WO2007009363A1 - Supercondensateur électrochimique utilisant un matériau composite à radical libre de polymère organique/carbone comme électrode positive - Google Patents

Supercondensateur électrochimique utilisant un matériau composite à radical libre de polymère organique/carbone comme électrode positive Download PDF

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Publication number
WO2007009363A1
WO2007009363A1 PCT/CN2006/001686 CN2006001686W WO2007009363A1 WO 2007009363 A1 WO2007009363 A1 WO 2007009363A1 CN 2006001686 W CN2006001686 W CN 2006001686W WO 2007009363 A1 WO2007009363 A1 WO 2007009363A1
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WO
WIPO (PCT)
Prior art keywords
carbon
organic polymer
radical
composite material
positive electrode
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Application number
PCT/CN2006/001686
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English (en)
Chinese (zh)
Inventor
Huiqiao Li
Yongyao Xia
Original Assignee
Fudan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fudan University filed Critical Fudan University
Publication of WO2007009363A1 publication Critical patent/WO2007009363A1/fr

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Classifications

    • 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
    • H01G11/32—Carbon-based
    • 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
    • H01G11/48—Conductive polymers
    • 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 technical field of electrochemical supercapacitors, and particularly relates to an electrochemical supercapacitor of an organic polymer radical/carbon composite material as a positive electrode material. Background technique
  • EDLC electrochemical double layer capacitor
  • the first category Carbon materials, whose capacity is derived from the separation of positive and negative charges on the surface of carbon materials, that is, the formation of interfacial electric double layers. Including activated carbon powder, carbon fiber, carbon nanotubes, carbon aerogel, etc. The cycle life and power characteristics of carbon materials are unmatched by other existing materials. Therefore, commercial electrochemical ultracapacitors mostly use activated carbon, and the specific power can be greater than 2000 W/kg. However, since the specific capacity of carbon and the voltage of the single capacitor are relatively low, the energy density is low and it is difficult to exceed 2 to 5 W /kg.
  • the second category transition metal oxides, mainly using its redox quasi-capacitance.
  • oxides of noble metals Ru and Ir and relatively inexpensive metal oxides or nitrides such as Ni, Co, Mn, Mo, W are used as quasi-capacitance electrode materials for ultracapacitors. Capacitor energy density using such materials is significantly higher than that of carbon double layer capacitors, but the specific power is reduced.
  • the third type conductive polymers such as polyaniline, polypyrrole, polythiophene, etc., generate a quasi-capacitance during doping and dedoping. Its energy density is higher than that of carbon materials, but its cycle life is poor. In recent years, a hybrid asymmetric capacitor has emerged.
  • This hybrid capacitor uses an electrochemically supercapacitor activated carbon material on one pole and a battery material on the other pole to greatly increase the specific energy of the capacitor.
  • the organic polymer radical carbon composite material of the invention is used as a positive electrode material of a capacitor, which not only solves the problem of poor conductivity, but also utilizes the electric double layer capacity of the carbon material itself.
  • the electrode material has the characteristics of a specific capacity, a large charge and discharge rate, and thus can produce a high specific energy, high power, and long life electrochemical ultracapacitor. Disclosure of invention
  • the electrochemical ultracapacitor proposed by the invention adopts an organic polymer radical/carbon composite material for the positive electrode, and the composite material is composed of an organic polymer radical and a carbon material composite.
  • the organic polymer radical refers to a stable polymer in which a group of amino groups or substituted amino groups are oxidized to nitrogen oxide radicals, wherein the group linked to the nitrogen element may be a linear alkane, a cyclic alkane and a derivative thereof. It may also be an aromatic, a heterocyclic ring or a derivative thereof, and such a nitrogen-oxygen radical may undergo the following reaction during charge and discharge:
  • Mw represents the average molecular weight per mole of radical (g/mol) and C represents the theoretical specific capacity (mA / g).
  • the carbon material compounded with the organic polymer radical material is mainly various types of activated carbon, mesoporous carbon, carbon nanotube, activated carbon fiber or carbon gel.
  • the temperature at which high temperature carbonization is carried out in the preparation of the above carbon material is generally 750 ° C or higher.
