates selected from sodium titanate, potassium titanate, and alkaline earth metal titanate. Therefore, the amount of gas generated (absolute amount) is smaller than that of the electricity storage devices of Comparative Examples 1 and 2, and the volume change rate is also small (more specifically, the volume change rate is 10% or less). became.
また、容量維持率（サイクル特性）についても、実施例１１～２３の蓄電デバイスは、比較例の蓄電デバイスに比べて高い容量維持率（サイクル特性）を発現するという結果となった。 As for the capacity retention rate (cycle characteristics), the power storage devices of Examples 11 to 23 also exhibited higher capacity retention rates (cycle characteristics) than the power storage devices of the comparative examples.
さらに、ＩＲドロップについても、実施例１１～２３の蓄電デバイスは、比較例の蓄電デバイスに比べてＩＲドロップの値が小さく、良好な結果となった。 Furthermore, with respect to the IR drop, the power storage devices of Examples 11 to 23 had smaller IR drop values than the power storage devices of the comparative examples, and gave favorable results.
なお、蓄電デバイス用ガス発生抑制剤の粉体ｐＨと蓄電デバイスの体積変化（各蓄電デバイスからのガス発生量）との関係をグラフ化すると、図２に示すように線形の関係が成り立ち、相関関係（決定係数Ｒ２）も０．９７という高いものとなった。そして、図２から、ガス発生の抑制効果をより高めるためには、粉体ｐＨが１０．５以上であることが好ましいという結果となった。そしてその中でも１１．０以上であることがより好ましく、１１．５以上であることが更に好ましいという結果となった。In addition, when the relationship between the powder pH of the gas generation inhibitor for electricity storage devices and the volume change of the electricity storage device (the amount of gas generated from each electricity storage device) is graphed, a linear relationship holds as shown in FIG. The relationship (coefficient of determination R 2 ) was also as high as 0.97. From FIG. 2, it was found that the pH of the powder is preferably 10.5 or more in order to further enhance the effect of suppressing gas generation. Among them, 11.0 or more is more preferable, and 11.5 or more is even more preferable.
以上の結果から、本発明に係る蓄電デバイス用ガス発生抑制剤によれば、ナトリウムのチタン酸塩、カリウムのチタン酸塩、アルカリ土類金属のチタン酸塩から選ばれる１種以上のチタン酸塩を含有することによって、従前の蓄電デバイスにおいて問題となっていた使用時や経時変化における炭酸ガス、水素ガス、フッ素ガスなどの各種のガスの発生を抑制することができることがわかった。
また、各種のガスの発生を抑制しつつ、高い容量維持率（サイクル特性）を発現させることができる蓄電デバイスを得ることができることがわかった。
さらに、ガス発生が抑制されることにより、蓄電デバイスの内部抵抗の上昇が効果的に抑制され、結果としてＩＲドロップを低減できることもわかった。
そして、この効果は、蓄電デバイス用ガス発生抑制剤の粉体ｐＨが、１０．５以上（より好ましくは１１．０以上であり、さらに好ましくは１１．５以上）である場合に特に顕著であることがわかった。From the above results, according to the gas generation inhibitor for an electricity storage device according to the present invention, at least one titanate selected from sodium titanate, potassium titanate, and alkaline earth metal titanate By containing, it is possible to suppress the generation of various gases such as carbon dioxide gas, hydrogen gas, and fluorine gas during use and aging, which has been a problem in conventional electricity storage devices.
In addition, it was found that an electricity storage device capable of exhibiting a high capacity retention rate (cycle characteristics) while suppressing the generation of various gases can be obtained.
Furthermore, it was found that suppressing gas generation effectively suppresses an increase in the internal resistance of the electricity storage device, resulting in a reduction in the IR drop.
This effect is particularly remarkable when the powder pH of the gas generation inhibitor for electrical storage devices is 10.5 or higher (more preferably 11.0 or higher, and still more preferably 11.5 or higher). I understood it.
本発明の蓄電デバイス用ガス発生抑制剤は、リチウムイオン電池や電気二重層キャパシタなどの蓄電デバイスに用いることができる。 The gas generation inhibitor for electrical storage devices of the present invention can be used for electrical storage devices such as lithium ion batteries and electric double layer capacitors.
１ 蓄電デバイス
２ 正極（蓄電デバイス用ガス発生抑制剤を含有）
３ セパレータ
４ 負極
５ タブリード
６ ケース1
3
Claims (3)
A gas generation inhibitor for a power storage device, comprising at least one titanate selected from sodium titanate, potassium titanate, and alkaline earth metal titanate.
Ｍｇ、Ｃａ、Ｓｒ、Ｂａから選ばれる１種以上のものであることを特徴とする請求項１に記載の蓄電デバイス用ガス発生抑制剤。
The alkaline earth metal is
2. The gas generation inhibitor for electrical storage devices according to claim 1, wherein the gas generation inhibitor is one or more selected from Mg, Ca, Sr and Ba.
An electricity storage device using the gas generation inhibitor for an electricity storage device according to claim 1 or 2.
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| JP2003297699A (en) | 2002-03-29 | 2003-10-17 | Nec Tokin Corp | Electric double-layer capacitor |
| JP2007229602A (en) | 2006-02-28 | 2007-09-13 | Murata Mfg Co Ltd | Carbon dioxide absorbing material and method for absorbing carbon dioxide by using the same |
| JP2009106812A (en) | 2007-10-26 | 2009-05-21 | Toshiba Corp | Carbon dioxide absorber, carbon dioxide separator, reformer and producing method of carbon dioxide absorber |
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| JP2003297699A (en) | 2002-03-29 | 2003-10-17 | Nec Tokin Corp | Electric double-layer capacitor |
| JP2007229602A (en) | 2006-02-28 | 2007-09-13 | Murata Mfg Co Ltd | Carbon dioxide absorbing material and method for absorbing carbon dioxide by using the same |
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