WO2020118880A1 - Graphite positive electrode and zinc negative electrode-based hybrid super capacitor - Google Patents

Graphite positive electrode and zinc negative electrode-based hybrid super capacitor Download PDF

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WO2020118880A1
WO2020118880A1 PCT/CN2019/073245 CN2019073245W WO2020118880A1 WO 2020118880 A1 WO2020118880 A1 WO 2020118880A1 CN 2019073245 W CN2019073245 W CN 2019073245W WO 2020118880 A1 WO2020118880 A1 WO 2020118880A1
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positive electrode
zinc
negative electrode
graphite
hybrid supercapacitor
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PCT/CN2019/073245
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French (fr)
Chinese (zh)
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崔光磊
陈政
赵井文
徐红霞
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中国科学院青岛生物能源与过程研究所
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • 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 energy storage, and in particular relates to a hybrid supercapacitor composed of a graphite positive electrode, a zinc negative electrode and an organic solvent electrolyte.
  • Lithium-ion batteries are currently widely used energy storage devices, which have the advantages of high energy density and low self-discharge rate, but they also have obvious disadvantages.
  • lithium-ion batteries have high costs, poor safety performance, and cannot be quickly charged and discharged.
  • Supercapacitors are a new type of energy storage devices between traditional capacitors and secondary batteries. From the charge storage mechanism, they can be divided into electric double layer capacitors without Faraday charge transfer and pseudocapacitors with Faraday charge transfer. Compared with batteries, supercapacitors have the advantages of high power density, short charging time, high safety, and environmental protection. Although the energy density of supercapacitors has been greatly improved compared to traditional capacitors, compared with lithium-ion batteries, the energy density is still low, generally less than 40Wh/kg, which greatly limits its scope of application.
  • the decomposition voltage of water in a standard state is 1.23V
  • the operating voltage of the aqueous zinc ion hybrid capacitor is low, and the corresponding energy density is also low.
  • another disadvantage of water-based zinc ion batteries or hybrid capacitors is that zinc dendrites are easily generated during charge and discharge cycles, and there is a potential danger of short circuits in the battery.
  • the negative electrode is a porous carbon material that can adsorb and desorb zinc ions.
  • the positive electrode is a graphite that can reversibly deintercalate anions. Carbon material.
  • the negative electrode of this patent occurs that the activated carbon material absorbs and desorbs zinc ions through the electric double layer capacitance effect, which is much lower than the specific capacity corresponding to the zinc ion deposition and dissolution reaction on the surface of the zinc or zinc alloy negative electrode, resulting in the dual ion battery. Or the energy density of the capacitor is low.
  • Graphite is a layered carbon material with high crystallinity and fixed interlayer spacing. It can quickly and reversibly intercalate and deintercalate anions between layers within a certain voltage range. It is a type of pseudocapacitor with Faraday charge transfer characteristics. Charge storage mechanism, this reaction has the advantages of high specific capacity and high output voltage compared to the double-layer capacitance behavior of activated carbon materials adsorbing and desorbing anions through the surface, because graphite as a cathode material can greatly improve the mixing based on zinc anode The energy density of supercapacitors.
  • the present invention provides a hybrid supercapacitor based on a zinc anode, a graphite cathode and an organic solvent electrolyte.
  • the hybrid supercapacitor is a new type of energy storage device, and one of its electrodes exhibits ion desorption Embedded or deposited dissolved battery reaction characteristics, the other side of the electrode exhibits the electric double layer capacitance or pseudocapacitance characteristics of the supercapacitor, so that it combines the characteristics of the battery's high capacity and the supercharger's rapid charge and discharge characteristics, so It has great potential application value in the fields of mobile communication, consumer electronics, electric vehicles, etc.
  • a hybrid supercapacitor based on graphite positive electrode and zinc negative electrode including a positive electrode, a negative electrode, a separator and an electrolyte interposed between the positive electrode and the negative electrode;
  • the negative electrode active material deposits zinc ions during charging and discharging Or dissolution reaction;
  • the positive electrode active material undergoes a reaction of anion insertion or extraction between graphite layers during charge and discharge;
  • the electrolyte includes a zinc salt electrolyte and an organic solvent.
  • the negative electrode active material is one or more of zinc flake, zinc foil, zinc powder, and zinc alloy.
  • the negative electrode material further includes a negative electrode current collector.
  • the positive electrode material is composed of a positive electrode active material with a mass fraction of 85-95%, a conductive agent of 0-5%, and a binder of 5-10%.
  • the positive electrode active material is graphite, including one or a combination of natural graphite and artificial graphite.
  • the cathode material further includes a cathode current collector.
  • the binder is one or a combination of at least two of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, and styrene-butadiene rubber.
  • the zinc salt electrolyte is ZnSO 4 , Zn(NO 3 ) 2 , Zn(ClO 4 ) 2 , Zn(BF 4 ) 2 , Zn(CF 3 SO 3 ) 2 , Zn[N(CF 3 SO 2 ) 2 ] 2.
  • Zn(PF 6 ) 2 are mixed at a certain ratio, and the concentration of zinc ions in the zinc salt electrolyte ranges from 0.1 to 5 mol/L.
  • the organic solvent is an organic solvent with a dielectric constant greater than 20, including one or more of acetonitrile, propylene carbonate, and ethylene carbonate mixed in a certain ratio.
  • the method for preparing the hybrid supercapacitor based on the graphitized carbon material positive electrode and the zinc negative electrode above assembles the positive electrode, the negative electrode, the separator and the electrolyte to obtain the hybrid supercapacitor.
  • the present invention has the following advantages:
  • the hybrid supercapacitor based on graphite positive electrode and zinc negative electrode uses low-cost and resource-rich graphite as the positive electrode active material, and metallic zinc as the negative electrode active material, which can greatly reduce the material cost of the hybrid supercapacitor; the electrolyte is used
  • the organic solvent containing zinc salt is used as the electrolytic solvent. It has been experimentally verified that the negative electrode does not have the problem of zinc dendrite growth (Figure 6), and the safety is high; the graphite positive electrode of the hybrid supercapacitor occurs between the graphite layers during charging and discharging.
  • FIG. 1 is a charge-discharge curve diagram under the test condition of 5000 mA/g current density in Example 1 of the present invention.
  • Example 2 is a cyclic voltammetry curve of a graphite positive electrode at a sweep speed of 1 mV/s in Example 2 of the present invention.
  • FIG. 3 is an XRD spectrum of a graphite positive electrode in a charged state and a discharged state in Example 3 of the present invention.
  • Example 4 is a graph of cycle performance under the current density test condition of 5000 mA/g in Example 4 of the present invention.
  • Example 5 is a graph of rate performance under different current density test conditions in Example 5 of the present invention.
  • Example 6 is a scanning electron micrograph of the surface of the zinc negative electrode after 1000 charge-discharge cycles under the 5000 mA/g current density test condition in Example 6 of the present invention.
  • Table 1 is the energy density comparison of the hybrid supercapacitors described in Examples 1-8 of the present invention and Comparative Examples 1-3.