  • the mass percentage of the organic polymer radical material in the composite material is 10% to 50%.
  • the capacity contribution is small, the capacity increase of the capacitor is limited, and the effect is not obvious.
  • the electrode is The conductivity is much lower, and the internal resistance causes the rate performance to drop rapidly.
  • the organic polymer radical/carbon composite material can be prepared by first recombining, that is, the organic polymer monomer is first dissolved in a reaction solvent (such as benzene or toluene), the carbon material is added, and the mixture is stirred to make the mixture uniform. Then, it was polymerized in a vacuum tube for several hours under a nitrogen atmosphere, and then -NH was oxidized to -N-0 radical with m-chloroperoxybenzoic acid, and the product was precipitated and filtered to obtain a polymer radical/carbon composite.
  • a reaction solvent such as benzene or toluene
  • first polymerize and recombine that is, first dissolve the organic polymer monomer in a reaction solvent, polymerize in a vacuum tube under nitrogen protection, and then oxidize -NH to -N-0 radical with m-chloroperoxybenzoic acid,
  • the polymer radical material is filtered to be mixed with the carbon material; the mixing may be carried out by dry mixing, that is, mechanical grinding, by ball milling in a ball mill at a speed of 200 rad/min to 400 rad/min for 1 to 2 hours.
  • the above composite material is used as a positive electrode, and a general carbon material is used as a negative electrode, and a nonaqueous system electrolyte such as tetraethylammonium tetrafluoroborate ((C 2 3 ⁇ 4 ) 4 NBF 4 ) or hexafluoroborate is used.
  • a nonaqueous system electrolyte such as tetraethylammonium tetrafluoroborate ((C 2 3 ⁇ 4 ) 4 NBF 4 ) or hexafluoroborate is used.
  • Ethyl ammonium (C 2 H 5 )NPF 6 ), tetraethylammonium perchlorate ((C 2 H 5 ) 4 NC10 4 ), lithium perchlorate (LiC10 4 ), lithium hexafluorophosphate (LiPF 6 ), tetrafluoroboric acid Lithium (LiBF 4 ) or lithium trifluoromethanesulfonate (CF 3 S0 3 Li), etc.
  • the organic solvent as the electrolyte solution may be dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene carbonate (EC). ) propylene carbonate (PC), vinyl acetate (EMC), methyl propyl carbonate (MPC), 1,2-dimethoxyethane (DME) or 1,4-butyrolactone (GBL), etc.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EC ethylene carbonate
  • PC propylene carbonate
  • PC vinyl
  • the above organic polymer radical/carbon composite material is used as a positive electrode, and the general carbon material is a negative electrode and the above electricity.
  • the mass ratio of the respective electrode materials is determined according to the positive electrode capacity equal to the negative electrode capacity, and the charge and discharge interval of the capacitor may be 0 to 3 V.
  • the preparation method of the electrochemical supercapacitor of the invention is identical to the preparation method of the general electrochemical supercapacitor except that the preparation of the positive electrode material is carried out.
  • the invention uses the organic polymer nitroxyl radical/carbon composite material as the positive electrode of the ultracapacitor, and assembles the capacitor into the capacitor with the general carbon material as the negative electrode, which overcomes the disadvantage that the free radical material has poor conductivity and is difficult to be applied, and in the carbon double
  • the adsorption capacity of the layer increases the redox capacitance of the organic radicals, which increases the specific energy of the system.
  • Figure 1 shows the charge and discharge curves of a Li/PTMA button cell.
  • the electrolyte lM LiCL0 4 /PC. The best way to implement the invention
  • Poly(4-methacryloyloxy-2,2,6,6-tetramethyl-piperidinol oxynitride oly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) represented by the above structural formula (1) (PTMA), for example, first use a button cell to test the capacity of the free radical material, using no capacity graphite as a conductive agent, and the positive pole piece is composed of PTMA: graphite: binder 1 : 8: 1
  • the negative electrode is a lithium plate, the separator is a commercial capacitor separator, and the electrolyte is l M LiCL0 4 /PC.
  • the voltage capacity curve is shown in Figure 1.
  • the charging platform is about 3.6 V
  • the discharge platform is about 3.5 V
  • the capacity is 82 mAh/g when charging and discharging in 1C.
  • the mass of PTMA itself in the electrode is 80% of the theoretical capacity (110 mA / g), which may be due to the inevitable inactivity of some of the materials in the preparation, and the capacity of ordinary activated carbon-carbon materials is only 30 ⁇ 35 mAh/g.
  • Both the positive and negative electrodes are made of commercial activated carbon (specific surface: 1600 cm 2 /g), hereinafter referred to as activated carbon, assembled into a symmetrical capacitor.
  • the active material of the control electrode i.e., the electrode material other than the conductive agent and the binder
