WO2018203523A1 - Inhibiteur de génération de gaz de dispositif de stockage d'énergie et dispositif de stockage d'énergie utilisant un inhibiteur de génération de gaz de dispositif de stockage d'énergie - Google Patents

Inhibiteur de génération de gaz de dispositif de stockage d'énergie et dispositif de stockage d'énergie utilisant un inhibiteur de génération de gaz de dispositif de stockage d'énergie Download PDF

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Publication number
WO2018203523A1
WO2018203523A1 PCT/JP2018/017186 JP2018017186W WO2018203523A1 WO 2018203523 A1 WO2018203523 A1 WO 2018203523A1 JP 2018017186 W JP2018017186 W JP 2018017186W WO 2018203523 A1 WO2018203523 A1 WO 2018203523A1
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WO
WIPO (PCT)
Prior art keywords
storage device
electricity storage
gas
generation inhibitor
power storage
Prior art date
Application number
PCT/JP2018/017186
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English (en)
Japanese (ja)
Inventor
良介 杉原
桂一 渡邉
覚 爪田
修一 石本
Original Assignee
テイカ株式会社
日本ケミコン株式会社
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Application filed by テイカ株式会社, 日本ケミコン株式会社 filed Critical テイカ株式会社
Priority to JP2019515721A priority Critical patent/JP7121730B2/ja
Publication of WO2018203523A1 publication Critical patent/WO2018203523A1/fr

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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
    • 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