  • the porous activated carbon and the binder styrene-butadiene rubber are mixed in a mass ratio of 9:1, and the mixed slurry is scraped on the cleaned aluminum foil positive electrode collector with a scraper to a film with a thickness of 150 ⁇ m, dried and cut to a diameter 12mm positive pole piece.
  • the negative pole piece uses zinc foil with a diameter of 12 mm.
  • a 1 mol/L concentration of Zn(CF 3 SO 3 ) 2 aqueous solution was used as an electrolyte, and a glass fiber with a diameter of 16.5 mm was used as a separator, and 150 ⁇ L of electrolyte was added dropwise on the separator.
  • the battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top.
  • the assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours to obtain the water-based hybrid supercapacitor described in this comparative example. Then use the blue electric tester to perform the electrochemical performance test, the test current is 5000mA/g, and the measured energy density calculation is shown in Table 1.
  • the porous activated carbon and the binder polyvinylidene fluoride are mixed at a mass ratio of 9:1, and the mixed slurry is scraped on the washed aluminum foil positive current collector with a scraper to a film with a thickness of 150 ⁇ m, dried and cut into A positive pole piece with a diameter of 12 mm.
  • the negative pole piece uses zinc foil with a diameter of 12 mm.
  • a Zn(CF 3 SO 3 ) 2 /acetonitrile solution at a concentration of 1 mol/L is used as an electrolyte, and a glass fiber with a diameter of 16.5 mm is used as a separator, and 150 ⁇ L of electrolyte is added dropwise on the separator.
  • the battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top.
  • the assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours to obtain an organic system hybrid supercapacitor based on the activated carbon positive electrode described in this comparative example. Then use the blue electric tester to perform the electrochemical performance test, the test current is 5000mA/g, and the measured energy density calculation is shown in Table 1.
  • Comparative Example 3 (asymmetric supercapacitor with negative electrode as activated carbon, positive electrode as graphite, and electrolyte solvent as organic solvent):
  • a Zn(CF 3 SO 3 ) 2 /acetonitrile solution at a concentration of 1 mol/L is used as an electrolyte, and a glass fiber with a diameter of 16.5 mm is used as a separator, and 150 ⁇ L of electrolyte is added dropwise on the separator.
  • the battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top.
  • the assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours to obtain the organic system hybrid supercapacitor based on the activated carbon negative electrode described in this comparative example. Then use the blue electric tester to perform the electrochemical performance test, the test current is 5000mA/g, and the measured energy density calculation is shown in Table 1.
  • the battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top.
  • the assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours, and then the electrochemical performance test is performed with a blue electric tester.
  • the working test voltage range is 1.2V-2.65V, and the charging and discharging curve is shown in Figure 1 under the current density test condition of 5000mA/g.
  • Figure 1 shows that the charging and discharging curve of the hybrid supercapacitor obtained in this example shows a typical super The characteristics of the capacitor, the specific capacity is 52mAh/g, the charging time is only 90 seconds, and the average output voltage is 2.2V, which is significantly higher than the output voltage of the water-based hybrid supercapacitor.
  • the artificial graphite and the binder polyvinylidene fluoride are mixed at a mass ratio of 95:5, and the mixed slurry is scraped on the washed aluminum foil positive electrode collector with a film with a thickness of 150 ⁇ m, dried, and cut into A positive pole piece with a diameter of 12 mm.
  • the negative pole piece uses a zinc plate with a diameter of 12 mm.
  • a ZnSO 4 /acetonitrile solution with a concentration of 0.2 mol/L is used as an electrolyte, and a glass fiber with a diameter of 16.5 mm is used as a separator, and 150 ⁇ L of electrolyte is added dropwise on the separator.
  • the battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top.
  • the assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours to obtain the hybrid supercapacitor described in this embodiment.
  • the positive electrode of the obtained supercapacitor was subjected to a cyclic voltammetry curve test (sweep rate: 1mV/s). The test result is shown in FIG.
  • the artificial graphite, the binder polytetrafluoroethylene and the conductive agent acetylene black are mixed in a mass ratio of 85:10:5, and the mixed slurry is scraped on the cleaned aluminum foil positive current collector with a scraper to a layer with a thickness of 150 ⁇ m After drying, the membrane is cut into 12mm diameter positive pole pieces.
  • the negative pole piece uses zinc foil with a diameter of 12 mm.
  • a 2 mol/L concentration of ZnCl 2 /propylene carbonate solution was used as an electrolyte, and a glass fiber with a diameter of 16.5 mm was used as a separator, and 150 ⁇ L of electrolyte was added dropwise on the separator.
  • the battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top.
  • the assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours to obtain the hybrid supercapacitor described in this embodiment.
  • the graphite positive electrode of the obtained supercapacitor was subjected to XRD test in the charged state and the discharged state. The test results are shown in FIG.
  • the artificial graphite, the binder polyvinylidene fluoride and the conductive agent acetylene black are mixed in a mass ratio of 90:5:5, and the mixed slurry is scraped on the cleaned aluminum foil cathode current collector with a thickness of 150 ⁇ m using a scraper After drying, the membrane is cut into 12mm diameter positive pole pieces.
  • the negative pole piece uses a zinc-copper alloy piece with a diameter of 12 mm and a mass ratio of 1:1.
  • a Zn[N(CF 3 SO 2 ) 2 ] 2 /acetonitrile solution with a concentration of 1 mol/L is used as an electrolyte, and a glass fiber with a diameter of 16.5 mm is used as a separator, and 150 ⁇ L of electrolyte is added dropwise on the separator.
  • the battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top.
  • the assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours, and then the electrochemical performance test is performed with a blue electric tester.
  • the working test voltage range is 1.2V-2.65V, and the cycle performance under 5000mA/g current density test conditions is shown in Figure 4.
  • the specific capacity retention rate after 1000 cycles is 99%, showing very good cycle stability.
  • the natural graphite and the binder polyvinylidene fluoride are mixed in a mass ratio of 9:1, and the mixed slurry is scraped on the washed aluminum foil positive electrode collector with a scraper to a film with a thickness of 150 ⁇ m, dried and cut into A positive pole piece with a diameter of 12 mm.
  • the negative pole piece uses zinc foil with a diameter of 12 mm.
  • a 3 mol/L concentration of Zn(ClO 4 ) 2 /ethylene carbonate solution was used as an electrolyte, and a glass fiber with a diameter of 16.5 mm was used as a separator, and 150 ⁇ L of electrolyte was added dropwise on the separator.
  • the battery packaging machine is used for packaging.
  • the negative electrode casing, the negative electrode sheet, the diaphragm, the positive electrode sheet, the gasket, the shrapnel, and the positive electrode casing From bottom to top, the negative electrode casing, the negative electrode sheet, the diaphragm, the positive electrode sheet, the gasket, the shrapnel, and the positive electrode casing.
  • the assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours, and then the electrochemical performance test is performed with a blue electric tester.
  • the working test voltage range is 1.2V-2.65V.
  • the rate performance under different current density test conditions is shown in Figure 5. It can be found that the specific capacity of the capacitor when charging and discharging at 100C rate can reach 47mAhg -1 , after calculation The energy density is as high as 101 Wh/kg.
