WO2018072457A1 - Procédé de préparation d'un supercondensateur intégré à ions multiples avec activation alcaline électrochimique - Google Patents

Procédé de préparation d'un supercondensateur intégré à ions multiples avec activation alcaline électrochimique Download PDF

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Publication number
WO2018072457A1
WO2018072457A1 PCT/CN2017/087852 CN2017087852W WO2018072457A1 WO 2018072457 A1 WO2018072457 A1 WO 2018072457A1 CN 2017087852 W CN2017087852 W CN 2017087852W WO 2018072457 A1 WO2018072457 A1 WO 2018072457A1
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Prior art keywords
ldh
cobalt
electrolyte
supercapacitor
nickel
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PCT/CN2017/087852
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English (en)
Chinese (zh)
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邵明飞
栗振华
卫敏
段雪
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北京化工大学
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    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention belongs to the field of synthesis of inorganic nano materials, and particularly relates to a more universal method for preparing multi-ion embedded supercapacitors by electrochemical alkali activation method.
  • supercapacitors In order to enable energy storage equipment to have both high power density and energy density, as well as good cycle stability, researchers have proposed the concept of supercapacitors. It combines the advantages of traditional batteries and traditional capacitors. It has the characteristics of short charging time, long service life, good temperature characteristics, energy saving and environmental protection. It is expected to become an emerging high-efficiency energy storage device.
  • Supercapacitors can be divided into electric double layer capacitors and tantalum capacitors from the energy storage mechanism.
  • the supercapacitor electrode materials currently studied are mainly concentrated on carbon materials, conductive polymers, and inorganic metal oxides/hydroxides. Although supercapacitors have many attractive advantages, their further development and practicality still face enormous challenges.
  • the electrolyte used in the ion-embedded supercapacitor is mainly a neutral metal salt electrolyte, so it has a higher energy storage potential window than the conventional supercapacitor.
  • the research on ion-embedded supercapacitor electrode materials mainly focuses on metal carbide (MC X ), metal sulfide (MS X ) and metal oxide (MO X ), of which MXene is a new type with good electrical conductivity.
  • Layered metal carbides attract the attention of researchers and have become the main force in the development of electrode materials for ion-embedded supercapacitors.
  • Electrode material has low ability to store metal ions, poor conductivity, and preparation cost. Higher, these need to further develop new electrode materials with better performance suitable for rapid insertion/extraction of cations; 2. Most electrode materials have better embedding/extraction properties only for Li + , and for other metal cations (Na + , K + , Ca 2+ , Mg 2+ , Zn 2+ , Al 3+ ) have no storage performance or poor performance. However, considering the content of the earth's crust, the content of Li + in the earth's crust is the lowest relative to other metal cations. Therefore, it is extremely urgent to develop electrode materials suitable for the embedding/extraction of other metal cations.
  • the invention aims at the shortcomings of the current ion-intercalating electrode material in the low capacity of storing metal ions, poor conductivity, high preparation cost, etc., and proposes a metal hydroxide (MOH X ) as a novel ion-embedded supercapacitor electrode material through simple An electrochemical alkali activation method is used to improve the metal ion storage performance of the electrode material.
  • MOH X metal hydroxide
  • An electrochemical alkali activation method is used to improve the metal ion storage performance of the electrode material.
  • Step 1) Activated cobalt or nickel-containing metal hydroxide nanomaterial as positive electrode, 20–50 mL of alkaline solution with a concentration of 1–5 g/L as electrolyte, by cyclic voltammetry, at 1 At a scan rate of –100mV s -1 , cyclically scan 1–50 times at a potential window of 0–(-0.1V) to 0–(-1.5V) for deactivation;
  • the activated cobalt or nickel-containing metal hydroxide of step 1) or the deactivated cobalt or nickel-containing metal hydroxide of step 2) is used as a positive electrode, and 1–5 g/L
  • the nitrate or sulfate electrolyte solution constitutes a multi-ion embedded supercapacitor for ion storage performance testing.
  • the alkaline solution as the electrolyte described in the step 1) or 2) is one or more of KOH, NaOH, and LiOH.