Definitions

  • (HF) is further dissociated Protons (H + ) generated by And when such protons couple
  • BF 4 decomposed from the electrolyte - is carbon dioxide and the anions and the unreacted lithium carbonate, such as produced by reactions - or PF 6.
  • Patent Document 5 describes a carbon dioxide gas absorbent obtained by mixing lithium carbonate powder, lithium oxide powder, and titanium dioxide powder in a specific ratio (see claim 1 and [0028] of Patent Document 5),
  • Non-Patent Document 1 discloses that lithium composite oxide can be a carbon dioxide absorbing material (see “Features of New CO 2 Absorbing Material” on page 12 of Non-Patent Document 1).
  • the present invention has been made in view of the above-mentioned conventional problems, and aims to provide a gas generation inhibitor for an electricity storage device. It is another object of the present invention to provide an electricity storage device using the gas generation inhibitor for electricity storage devices.
  • the gas generation inhibitor for an electricity storage device comprises at least one titanic acid selected from sodium titanate, potassium titanate, and alkaline earth metal titanate. It contains a salt.
  • the gas generation inhibitor for an electricity storage device is characterized in that the alkaline earth metal is one or more selected from Mg, Ca, Sr, and Ba.
  • the 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.
  • the gas generation inhibitor for an electricity storage device of the present invention has a basic structure containing at least one titanate selected from sodium titanate, potassium titanate, and alkaline earth metal titanate. To do.
  • the gas generation inhibitor for an electricity storage device of the present invention contains a specific alkali metal titanate or / and a specific alkaline earth metal titanate.
  • the generation of various gases such as carbon dioxide, hydrogen gas, and fluorine gas during use or changes with time can be suppressed.
  • it is generated in the electricity storage device with the alkali metal ion or alkaline earth metal ion of the gas generation inhibitor for the electricity storage device of the present invention.
  • the alkali metal titanates used in the gas generation inhibitor for an electricity storage device of the present invention are sodium titanate and potassium titanate.
  • a specific alkali metal titanate as described above it is possible to develop an effect of suppressing gas generation, which is not found in lithium compounds such as lithium titanate that are mainly used in conventional power storage devices. It is.
  • These alkali metal titanates may be used alone or in combination.
  • alkaline earth metal titanates Specific examples of the alkaline earth metal titanates used in the gas generation inhibitor for power storage devices of the present invention include magnesium titanate, calcium titanate, strontium titanate, barium titanate, and radium titanate. Of these, magnesium titanate, calcium titanate, strontium titanate, and barium titanate are preferably used. Also, the alkaline earth metal titanate may be used alone or in combination with the alkali metal titanate described above.
  • the amount of titanate is not particularly limited, but is preferably 5 to 70 wt% with respect to the positive electrode active material, and more preferably 10 to 50 wt%.
  • the powder pH measured by the method mentioned later is 10.5 or more. Among them, it is more preferably 11.0 or more, and further preferably 11.5 or more. The reason is that the higher the powder pH, the easier it is for cations such as sodium ions, potassium ions, alkaline earth metal ions to dissociate from the gas generation inhibitor (titanate) for the electricity storage device of the present invention. Along with this, it is considered that the ion exchange reaction of the reaction formula shown in paragraph [0015] is promoted, and as a result, protons (H + ) can be easily incorporated. That is, it is considered that the effect of suppressing gas generation is further enhanced by facilitating the capture of protons (H + ) that are the source of gas generation.
  • the electrical storage device of this invention contains the gas generation inhibitor for electrical storage devices of this invention, it is preferable to contain in the material of a positive electrode or a separator among them.
  • the generation of various gases such as carbon dioxide gas, hydrogen gas, and fluorine gas during use or change with time, which has been a problem in conventional electricity storage devices, is suppressed. Can do.
  • the above effect can be further improved by using a titanate using a specific alkaline earth metal.
  • Example 1 An anatase-type titanium oxide (Taika AMT-100) 300 g and sodium hydroxide (Sigma Aldrich) 399 g were wet-mixed and then fired in the atmosphere at 750 ° C. for 2 hr, whereby the gas for the electricity storage device of Example 1 A generation inhibitor (sodium titanate (Na 2 TiO 3 )) was prepared.
  • 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 133 g.
  • Example 3 A gas generation inhibitor for an electricity storage device (sodium titanate (Na 2 Ti 3 O 7 )) of Example 3 was produced in the same manner as in Example 1 except that the amount of sodium hydroxide was changed to 111 g.
  • Example 4 The gas generation inhibitor for an electricity storage device of Example 4 (potassium titanate (K 2 Ti 2 O 5 )) was used in the same manner as in Example 1 except that 249 g of potassium hydroxide (Sigma Aldrich) was used. Produced.
  • potassium hydroxide Sigma Aldrich
  • Example 5 A gas generation inhibitor (potassium titanate (K 2 Ti 6 O 13 )) for an electricity storage device of Example 5 was produced in the same manner as in Example 4 except that the amount of potassium hydroxide was 108 g.
  • Example 6 A gas generation inhibitor for an electricity storage device (potassium titanate (K 2 Ti 4 O 9 )) of Example 6 was produced in the same manner as in Example 4 except that the amount of potassium hydroxide was 144 g.
  • Example 7 A gas generation inhibitor for an electricity storage device (magnesium titanate (MgTiO 3 )) of Example 7 was produced in the same manner as in Example 1 except that sodium hydroxide was changed to 438 g of magnesium hydroxide (manufactured by Sigma-Aldrich).
  • Example 8 A gas generation inhibitor (calcium titanate (CaTiO 3 )) for an electricity storage device of Example 8 was prepared in the same manner as in Example 1 except that sodium hydroxide was changed to 564 g of calcium hydroxide (manufactured by Sigma-Aldrich).
  • Example 9 Gas generation inhibitor for electricity storage device of Example 9 (strontium titanate (SrTiO 3 )) in the same manner as in Example 1 except that sodium hydroxide was changed to 997 g of strontium hydroxide octahydrate (manufactured by Sigma-Aldrich) Was made.
  • Example 10 Gas generation inhibitor for electricity storage device of Example 10 (barium titanate (BaTiO 3 )) in the same manner as in Example 1 except that sodium hydroxide was changed to 1194 g of barium hydroxide octahydrate (manufactured by Sigma-Aldrich) Was made.
  • barium hydroxide octahydrate manufactured by Sigma-Aldrich
  • the electrical storage device using the positive electrode was produced, and the suppression effect of gas generation, and the electrical storage device performance (cycle characteristics) Evaluation was performed.
  • each positive electrode paint produced above was applied to an aluminum foil and dried to produce each positive electrode for an electricity storage device.
  • the weight of the gas generation inhibitor for each power storage device of the example existing in the power storage device at this time is 16.5 mg
  • the weight ratio of the gas generation inhibitor for each power storage device of the example and activated carbon is 32: 68.
  • the amounts of the gas generation inhibitor for activated electricity storage device and the 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, as described later).
  • the weight of the gas generation inhibitor for the electricity storage device present in the electricity storage device is 3.9 mg, 33.6 mg, and 77.9 mg).
  • the weight ratios of the gas generation inhibitor for an electricity storage device and activated carbon in Example 3 were 19:81, 49:51, and 69:31, respectively.
  • a negative electrode for an electricity storage device was prepared by applying the negative electrode paint prepared above to an aluminum foil and drying it.
  • AMT-100 manufactured by Teica anatase type titanium oxide
  • volume change rate (%) volume change (ml) ⁇ initial volume (ml) ⁇ 100
  • IR drop measurement Next, discharge of each produced electricity storage device was started at a constant voltage of 2.9 V (that is, 2900 mV) under the condition of 60 ° C., and held for 1000 hours. Thereafter, the voltage 0.5 seconds after the start of discharge was measured, and IR drop was calculated from the following formula.
  • the IR drop is a value representing the internal resistance of the electricity storage device, and the smaller the value, the more preferable.
  • IR drop (mV) 2900 (mV) -voltage 0.5 seconds after the start of discharge (mV)
  • the electricity storage devices of Examples 11 to 23 exhibited a higher capacity maintenance rate (cycle characteristics) than the electricity storage devices of the comparative examples.
  • the electricity storage devices of Examples 11 to 23 had a good IR drop value as compared with the electricity storage device of the comparative example.
  • the gas generation inhibitor for an electricity storage device one or more titanates selected from sodium titanate, potassium titanate, and alkaline earth metal titanate. It has been found that the generation of various gases such as carbon dioxide gas, hydrogen gas, and fluorine gas during use or change with time, which has been a problem in conventional power storage devices, can be suppressed by containing the above. It was also found that an electricity storage device capable of exhibiting a high capacity retention rate (cycle characteristics) while suppressing generation of various gases can be obtained. Furthermore, it was also found that by suppressing gas generation, an increase in internal resistance of the electricity storage device is effectively suppressed, and as a result, IR drop can be reduced. This effect is particularly remarkable when the powder pH of the gas generation inhibitor for an electricity storage device is 10.5 or more (more preferably 11.0 or more, more preferably 11.5 or more). I understood it.
  • the gas generation inhibitor for an electricity storage device of the present invention can be used for an electricity storage device such as a lithium ion battery or an electric double layer capacitor.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • 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)