  • Table 1 it is shown that the energy density of the hybrid supercapacitor obtained in this example is significantly higher than that of the hybrid capacitors in several other comparative examples.
  • the artificial graphite and the binder polyvinylidene fluoride are mixed at a mass ratio of 9:1, and the mixed slurry is scraped on the washed aluminum foil positive electrode collector with a scraper to a film with a thickness of 150 ⁇ m, dried and cut into A positive pole piece with a diameter of 12 mm.
  • the negative pole piece uses zinc foil with a diameter of 12 mm.
  • a 4 mol/L concentration of Zn(PF 6 ) 2 /acetonitrile solution was used as an electrolyte, and a glass fiber with a diameter of 16.5 mm was used as a separator, and 150 ⁇ L of electrolyte was added dropwise on the separator.
  • the battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top.
  • the assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours, and then the electrochemical performance test is performed with a blue electric tester.
  • the working test voltage range is 1.2V-2.65V, and the scanning electron micrograph of the surface of the zinc negative electrode after 1000 charge and discharge cycles under 5000mA/g current density test conditions is shown in Figure 6. No zinc dendrites are generated, indicating that the mixed type The safety of supercapacitors is high.
  • the natural graphite and the binder polyvinylidene fluoride are mixed at a mass ratio of 9:1, and the mixed slurry is scraped on the washed aluminum foil positive electrode collector with a scraper to a film with a thickness of 150 ⁇ m, dried and cut into A positive pole piece with a diameter of 12 mm.
  • the negative pole piece uses zinc foil with a diameter of 12 mm.
  • a 5 mol/L concentration of Zn(BF 4 ) 2 /ethylene carbonate solution was used as an electrolyte, and a glass fiber with a diameter of 16.5 mm was used as a separator, and 150 ⁇ L of electrolyte was added dropwise on the separator.
  • the battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top.
  • the assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours, and then the electrochemical performance test is performed with a blue electric tester.
  • the energy density of the hybrid supercapacitor is calculated and shown in Table 1.
  • the natural graphite and the binder carboxymethyl cellulose are mixed in a mass ratio of 9:1, and the mixed slurry is scraped on the washed aluminum foil positive current collector with a scraper to a film with a thickness of 150 ⁇ m, dried and cut A positive pole piece with a diameter of 12 mm is formed.
  • the negative pole piece uses zinc foil with a diameter of 12 mm.
  • a Zn(NO 3 ) 2 /acetonitrile solution at a concentration of 1 mol/L is used as an electrolyte, and a glass fiber with a diameter of 16.5 mm is used as a separator, and 150 ⁇ L of electrolyte is added dropwise on the separator.
  • the battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top.
  • the assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours, and then the electrochemical performance test is performed with a blue electric tester.
  • the energy density of the hybrid supercapacitor is calculated and shown in Table 1.
  • Example 1 Numbering Energy density (Wh/kg) Example 1 99
  • Example 2 91
  • Example 3 93
  • Example 4 96
  • Example 5 98
  • Example 6 101
  • Example 7 96
  • Example 8 94 Comparative Example 1 14 Comparative Example 2 35 Comparative Example 3 37

Abstract

The present invention relates to the technical field of electrochemical energy storage, and relates to a zinc negative electrode and a graphite positive electrode-based hybrid super capacitor. The hybrid super capacitor comprises a positive electrode, a negative electrode, an electrolytic solution, and a separator, wherein an active material of the positive electrode is graphite, an active material of the negative electrode is metal zinc, and the electrolytic solution comprises a zinc salt electrolyte and an organic solvent. During the charging and discharging of the hybrid super capacitor, the negative electrode undergoes a deposition/dissolution zinc ion reaction, and the positive electrode undergoes an intercalation/deintercalation anion reaction between graphite layers, which has the features of pseudocapacitance. The specific capacity is as high as 52 mAh/g so that the energy density of the hybrid super capacitor may may reach 101Wh/kg. The present hybrid super capacitor further has the advantages of being low cost, has good cycle stability, and a high safety performance, and has broad application prospects in the field of energy storage.

Description

一种基于石墨正极和锌负极的混合型超级电容器Hybrid supercapacitor based on graphite positive electrode and zinc negative electrode 技术领域Technical field
本发明属于电化学储能技术领域，具体涉及一种由石墨正极、锌负极和有机溶剂电解液组成的混合型超级电容器。The invention belongs to the technical field of electrochemical energy storage, and in particular relates to a hybrid supercapacitor composed of a graphite positive electrode, a zinc negative electrode and an organic solvent electrolyte.
背景技术Background technique
随着智能电子设备、电动汽车等领域的发展，人们对储能设备的能量密度、快速充放电性能和安全性能要求越来越高。锂离子电池是目前广泛应用的储能器件，具有能量密度高、自放电率低等优点，但是它也存在明显的缺点，比如，锂离子电池的成本高、安全性能差、不能快速充放电。超级电容器是一种介于传统电容器和二次电池之间的新型储能器件，从电荷储存机理上可以分为没有法拉第电荷转移的双电层电容器和有法拉第电荷转移的赝电容器。与电池相比，超级电容器具有功率密度高、充电时间短、安全性高、绿色环保等优点。虽然超级电容器相比于传统的电容器能量密度有了极大的提升，但是相比于锂离子电池，能量密度仍然较低，一般小于40Wh/kg，这大大限制了它的应用范围。With the development of smart electronic equipment, electric vehicles and other fields, people are increasingly demanding energy density, fast charge and discharge performance and safety performance of energy storage equipment. Lithium-ion batteries are currently widely used energy storage devices, which have the advantages of high energy density and low self-discharge rate, but they also have obvious disadvantages. For example, lithium-ion batteries have high costs, poor safety performance, and cannot be quickly charged and discharged. Supercapacitors are a new type of energy storage devices between traditional capacitors and secondary batteries. From the charge storage mechanism, they can be divided into electric double layer capacitors without Faraday charge transfer and pseudocapacitors with Faraday charge transfer. Compared with batteries, supercapacitors have the advantages of high power density, short charging time, high safety, and environmental protection. Although the energy density of supercapacitors has been greatly improved compared to traditional capacitors, compared with lithium-ion batteries, the energy density is still low, generally less than 40Wh/kg, which greatly limits its scope of application.
在公开号为CN103545123B的中国发明专利中，中国第一汽车股份有限公司提出了基于锌离子电池和超级电容器的混合储能器件，电解液是由锌盐和去离子水组成。在公开号为CN106981371A的中国发明专利中，黄潮等人提出了采用锌负极和碳材料正极的超级电容电池，电解质是pH值大于2.5的水溶液。以上两个专利提出的锌离子混合型电容器都是使用水系电解液，由于水在标准状态下的分解电压是1.23V，因此水系锌离子混合型电容器的工作电压低，相应的能量密度也低。除此之外，水系锌离子电池或混合型电容器的另一个缺点是在充放电循环时容易生成锌枝晶，存在电池产生短路的潜在危险。In the Chinese invention patent with publication number CN103545123B, China First Automobile Co., Ltd. proposed a hybrid energy storage device based on a zinc ion battery and a super capacitor. The electrolyte is composed of zinc salt and deionized water. In the Chinese invention patent with publication number CN106981371A, Huang Chao et al. proposed a supercapacitor battery using a zinc anode and a carbon anode, and the electrolyte is an aqueous solution with a pH value greater than 2.5. The zinc ion hybrid capacitors proposed in the above two patents all use an aqueous electrolyte. Since the decomposition voltage of water in a standard state is 1.23V, the operating voltage of the aqueous zinc ion hybrid capacitor is low, and the corresponding energy density is also low. In addition, another disadvantage of water-based zinc ion batteries or hybrid capacitors is that zinc dendrites are easily generated during charge and discharge cycles, and there is a potential danger of short circuits in the battery.