  • the cobalt-containing hydroxide used in the step 1) is one or more of Co(OH) 2 , CoNi-LDH, CoFe-LDH, CoAl-LDH, CoMn-LDH, and CoV-LDH.
  • the nickel-containing hydroxide used in the step 1) is one or more of Ni(OH) 2 , NiFe-LDH, NiAl-LDH, NiMn-LDH, and NiV-LDH.
  • the metal nitrate electrolyte used in the step 3) is: LiNO 3 , NaNO 3 , KNO 3 , Ca(NO 3 ) 2 , Mg(NO 3 ) 2 or Zn(NO 3 ) 2 .
  • the metal sulfate electrolyte used in the step 3) is: Li 2 SO 4 , Na 2 SO 4 , K 2 SO 4 , CaSO 4 , MgSO 4 or ZnSO 4 .
  • the invention has the advantages that the activation or deactivation treatment of the cobalt or nickel-containing hydroxide by a simple and rapid electrochemical alkali activation method realizes the storage capacity of the hydroxide electrode material for various metal cations.
  • Intelligent regulation can be effectively applied to ion-embedded supercapacitors; it provides a new and more versatile method to greatly improve the energy storage performance of ion-embedded supercapacitor electrode materials; further broaden the transition metal hydroxide electrode The range of applications of materials in the field of energy storage.
  • Figure 1 is a diagram showing the mechanism of electrochemical alkali activation and deactivation of a metal hydroxide in Example 1, and metal ion cation insertion and removal.
  • Figure 2 is a cyclic voltammetry curve for the storage of different metal cations of cobalt iron hydrotalcite before and after electrochemical alkali activation treatment (represented by AA and BA, respectively) in Example 1.
  • Figure 3 is a graph showing the charge and discharge curves of cobalt iron hydrotalcite for storage of different metal cations before and after electrochemical alkali activation treatment (represented by AA and BA, respectively) in Example 1.
  • Figure 4 is an intelligently controlled cyclic voltammetry curve for lithium ion storage capacity of cobalt iron hydrotalcite treated by electrochemical alkali activation (denoted by AA) and deactivated (represented by DA) in Example 1.
  • Fig. 5 is a graph showing the stability of the cobalt-iron hydrotalcite after the electrochemical alkali activation treatment in Example 1 after 10,000 consecutive charge and discharge tests.
  • step b using the activated cobalt-hydrotalcite nano-array of step 1) as a positive electrode, by cyclic voltammetry, at a scanning rate of 100 mV s -1 , under a potential window of 0 - (-0.6 V), cyclic scanning 5 Deactivation treatment;
  • the cobalt iron hydrotalcite subjected to the activation treatment or deactivation treatment in step 1) or 2) is used as a positive electrode at a concentration of 5 g/L of nitrate (LiNO 3 , NaNO 3 , KNO 3 , Ca(NO 3 ) 2 , Mg(NO). 3 ) 2 , Zn(NO 3 ) 2 ) or sulfate (Li 2 SO 4 , Na 2 SO 4 , K 2 SO 4 , CaSO 4 , MgSO 4 , ZnSO 4 ) electrolyte solution for ion storage performance test.
  • nitrate LiNO 3 , NaNO 3 , KNO 3 , Ca(NO 3 ) 2 , Mg(NO). 3 ) 2 , Zn(NO 3 ) 2
  • sulfate Li 2 SO 4 , Na 2 SO 4 , K 2 SO 4 , CaSO 4 , MgSO 4 , ZnSO 4
  • step 1) using the activated cobalt-hydrotalcite nanocrystal array of step 1) as a positive electrode, cyclically scanning 10 by a cyclic voltammetry at a scanning rate of 50 mV s -1 at a potential window of 0 - (-0.5 V) Deactivation treatment;
  • b using a cobalt hydroxide nano-array as a positive electrode, by cyclic voltammetry, at a scanning rate of 100 mV s -1 , under a potential window of 0 - 0.1 V, cyclic scanning 20 times, for activation treatment;
  • step b using the activated cobalt oxide nano-array of step 1) as a positive electrode, cyclically scanning 10 by cyclic voltammetry at a scanning rate of 100 mV s -1 under a potential window of 0 - (-0.1 V) Deactivation treatment;
  • the step 1) or 2) activated or deactivated cobalt hydroxide is used as the positive electrode at 5 g/L of nitrate (LiNO 3 , NaNO 3 , KNO 3 , Ca(NO 3 ) 2 , Mg(NO). 3 ) 2 , Zn(NO 3 ) 2 ) or sulfate (Li 2 SO 4 , Na 2 SO 4 , K 2 SO 4 , CaSO 4 , MgSO 4 , ZnSO 4 ) electrolyte solution for ion storage performance test.
  • nitrate LiNO 3 , NaNO 3 , KNO 3 , Ca(NO 3 ) 2 , Mg(NO). 3 ) 2 , Zn(NO 3 ) 2
  • sulfate Li 2 SO 4 , Na 2 SO 4 , K 2 SO 4 , CaSO 4 , MgSO 4 , ZnSO 4
  • b using a nickel hydroxide nano-array as a positive electrode, by cyclic voltammetry, at a scanning rate of 1-100 mV s -1 , under a potential window of 0-0.1 V, cyclically scanning 5 times for activation treatment;
  • step b using the activated nickel hydroxide nano-array of step 1) as a positive electrode, by cyclic voltammetry, at a scanning rate of 100 mV s -1 , under a potential window of 0 - (-0.1 V), cyclic scanning 5 Deactivation treatment;
  • Step 1) or 2) Activated or deactivated nickel hydroxide is used as the positive electrode at 5 g/L of nitrate (LiNO 3 , NaNO 3 , KNO 3 , Ca(NO 3 ) 2 , Mg ( The ion storage performance test was carried out in an electrolyte solution of NO 3 ) 2 , Zn(NO 3 ) 2 ) or sulfate (Li 2 SO 4 , Na 2 SO 4 , K 2 SO 4 , CaSO 4 , MgSO 4 , ZnSO 4 ).