Abstract

Le problème décrit par la présente invention est de fournir un inhibiteur de génération de gaz de dispositif de stockage d'énergie qui peut inhiber la génération de gaz, tels que du gaz carbonique, du gaz hydrogène, et du gaz fluorure, qui a posé problème dans les dispositifs de stockage d'énergie antérieurs pendant l'utilisation et suite au vieillissement. La solution selon l'invention porte sur un inhibiteur de génération de gaz de dispositif de stockage d'énergie qui est caractérisé en ce qu'il contient au moins un type de titanate choisi parmi les titanates de sodium, les titanates de potassium et les titanates de métaux alcalino-terreux.
PCT/JP2018/017186 2017-05-01 2018-04-27 Inhibiteur de génération de gaz de dispositif de stockage d'énergie et dispositif de stockage d'énergie utilisant un inhibiteur de génération de gaz de dispositif de stockage d'énergie WO2018203523A1 (fr)

Priority Applications (1)

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JP2019515721A JP7121730B2 (ja) 2017-05-01 2018-04-27 蓄電デバイス用ガス発生抑制剤および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

Applications Claiming Priority (4)

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JP2017091481 2017-05-01
JP2017-091481 2017-05-01
JP2017-135140 2017-07-11
JP2017135140 2017-07-11

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003297699A (ja) * 2002-03-29 2003-10-17 Nec Tokin Corp 電気二重層キャパシタ
JP2007229602A (ja) * 2006-02-28 2007-09-13 Murata Mfg Co Ltd 炭酸ガス吸収材およびそれを用いた炭酸ガス吸収方法
JP2009106812A (ja) * 2007-10-26 2009-05-21 Toshiba Corp 炭酸ガス吸収材、炭酸ガス分離装置、改質装置、およびこの炭酸ガス吸収材の製造方法
JP2016197647A (ja) * 2015-04-03 2016-11-24 日本ケミコン株式会社 ハイブリッドキャパシタ用セパレータおよびハイブリッドキャパシタ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003297699A (ja) * 2002-03-29 2003-10-17 Nec Tokin Corp 電気二重層キャパシタ
JP2007229602A (ja) * 2006-02-28 2007-09-13 Murata Mfg Co Ltd 炭酸ガス吸収材およびそれを用いた炭酸ガス吸収方法
JP2009106812A (ja) * 2007-10-26 2009-05-21 Toshiba Corp 炭酸ガス吸収材、炭酸ガス分離装置、改質装置、およびこの炭酸ガス吸収材の製造方法
JP2016197647A (ja) * 2015-04-03 2016-11-24 日本ケミコン株式会社 ハイブリッドキャパシタ用セパレータおよびハイブリッドキャパシタ

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JPWO2018203523A1 (ja) 2020-04-09

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