在公开号为CN108172833A的中国发明专利中，深圳先进技术研究院提出了锌基双离子电池或电容器，负极是可以吸附和脱附锌离子的多孔碳材料，正极是能够可逆脱嵌阴离子的石墨类碳材料。该专利的负极发生的是活性炭材料通过双电层电容效应吸附和脱附锌离子反应，比锌或锌合金负极表面发生锌离子的沉积溶解反应对应的比容量低很多，造成了该双离子电池或电容器的能量密度较低。In the Chinese invention patent published as CN108172833A, Shenzhen Advanced Technology Research Institute proposed a zinc-based dual-ion battery or capacitor. The negative electrode is a porous carbon material that can adsorb and desorb zinc ions. The positive electrode is a graphite that can reversibly deintercalate anions. Carbon material. The negative electrode of this patent occurs that the activated carbon material absorbs and desorbs zinc ions through the electric double layer capacitance effect, which is much lower than the specific capacity corresponding to the zinc ion deposition and dissolution reaction on the surface of the zinc or zinc alloy negative electrode, resulting in the dual ion battery. Or the energy density of the capacitor is low.
在公开号为CN107369567A的中国发明专利中，深圳中科瑞能实业有限公司提出了基于锌离子的混合电容器，采用锌或锌合金为负极，正极材料是能够可逆吸附/脱附阴离子的碳材料。这个专利的正极碳材料是通过双电层将阴离子吸附在其表面，是一个不发生氧化还原反应的非法拉第过程，由于双电层储存的电荷数量有限，因此该混合型电容器的比容量和能量密度也较低。In the Chinese invention patent with publication number CN107369567A, Shenzhen Zhongke Ruineng Industrial Co., Ltd. proposed a hybrid capacitor based on zinc ions, using zinc or zinc alloy as the negative electrode, and the positive electrode material is a carbon material that can reversibly adsorb/desorb anions. This patented positive electrode carbon material adsorbs anions on its surface through an electric double layer, which is an illegal Faraday process that does not undergo a redox reaction. Due to the limited amount of charge stored in the electric double layer, the specific capacity and energy of the hybrid capacitor The density is also low.
石墨是一种具有高结晶度和固定层间距的层状碳材料，在一定的电压范围内它的层间能够快速可逆地发生阴离子的嵌入脱出反应，是一类具有法拉第电荷转移特征的赝电 容电荷储存机理，该反应与活性碳材料通过表面吸附脱附阴离子的双电层电容行为相比，具有比容量高、输出电压高的优点，因为石墨作为正极材料，可以大大提高基于锌负极的混合型超级电容器的能量密度。Graphite is a layered carbon material with high crystallinity and fixed interlayer spacing. It can quickly and reversibly intercalate and deintercalate anions between layers within a certain voltage range. It is a type of pseudocapacitor with Faraday charge transfer characteristics. Charge storage mechanism, this reaction has the advantages of high specific capacity and high output voltage compared to the double-layer capacitance behavior of activated carbon materials adsorbing and desorbing anions through the surface, because graphite as a cathode material can greatly improve the mixing based on zinc anode The energy density of supercapacitors.
发明内容Summary of the invention
为解决上述问题，本发明提供了一种基于锌负极、石墨正极和有机溶剂电解液组成的混合型超级电容器，混合型超级电容器是一种新型的储能器件，它的一侧电极呈现离子脱嵌或沉积溶解的电池反应特征，另一侧电极呈现超级电容器具备的双电层电容或赝电容特征，这样它既结合了电池高容量的特点，也结合了超级电容器快速充放电的特性，因此它在移动通讯、消费电子、电动交通工具等领域具有很大的潜在应用价值。In order to solve the above problems, the present invention provides a hybrid supercapacitor based on a zinc anode, a graphite cathode and an organic solvent electrolyte. The hybrid supercapacitor is a new type of energy storage device, and one of its electrodes exhibits ion desorption Embedded or deposited dissolved battery reaction characteristics, the other side of the electrode exhibits the electric double layer capacitance or pseudocapacitance characteristics of the supercapacitor, so that it combines the characteristics of the battery's high capacity and the supercharger's rapid charge and discharge characteristics, so It has great potential application value in the fields of mobile communication, consumer electronics, electric vehicles, etc.
本发明采用以下技术方案：The present invention adopts the following technical solutions:
一种基于石墨正极和锌负极的混合型超级电容器，包括正极、负极以及介于所述正极与所述负极之间的隔膜和电解液；所述负极活性物质在充放电时发生锌离子的沉积或溶解反应；所述正极活性物质在充放电时发生阴离子嵌入或脱出石墨层间的反应；所述电解液包括锌盐电解质和有机溶剂。A hybrid supercapacitor based on graphite positive electrode and zinc negative electrode, including a positive electrode, a negative electrode, a separator and an electrolyte interposed between the positive electrode and the negative electrode; the negative electrode active material deposits zinc ions during charging and discharging Or dissolution reaction; the positive electrode active material undergoes a reaction of anion insertion or extraction between graphite layers during charge and discharge; the electrolyte includes a zinc salt electrolyte and an organic solvent.
所述负极活性材料为锌片、锌箔、锌粉、锌合金中的一种或多种。The negative electrode active material is one or more of zinc flake, zinc foil, zinc powder, and zinc alloy.
优选地，所述负极材料还包括负极集流体。Preferably, the negative electrode material further includes a negative electrode current collector.
所述正极材料由质量分数为85-95％的正极活性材料、0-5％的导电剂和5-10％粘结剂组成。The positive electrode material is composed of a positive electrode active material with a mass fraction of 85-95%, a conductive agent of 0-5%, and a binder of 5-10%.
所述正极活性材料为石墨，包括天然石墨和人造石墨中的一种或两种的组合。The positive electrode active material is graphite, including one or a combination of natural graphite and artificial graphite.
优选地，所述正极材料还包括正极集流体。Preferably, the cathode material further includes a cathode current collector.
所述粘结剂为聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、丁苯橡胶中的一种或至少两种的组合。The binder is one or a combination of at least two of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, and styrene-butadiene rubber.