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention concerne un procédé de préparation d'un supercondensateur intégré à ions multiples avec activation alcaline électrochimique. Un procédé d'activation alcaline électrochimique simple et rapide est employé pour effectuer un traitement d'activation ou de désactivation sur un hydroxyde de métal de transition contenant du cobalt ou du nickel pour réaliser une régulation et une commande intelligentes des matériaux d'électrode à base d'hydroxyde sur la capacité de stockage de divers cations métalliques, et est appliqué à un supercondensateur intégré aux ions. L'invention concerne un procédé universel capable d'améliorer la capacité de stockage de matériaux d'électrode d'un supercondensateur intégré aux ions, et la plage d'application des matériaux d'électrode à hydroxyde de métal de transition est encore élargie dans le domaine du stockage d'énergie.
PCT/CN2017/087852 2016-10-21 2017-06-11 Procédé de préparation d'un supercondensateur intégré à ions multiples avec activation alcaline électrochimique WO2018072457A1 (fr)

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CN111575730A (zh) * 2020-04-27 2020-08-25 大连理工大学 一种用于海水电解的整体式碳基电极的制备方法
CN113077990A (zh) * 2021-03-17 2021-07-06 三峡大学 一种双电位区间活化提高Co(OH)2超级电容器性能的方法
CN113279009A (zh) * 2021-04-28 2021-08-20 北京化工大学 一种具有空穴传输和助催化双功能光电催化界面的复合光阳极的制备方法
CN116741977A (zh) * 2023-08-16 2023-09-12 中石油深圳新能源研究院有限公司 一种溶解沉积型锰氧化物正极材料及其制备方法和应用
CN117684202A (zh) * 2024-02-02 2024-03-12 东华大学 一种表面修饰的析氧电催化剂及其制备方法

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CN106409532B (zh) * 2016-10-21 2019-08-13 北京化工大学 一种电化学碱活化法制备多离子嵌入式超级电容器的方法
CN107369566A (zh) * 2017-07-27 2017-11-21 桂林理工大学 一种超级电容器用钴镍水滑石电极材料的制备方法及应用
CN110346437B (zh) * 2019-07-15 2022-03-15 北京工商大学 一种基于LDHs/MXene的电化学葡萄糖传感器及其制备和应用
CN111029172A (zh) * 2019-12-31 2020-04-17 青岛科技大学 一种二维层状超级电容器电极材料Ti3C2 MXene的层间结构调控方法
CN112467077A (zh) * 2020-11-29 2021-03-09 西北工业大学 有效增强多种过渡金属氧化物储电性能的普适性电化学改性制备方法
CN112928256A (zh) * 2021-01-25 2021-06-08 北京化工大学 新型钠离子正极材料制备方法
CN113512737B (zh) * 2021-04-01 2022-07-19 安徽大学 一种氢氧化镍电催化剂、制备方法、电化学活化方法及其应用
CN114360927B (zh) * 2022-01-21 2022-09-09 重庆源皓科技有限责任公司 一种氢氧化镍电极材料的制备方法

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Publication number Priority date Publication date Assignee Title
CN111575730A (zh) * 2020-04-27 2020-08-25 大连理工大学 一种用于海水电解的整体式碳基电极的制备方法
CN111575730B (zh) * 2020-04-27 2022-08-19 大连理工大学 一种用于海水电解的整体式碳基电极的制备方法
CN113077990A (zh) * 2021-03-17 2021-07-06 三峡大学 一种双电位区间活化提高Co(OH)2超级电容器性能的方法
CN113279009A (zh) * 2021-04-28 2021-08-20 北京化工大学 一种具有空穴传输和助催化双功能光电催化界面的复合光阳极的制备方法
CN113279009B (zh) * 2021-04-28 2022-05-27 北京化工大学 一种具有空穴传输和助催化双功能光电催化界面的复合光阳极的制备方法
CN116741977A (zh) * 2023-08-16 2023-09-12 中石油深圳新能源研究院有限公司 一种溶解沉积型锰氧化物正极材料及其制备方法和应用
CN116741977B (zh) * 2023-08-16 2024-01-26 中石油深圳新能源研究院有限公司 一种溶解沉积型锰氧化物正极材料及其制备方法和应用
CN117684202A (zh) * 2024-02-02 2024-03-12 东华大学 一种表面修饰的析氧电催化剂及其制备方法
CN117684202B (zh) * 2024-02-02 2024-05-31 东华大学 一种表面修饰的析氧电催化剂及其制备方法

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