  • a lithium foil was used as a negative electrode, and a separator and an electrolyte were assembled into a button cell for the single electrode capacity test in the same manner as in Example 1.
  • the specific capacity of the activated carbon material was 35 mAh/g in the range of 3 to 4.5 V.
  • the positive and negative electrodes are made of activated carbon electrode, the diaphragm is still a commercial capacitor separator, and the electrolyte is still 1 M LiCL0 4 /PC, assembled into Button-type symmetrical capacitors.
  • the capacitor was electrochemically tested, and its capacity (calculated as the total weight of the negative electrode active material, the same below) was 17.5 mAh/g, and the cycle life and rate performance are shown in Table 1.
  • a wet method the PTMA is dissolved in a certain amount of N-methylpyrrolidone, activated carbon is added, stirred well, and the solvent is slowly evaporated to obtain a complex.
  • the composite was used as the positive electrode, and the lithium plate was used as the negative electrode to form a button type battery, and the capacity test was performed, and the specific capacity was 39.5 mAh/g in the range of 3 to 4.5 V.
  • the button type asymmetric capacitor was assembled according to the method of Example 2, wherein the surface density of the negative electrode carbon film was still 10 mg/cm 2 , but the surface density of the positive electrode composite material was 8.8. Mg/cm 2 .
  • the specific capacity of the capacitor is 18.4 mAh/g. Its cycle life and rate performance are listed in Table 1. Compared with carbon/carbon double-layer capacitors, it can be seen that its capacity increase is not much, but its cycle life and rate performance are close to those of carbon/carbon double-layer capacitors. It can be seen that when the loading amount of the organic radical of the polymer is small, the cycle performance and the rate characteristic of the activated carbon can be well maintained without being greatly affected.
  • a PTMA/activated carbon composite material was prepared in the same manner as in Example 3, and the compounding amount was 30%. Using a lithium plate as the counter electrode, a single-electrode test was performed with a capacity of 48 mA / g in the range of 3 to 4.5 V, which was 1.5 times that of the activated carbon electrode (35 mAh/g).
  • An asymmetric capacitor was assembled in the same manner as in Example 2, in which the areal densities of the positive and negative electrodes were 7.2 mg/cm 2 and 10 mg/cm 2 , respectively . In the interval of 0 ⁇ 3 V, the specific capacity of the capacitor is 20.2 mA / g, and the cycle performance and rate performance are differently lower than that of the electric double layer capacitor, as shown in Table 1.
  • the PTMA/activated carbon material was compounded by mechanical mixing, and the content of free radical material was still 30%.
  • the PTMA powder and activated carbon powder with mass ratio of 3:7 were mechanically ground for 1 h and used as electrode materials.
  • the single electrode capacity test and the assembly of the asymmetric capacitor were the same as in Example 4.
  • the electrical properties are listed in Table 1. It can be seen that the specific capacity of the capacitor during dry compounding is not significantly different from that of Example 4, but the cycle life and rate performance are not as good as in Example 4, which may be due to dry mixing.
  • Activated carbon and PTMA are only simple mixed packings between particles, which have little effect on increasing the conductivity of PTMA.
  • PTMA When mixed by wet method, since PTMA has been dissolved in advance, after adding activated carbon, the solvent infiltrates the activated carbon, and the PTMA dissolved therein can also reach the pores inside the activated carbon particles. When the solvent is slowly volatilized, PTMA is The surface of the activated carbon gradually precipitates, so that PTMA can be uniformly dispersed on the specific surface of the activated carbon, and it is difficult to form large particles to crystallize. At the same time, since the amount of PTMA is small relative to activated carbon, it covers only a thin layer on the surface of activated carbon. The thinner dispersion layer and better dispersion uniformity make the wet composite electrode have a smaller internal resistance and thus exhibit better electrical properties than dry composite.
  • the radical material was tested by the method of Example 1 using the poly(N-tert-butyl-acrylamideoxy) (PBAA) represented by the above structural formula (2).
  • the capacity is 146 mAh/g.
  • a PTMA/activated carbon composite material was prepared in the same manner as in Example 3, and the compounding amount was 10%.
  • the single-electrode test has a capacity of 46 mAh/g in the range of 3 to 4.5 V, which is a greater improvement than the activated carbon electrode (35 mAh/g).
  • Positive control, negative electrode surface density were 7.6 mg / C m 2 and 10 mg / cm 2, in the same manner as in Example 2 is assembled asymmetric capacitor.
  • the content of 0 to 3 V interval is 19.8 mAh/g, and the cycle life and rate performance are shown in Table 1.