所述锌盐电解质为ZnSO 4、Zn(NO 3) 2、Zn(ClO 4) 2、Zn(BF 4) 2、Zn(CF 3SO 3) 2、Zn[N(CF 3SO 2) 2] 2、Zn(PF 6) 2中的一种或两种以上按一定比例混合而成，所述锌盐电解质中锌离子的浓度范围为0.1-5mol/L。 The zinc salt electrolyte is ZnSO 4 , Zn(NO 3 ) 2 , Zn(ClO 4 ) 2 , Zn(BF 4 ) 2 , Zn(CF 3 SO 3 ) 2 , Zn[N(CF 3 SO 2 ) 2 ] 2. One or two or more of Zn(PF 6 ) 2 are mixed at a certain ratio, and the concentration of zinc ions in the zinc salt electrolyte ranges from 0.1 to 5 mol/L.
所述有机溶剂为介电常数大于20的有机溶剂，包括乙腈、碳酸丙烯酯、碳酸乙烯酯中的一种或两种以上按一定比例混合而成。The organic solvent is an organic solvent with a dielectric constant greater than 20, including one or more of acetonitrile, propylene carbonate, and ethylene carbonate mixed in a certain ratio.
上述基于石墨化碳材料正极和锌负极的混合型超级电容器的制备方法，将正极、负极、隔膜和电解液进行组装，得到所述混合型超级电容器。The method for preparing the hybrid supercapacitor based on the graphitized carbon material positive electrode and the zinc negative electrode above assembles the positive electrode, the negative electrode, the separator and the electrolyte to obtain the hybrid supercapacitor.
与已有技术相比，本发明具有如下优点：Compared with the prior art, the present invention has the following advantages:
本发明提供的基于石墨正极和锌负极的混合型超级电容器，以成本低廉、资源丰富的石墨作为正极活性物质，金属锌为负极活性物质，可大幅降低混合型超级电容器的材料成本；电解液采用了含有锌盐的有机溶剂作为电解溶剂，经实验验证负极不存在锌枝晶生长问题(图6)，安全性较高；该混合型超级电容器的石墨正极在充放电过程中石墨层间发生具有赝电容特征的嵌入脱出阴离子反应(图2、图3)，因此比容量高达52 mAh/g(图1)，导致该混合型超级电容器的能量密度高，可达到101Wh/kg(表1)；此外，该混合型超级电容器循环稳定高，循环寿命大于1000次(图4)。The hybrid supercapacitor based on graphite positive electrode and zinc negative electrode provided by the present invention uses low-cost and resource-rich graphite as the positive electrode active material, and metallic zinc as the negative electrode active material, which can greatly reduce the material cost of the hybrid supercapacitor; the electrolyte is used The organic solvent containing zinc salt is used as the electrolytic solvent. It has been experimentally verified that the negative electrode does not have the problem of zinc dendrite growth (Figure 6), and the safety is high; the graphite positive electrode of the hybrid supercapacitor occurs between the graphite layers during charging and discharging. Pseudo-capacitance features are embedded in the anion reaction (Figure 2 and Figure 3), so the specific capacity is as high as 52 mAh/g (Figure 1), resulting in a high energy density of the hybrid supercapacitor, which can reach 101Wh/kg (Table 1); In addition, the hybrid supercapacitor has a high cycle stability and a cycle life of more than 1000 times (Figure 4).
附图表说明BRIEF DESCRIPTION OF DRAWINGS
图1是本发明实施例1中在5000mA/g电流密度测试条件下充放电曲线图。FIG. 1 is a charge-discharge curve diagram under the test condition of 5000 mA/g current density in Example 1 of the present invention.
图2是本发明实施例2中石墨正极在1mV/s扫速下的循环伏安曲线。2 is a cyclic voltammetry curve of a graphite positive electrode at a sweep speed of 1 mV/s in Example 2 of the present invention.
图3是本发明实施例3中石墨正极在充电态和放电态的XRD谱图。FIG. 3 is an XRD spectrum of a graphite positive electrode in a charged state and a discharged state in Example 3 of the present invention.
图4是本发明实施例4中在5000mA/g电流密度测试条件下循环性能图。4 is a graph of cycle performance under the current density test condition of 5000 mA/g in Example 4 of the present invention.
图5是本发明实施例5中在不同电流密度测试条件下倍率性能图。5 is a graph of rate performance under different current density test conditions in Example 5 of the present invention.
图6是本发明实施例6中在5000mA/g电流密度测试条件下充放电循环1000次后锌负极表面的扫描电镜图。6 is a scanning electron micrograph of the surface of the zinc negative electrode after 1000 charge-discharge cycles under the 5000 mA/g current density test condition in Example 6 of the present invention.
表1是本发明实施例1-8与对比例1-3中所述的混合型超级电容器测试得到的能量密度对比。Table 1 is the energy density comparison of the hybrid supercapacitors described in Examples 1-8 of the present invention and Comparative Examples 1-3.
具体实施方式detailed description
下面结合实例，对本发明作进一步详细说明。The present invention will be further described in detail below with reference to examples.
对比例1(负极为锌、正极为活性炭、电解液溶剂为水的混合型超级电容器)：Comparative Example 1 (hybrid supercapacitor with negative electrode as zinc, positive electrode as activated carbon, and electrolyte solvent as water):
将多孔活性炭和粘结剂丁苯橡胶以9:1的质量比混合，用刮刀将混合浆料在洗净的铝箔正极集流体上刮上厚度为150μm的一层膜，烘干后裁成直径为12mm的正极极片。负极极片采用直径为12mm的锌箔。1mol/L浓度的Zn(CF 3SO 3) 2水溶液作为电解液，直径为16.5mm的玻璃纤维作为隔膜，在隔膜上滴加150μL电解液。采用电池封装机进行封装，从下往上依次是负极壳、负极极片、隔膜、正极极片、垫片、弹片、正极壳。组装好的混合型超级电容器在室温下静置2小时，即得本对比例所述的水系混合型超级电容器。然后用蓝电测试仪进行电化学性能测试，测试电流为5000mA/g，测得的能量密度计算如表1所示。 The porous activated carbon and the binder styrene-butadiene rubber are mixed in a mass ratio of 9:1, and the mixed slurry is scraped on the cleaned aluminum foil positive electrode collector with a scraper to a film with a thickness of 150 μm, dried and cut to a diameter 12mm positive pole piece. The negative pole piece uses zinc foil with a diameter of 12 mm. A 1 mol/L concentration of Zn(CF 3 SO 3 ) 2 aqueous solution was used as an electrolyte, and a glass fiber with a diameter of 16.5 mm was used as a separator, and 150 μL of electrolyte was added dropwise on the separator. The battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top. The assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours to obtain the water-based hybrid supercapacitor described in this comparative example. Then use the blue electric tester to perform the electrochemical performance test, the test current is 5000mA/g, and the measured energy density calculation is shown in Table 1.
对比例2(负极为锌、正极为活性炭、电解液溶剂为有机溶剂的混合型超级电容器)：Comparative Example 2 (hybrid supercapacitor with negative electrode as zinc, positive electrode as activated carbon, and electrolyte solvent as organic solvent):
将多孔活性炭和粘结剂聚偏氟乙烯以9:1的质量比混合，用刮刀将混合浆料在洗净的铝箔正极集流体上刮上厚度为150μm的一层膜，烘干后裁成直径为12mm的正极极片。负极极片采用直径为12mm的锌箔。1mol/L浓度的Zn(CF 3SO 3) 2/乙腈溶液作为电解液，直径为16.5mm的玻璃纤维作为隔膜，在隔膜上滴加150μL电解液。采用电池封装机进行封装，从下往上依次是负极壳、负极极片、隔膜、正极极片、垫片、弹片、正极壳。组装好的混合型超级电容器在室温下静置2小时，即得本对比例所述的基于活性炭正极的有机体系混合型超级电容器。然后用蓝电测试仪进行电化学性能测试，测试电流为5000mA/g，测得的能量密度计算如表1所示。 The porous activated carbon and the binder polyvinylidene fluoride are mixed at a mass ratio of 9:1, and the mixed slurry is scraped on the washed aluminum foil positive current collector with a scraper to a film with a thickness of 150 μm, dried and cut into A positive pole piece with a diameter of 12 mm. The negative pole piece uses zinc foil with a diameter of 12 mm. A Zn(CF 3 SO 3 ) 2 /acetonitrile solution at a concentration of 1 mol/L is used as an electrolyte, and a glass fiber with a diameter of 16.5 mm is used as a separator, and 150 μL of electrolyte is added dropwise on the separator. The battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top. The assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours to obtain an organic system hybrid supercapacitor based on the activated carbon positive electrode described in this comparative example. Then use the blue electric tester to perform the electrochemical performance test, the test current is 5000mA/g, and the measured energy density calculation is shown in Table 1.
对比例3(负极为活性炭、正极为石墨、电解液溶剂为有机溶剂的不对称超级电容器)：Comparative Example 3 (asymmetric supercapacitor with negative electrode as activated carbon, positive electrode as graphite, and electrolyte solvent as organic solvent):
将天然石墨和粘结剂丁苯橡胶以9:1的质量比混合，用刮刀将混合浆料在洗净的铝箔正极集流体上刮上厚度为150μm的一层膜，烘干后裁成直径为12mm的正极极片。将多孔活性炭和粘结剂丁苯橡胶以9:1的质量比混合，用刮刀将混合浆料在洗净的铜箔负极集流体上刮上厚度为150μm的一层膜，烘干后裁成直径为12mm的负极极片。1mol/L浓度的Zn(CF 3SO 3) 2/乙腈溶液作为电解液，直径为16.5mm的玻璃纤维作为隔膜，在隔膜上滴加150μL电解液。采用电池封装机进行封装，从下往上依次是负极壳、负极极片、隔膜、正极极片、垫片、弹片、正极壳。组装好的混合型超级电容器在室温下静置2小时，即得本对比例所述的基于活性炭负极的有机体系混合型超级电容器。然后用蓝电测试仪进行电化学性能测试，测试电流为5000mA/g，测得的能量密度计算如表1所示。 Mix natural graphite and binder styrene-butadiene rubber at a mass ratio of 9:1, use a spatula to scrape the mixed slurry on the washed aluminum foil positive current collector with a layer of film with a thickness of 150μm, and cut it to a diameter after drying 12mm positive pole piece. The porous activated carbon and the binder styrene-butadiene rubber are mixed in a mass ratio of 9:1, and the mixed slurry is scraped on the washed copper foil negative electrode current collector with a film with a thickness of 150 μm, dried and cut into A negative pole piece with a diameter of 12 mm. A Zn(CF 3 SO 3 ) 2 /acetonitrile solution at a concentration of 1 mol/L is used as an electrolyte, and a glass fiber with a diameter of 16.5 mm is used as a separator, and 150 μL of electrolyte is added dropwise on the separator. The battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top. The assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours to obtain the organic system hybrid supercapacitor based on the activated carbon negative electrode described in this comparative example. Then use the blue electric tester to perform the electrochemical performance test, the test current is 5000mA/g, and the measured energy density calculation is shown in Table 1.
实施例1：Example 1:
将天然石墨和粘结剂丁苯橡胶以9:1的质量比混合，用刮刀将混合浆料在洗净的铝箔正极集流体上刮上厚度为150μm的一层膜，烘干后裁成直径为12mm的正极极片。负极极片采用直径为12mm的锌箔。1mol/L浓度的Zn(CF 3SO 3) 2/乙腈溶液作为电解液，直径为16.5mm的玻璃纤维作为隔膜，在隔膜上滴加150μL电解液。采用电池封装机进行封装，从下往上依次是负极壳、负极极片、隔膜、正极极片、垫片、弹片、正极壳。组装好的混合型超级电容器在室温下静置2小时，然后用蓝电测试仪进行电化学性能测试。工作测试电压范围为1.2V-2.65V，在5000mA/g电流密度测试条件下充放电曲线如图1所示，图1显示本实施例所得的混合型超级电容器的充放电曲线呈现出典型的超级电容器特征，比容量为52mAh/g，充电时间仅为90秒，并且平均输出电压为2.2V，显著高于水系混合型超级电容器的输出电压。 Mix natural graphite and binder styrene-butadiene rubber at a mass ratio of 9:1, use a spatula to scrape the mixed slurry on the washed aluminum foil positive current collector with a layer of film with a thickness of 150μm, and cut it to a diameter after drying 12mm positive pole piece. The negative pole piece uses zinc foil with a diameter of 12 mm. A Zn(CF 3 SO 3 ) 2 /acetonitrile solution at a concentration of 1 mol/L is used as an electrolyte, and a glass fiber with a diameter of 16.5 mm is used as a separator, and 150 μL of electrolyte is added dropwise on the separator. The battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top. The assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours, and then the electrochemical performance test is performed with a blue electric tester. The working test voltage range is 1.2V-2.65V, and the charging and discharging curve is shown in Figure 1 under the current density test condition of 5000mA/g. Figure 1 shows that the charging and discharging curve of the hybrid supercapacitor obtained in this example shows a typical super The characteristics of the capacitor, the specific capacity is 52mAh/g, the charging time is only 90 seconds, and the average output voltage is 2.2V, which is significantly higher than the output voltage of the water-based hybrid supercapacitor.
实施例2：Example 2:
将人造石墨和粘结剂聚偏氟乙烯以95:5的质量比混合，用刮刀将混合浆料在洗净的铝箔正极集流体上刮上厚度为150μm的一层膜，烘干后裁成直径为12mm的正极极片。负极极片采用直径为12mm的锌片。0.2mol/L浓度的ZnSO 4/乙腈溶液作为电解液，直径为16.5mm的玻璃纤维作为隔膜，在隔膜上滴加150μL电解液。采用电池封装机进行封装，从下往上依次是负极壳、负极极片、隔膜、正极极片、垫片、弹片、正极壳。组装好的混合型超级电容器在室温下静置2小时，即得本实施例所述的混合型超级电容器。对所得超级电容器的正极进行循环伏安曲线测试(扫速：1mV/s)，测试结果如图2所示，图2显示本实施例所得混合型超级电容器的石墨正极循环伏安曲线展现出三对显著的氧化还原峰，表明充放电过程中石墨正极伴随着法拉第电荷转移的赝电容行为。 The artificial graphite and the binder polyvinylidene fluoride are mixed at a mass ratio of 95:5, and the mixed slurry is scraped on the washed aluminum foil positive electrode collector with a film with a thickness of 150 μm, dried, and cut into A positive pole piece with a diameter of 12 mm. The negative pole piece uses a zinc plate with a diameter of 12 mm. A ZnSO 4 /acetonitrile solution with a concentration of 0.2 mol/L is used as an electrolyte, and a glass fiber with a diameter of 16.5 mm is used as a separator, and 150 μL of electrolyte is added dropwise on the separator. The battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top. The assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours to obtain the hybrid supercapacitor described in this embodiment. The positive electrode of the obtained supercapacitor was subjected to a cyclic voltammetry curve test (sweep rate: 1mV/s). The test result is shown in FIG. 2, which shows that the graphite positive electrode cyclic voltammetry curve of the hybrid supercapacitor obtained in this example shows three The significant redox peaks indicate the pseudocapacitive behavior of the graphite positive electrode with Faraday charge transfer during charge and discharge.