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

Abstract

Supercondensateur électrochimique et son procédé de fabrication, le supercondensateur électrochimique comportant comme matériau d'électrode positive un matériau composite radical libre de polymère organique/carbone. Le supercondensateur ainsi préparé applique à la fois le radical libre de polymère organique et le matériau composite au carbone, si bien que non seulement il résout le problème de la faible conductivité, mais il peut également exploiter la capacité électrique double couche du matériau de carbone.
PCT/CN2006/001686 2005-07-15 2006-07-14 Supercondensateur électrochimique utilisant un matériau composite à radical libre de polymère organique/carbone comme électrode positive WO2007009363A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200510027782.9 2005-07-15
CN 200510027782 CN1741214A (zh) 2005-07-15 2005-07-15 有机聚合物自由基/碳复合材料为正极的电化学超电容器

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WO2007009363A1 true WO2007009363A1 (fr) 2007-01-25

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115275192A (zh) * 2022-09-02 2022-11-01 天津大学 高掺杂可用性导电聚合物正极材料的制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102263264A (zh) * 2011-06-28 2011-11-30 中国科学院化学研究所 一种自由基聚合物/石墨烯复合材料及其制备方法与应用
CN107892731A (zh) * 2017-11-07 2018-04-10 陕西科技大学 一种磺酸盐内掺杂氮氧自由基聚合物及其制备方法
CN111029158B (zh) * 2019-12-22 2021-12-17 北京蒙京石墨新材料科技研究院有限公司 一种锂离子超级电容器预嵌锂方法
CN114694974A (zh) * 2020-12-30 2022-07-01 禾达材料科技股份有限公司 卷绕型电解电容器封装结构及其卷绕式抗腐蚀负极箔片

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CN1310485A (zh) * 2000-02-25 2001-08-29 日本电气株式会社 二次电池
CN1500293A (zh) * 2001-04-03 2004-05-26 日本电气株式会社 电荷存储设备
JP2004200058A (ja) * 2002-12-19 2004-07-15 Nec Corp 蓄電デバイス
JP2004200059A (ja) * 2002-12-19 2004-07-15 Nec Corp 蓄電デバイス
JP2004227946A (ja) * 2003-01-23 2004-08-12 Nec Corp 二次電池、単量体および重合体
CN1529334A (zh) * 2003-10-17 2004-09-15 �廪��ѧ 聚苯胺/碳纳米管混杂型超电容器
CN1597781A (zh) * 2004-08-12 2005-03-23 河北工业大学 聚吡咯/炭黑纳米复合材料及其制备方法
WO2005078830A1 (fr) * 2004-02-16 2005-08-25 Nec Corporation Dispositif de stockage électrique

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1310485A (zh) * 2000-02-25 2001-08-29 日本电气株式会社 二次电池
CN1500293A (zh) * 2001-04-03 2004-05-26 日本电气株式会社 电荷存储设备
JP2004200058A (ja) * 2002-12-19 2004-07-15 Nec Corp 蓄電デバイス
JP2004200059A (ja) * 2002-12-19 2004-07-15 Nec Corp 蓄電デバイス
JP2004227946A (ja) * 2003-01-23 2004-08-12 Nec Corp 二次電池、単量体および重合体
CN1529334A (zh) * 2003-10-17 2004-09-15 �廪��ѧ 聚苯胺/碳纳米管混杂型超电容器
WO2005078830A1 (fr) * 2004-02-16 2005-08-25 Nec Corporation Dispositif de stockage électrique
CN1597781A (zh) * 2004-08-12 2005-03-23 河北工业大学 聚吡咯/炭黑纳米复合材料及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115275192A (zh) * 2022-09-02 2022-11-01 天津大学 高掺杂可用性导电聚合物正极材料的制备方法
CN115275192B (zh) * 2022-09-02 2024-04-30 天津大学 高掺杂可用性导电聚合物正极材料的制备方法

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