实施例3：Example 3:
将人造石墨、粘结剂聚四氟乙烯和导电剂乙炔黑以85:10:5的质量比混合，用刮刀将混合浆料在洗净的铝箔正极集流体上刮上厚度为150μm的一层膜，烘干后裁成直径为12mm的正极极片。负极极片采用直径为12mm的锌箔。2mol/L浓度的ZnCl 2/碳酸丙烯酯溶液作为电解液，直径为16.5mm的玻璃纤维作为隔膜，在隔膜上滴加150μL 电解液。采用电池封装机进行封装，从下往上依次是负极壳、负极极片、隔膜、正极极片、垫片、弹片、正极壳。组装好的混合型超级电容器在室温下静置2小时，即得本实施例所述的混合型超级电容器。对所得超级电容器的石墨正极进行充电态和放电态的XRD测试，测试结果如图3所示，图3显示本实施例所得混合型超级电容器的石墨正极在充电态时对应于石墨(002)晶面的XRD衍射峰发生了显著变化，表明充放电过程中发生了阴离子嵌入脱出石墨层间的反应。 The artificial graphite, the binder polytetrafluoroethylene and the conductive agent acetylene black are mixed in a mass ratio of 85:10:5, and the mixed slurry is scraped on the cleaned aluminum foil positive current collector with a scraper to a layer with a thickness of 150 μm After drying, the membrane is cut into 12mm diameter positive pole pieces. The negative pole piece uses zinc foil with a diameter of 12 mm. A 2 mol/L concentration of ZnCl 2 /propylene carbonate solution was used as an electrolyte, and a glass fiber with a diameter of 16.5 mm was used as a separator, and 150 μL of electrolyte was added dropwise on the separator. The battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top. The assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours to obtain the hybrid supercapacitor described in this embodiment. The graphite positive electrode of the obtained supercapacitor was subjected to XRD test in the charged state and the discharged state. The test results are shown in FIG. 3, which shows that the graphite positive electrode of the hybrid supercapacitor obtained in this embodiment corresponds to the graphite (002) crystal in the charged state The XRD diffraction peak of the surface has changed significantly, indicating that the reaction of anion insertion and extraction between the graphite layers occurred during the charging and discharging process.
实施例4：Example 4:
将人造石墨、粘结剂聚偏氟乙烯和导电剂乙炔黑以90:5:5的质量比混合，用刮刀将混合浆料在洗净的铝箔正极集流体上刮上厚度为150μm的一层膜，烘干后裁成直径为12mm的正极极片。负极极片采用直径为12mm、质量比为1：1的锌铜合金片。1mol/L浓度的Zn[N(CF 3SO 2) 2] 2/乙腈溶液作为电解液，直径为16.5mm的玻璃纤维作为隔膜，在隔膜上滴加150μL电解液。采用电池封装机进行封装，从下往上依次是负极壳、负极极片、隔膜、正极极片、垫片、弹片、正极壳。组装好的混合型超级电容器在室温下静置2小时，然后用蓝电测试仪进行电化学性能测试。工作测试电压范围为1.2V-2.65V，在5000mA/g电流密度测试条件下循环性能如图4所示，循环1000圈后的比容量保持率为99％，显示出非常好的循环稳定性。 The artificial graphite, the binder polyvinylidene fluoride and the conductive agent acetylene black are mixed in a mass ratio of 90:5:5, and the mixed slurry is scraped on the cleaned aluminum foil cathode current collector with a thickness of 150 μm using a scraper After drying, the membrane is cut into 12mm diameter positive pole pieces. The negative pole piece uses a zinc-copper alloy piece with a diameter of 12 mm and a mass ratio of 1:1. A Zn[N(CF 3 SO 2 ) 2 ] 2 /acetonitrile solution with a concentration of 1 mol/L is used as an electrolyte, and a glass fiber with a diameter of 16.5 mm is used as a separator, and 150 μL of electrolyte is added dropwise on the separator. The battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top. The assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours, and then the electrochemical performance test is performed with a blue electric tester. The working test voltage range is 1.2V-2.65V, and the cycle performance under 5000mA/g current density test conditions is shown in Figure 4. The specific capacity retention rate after 1000 cycles is 99%, showing very good cycle stability.
实施例5：Example 5:
将天然石墨和粘结剂聚偏氟乙烯以9:1的质量比混合，用刮刀将混合浆料在洗净的铝箔正极集流体上刮上厚度为150μm的一层膜，烘干后裁成直径为12mm的正极极片。负极极片采用直径为12mm的锌箔。3mol/L浓度的Zn(ClO 4) 2/碳酸乙烯酯溶液作为电解液，直径为16.5mm的玻璃纤维作为隔膜，在隔膜上滴加150μL电解液。采用电池封装机进行封装，从下往上依次是负极壳、负极极片、隔膜、正极极片、垫片、弹片、正极壳。组装好的混合型超级电容器在室温下静置2小时，然后用蓝电测试仪进行电化学性能测试。工作测试电压范围为1.2V-2.65V，不同电流密度测试条件下的倍率性能如图5所示，可以发现即使在100C倍率下充放电时的电容器的比容量也能达到47mAhg -1，计算后的能量密度高达101Wh/kg，如表1所示，显示本实施例所得的混合型超级电容器的能量密度显著高于其它几个对比例中混合电容器的能量密度。 The natural graphite and the binder polyvinylidene fluoride are mixed in a mass ratio of 9:1, and the mixed slurry is scraped on the washed aluminum foil positive electrode collector with a scraper to a film with a thickness of 150 μm, dried and cut into A positive pole piece with a diameter of 12 mm. The negative pole piece uses zinc foil with a diameter of 12 mm. A 3 mol/L concentration of Zn(ClO 4 ) 2 /ethylene carbonate solution was used as an electrolyte, and a glass fiber with a diameter of 16.5 mm was used as a separator, and 150 μL of electrolyte was added dropwise on the separator. The battery packaging machine is used for packaging. From bottom to top, the negative electrode casing, the negative electrode sheet, the diaphragm, the positive electrode sheet, the gasket, the shrapnel, and the positive electrode casing. The assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours, and then the electrochemical performance test is performed with a blue electric tester. The working test voltage range is 1.2V-2.65V. The rate performance under different current density test conditions is shown in Figure 5. It can be found that the specific capacity of the capacitor when charging and discharging at 100C rate can reach 47mAhg -1 , after calculation The energy density is as high as 101 Wh/kg. As shown in Table 1, it is shown that the energy density of the hybrid supercapacitor obtained in this example is significantly higher than that of the hybrid capacitors in several other comparative examples.
实施例6：Example 6:
将人造石墨和粘结剂聚偏氟乙烯以9:1的质量比混合，用刮刀将混合浆料在洗净的铝箔正极集流体上刮上厚度为150μm的一层膜，烘干后裁成直径为12mm的正极极片。负极极片采用直径为12mm的锌箔。4mol/L浓度的Zn(PF 6) 2/乙腈溶液作为电解液，直径为16.5mm的玻璃纤维作为隔膜，在隔膜上滴加150μL电解液。采用电池封装机进行封装，从下往上依次是负极壳、负极极片、隔膜、正极极片、垫片、弹片、正极壳。组装好的混合型超级电容器在室温下静置2小时，然后用蓝电测试仪进行电化学性能测试。工作测试电压范围为1.2V-2.65V，在5000mA/g电流密度测试条件下充放电循环1000次后锌负极表面的扫描电镜图如图6所示，没有锌枝晶的生成，表明该混合型超级 电容器的安全性较高。 The artificial graphite and the binder polyvinylidene fluoride are mixed at a mass ratio of 9:1, and the mixed slurry is scraped on the washed aluminum foil positive electrode collector with a scraper to a film with a thickness of 150 μm, dried and cut into A positive pole piece with a diameter of 12 mm. The negative pole piece uses zinc foil with a diameter of 12 mm. A 4 mol/L concentration of Zn(PF 6 ) 2 /acetonitrile solution was used as an electrolyte, and a glass fiber with a diameter of 16.5 mm was used as a separator, and 150 μL of electrolyte was added dropwise on the separator. The battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top. The assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours, and then the electrochemical performance test is performed with a blue electric tester. The working test voltage range is 1.2V-2.65V, and the scanning electron micrograph of the surface of the zinc negative electrode after 1000 charge and discharge cycles under 5000mA/g current density test conditions is shown in Figure 6. No zinc dendrites are generated, indicating that the mixed type The safety of supercapacitors is high.
实施例7：Example 7:
将天然石墨和粘结剂聚偏氟乙烯以9:1的质量比混合，用刮刀将混合浆料在洗净的铝箔正极集流体上刮上厚度为150μm的一层膜，烘干后裁成直径为12mm的正极极片。负极极片采用直径为12mm的锌箔。5mol/L浓度的Zn(BF 4) 2/碳酸乙烯酯溶液作为电解液，直径为16.5mm的玻璃纤维作为隔膜，在隔膜上滴加150μL电解液。采用电池封装机进行封装，从下往上依次是负极壳、负极极片、隔膜、正极极片、垫片、弹片、正极壳。组装好的混合型超级电容器在室温下静置2小时，然后用蓝电测试仪进行电化学性能测试，计算得到该混合型超级电容器的能量密度如表1所示。 The natural graphite and the binder polyvinylidene fluoride are mixed at a mass ratio of 9:1, and the mixed slurry is scraped on the washed aluminum foil positive electrode collector with a scraper to a film with a thickness of 150 μm, dried and cut into A positive pole piece with a diameter of 12 mm. The negative pole piece uses zinc foil with a diameter of 12 mm. A 5 mol/L concentration of Zn(BF 4 ) 2 /ethylene carbonate solution was used as an electrolyte, and a glass fiber with a diameter of 16.5 mm was used as a separator, and 150 μL of electrolyte was added dropwise on the separator. The battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top. The assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours, and then the electrochemical performance test is performed with a blue electric tester. The energy density of the hybrid supercapacitor is calculated and shown in Table 1.
实施例8：Example 8:
将天然石墨和粘结剂羧甲基纤维素以9:1的质量比混合，用刮刀将混合浆料在洗净的铝箔正极集流体上刮上厚度为150μm的一层膜，烘干后裁成直径为12mm的正极极片。负极极片采用直径为12mm的锌箔。1mol/L浓度的Zn(NO 3) 2/乙腈溶液作为电解液，直径为16.5mm的玻璃纤维作为隔膜，在隔膜上滴加150μL电解液。采用电池封装机进行封装，从下往上依次是负极壳、负极极片、隔膜、正极极片、垫片、弹片、正极壳。组装好的混合型超级电容器在室温下静置2小时，然后用蓝电测试仪进行电化学性能测试，计算得到该混合型超级电容器的能量密度如表1所示。 The natural graphite and the binder carboxymethyl cellulose are mixed in a mass ratio of 9:1, and the mixed slurry is scraped on the washed aluminum foil positive current collector with a scraper to a film with a thickness of 150 μm, dried and cut A positive pole piece with a diameter of 12 mm is formed. The negative pole piece uses zinc foil with a diameter of 12 mm. A Zn(NO 3 ) 2 /acetonitrile solution at a concentration of 1 mol/L is used as an electrolyte, and a glass fiber with a diameter of 16.5 mm is used as a separator, and 150 μL of electrolyte is added dropwise on the separator. The battery packaging machine is used for packaging, and the negative electrode shell, the negative electrode piece, the separator, the positive electrode piece, the gasket, the shrapnel, and the positive electrode case are arranged in order from bottom to top. The assembled hybrid supercapacitor is allowed to stand at room temperature for 2 hours, and then the electrochemical performance test is performed with a blue electric tester. The energy density of the hybrid supercapacitor is calculated and shown in Table 1.
表1Table 1
编号Numbering 能量密度(Wh/kg)Energy density (Wh/kg)
实施例1Example 1 9999
实施例2Example 2 9191
实施例3Example 3 9393
实施例4Example 4 9696
实施例5Example 5 9898
实施例6Example 6 101101
实施例7Example 7 9696
实施例8Example 8 9494
对比例1Comparative Example 1 1414
对比例2Comparative Example 2 3535
对比例3Comparative Example 3 3737

Claims (9)

  1. 一种基于石墨正极和锌负极的混合型超级电容器，由正极、负极以及介于所述正极与所述负极之间的隔膜和电解液组成，其特征在于：所述负极的活性材料为锌；所述正极包含石墨组成的正极活性材料、导电剂和粘结剂；所述电解液包括锌盐电解质和有机溶剂。A hybrid supercapacitor based on a graphite positive electrode and a zinc negative electrode is composed of a positive electrode, a negative electrode, a separator and an electrolyte interposed between the positive electrode and the negative electrode, and is characterized in that the active material of the negative electrode is zinc; The positive electrode includes a positive electrode active material composed of graphite, a conductive agent and a binder; the electrolytic solution includes a zinc salt electrolyte and an organic solvent.
  2. 根据权利要求1所述的混合型超级电容器，其特征在于：所述正极包括正极活性材料、导电剂和黏结剂，按重量百分比计，所述正极材料由质量分数为85-95％的正极活性材料、0-5％的导电剂和5-10％粘结剂组成。The hybrid supercapacitor according to claim 1, wherein the positive electrode includes a positive electrode active material, a conductive agent, and a binder, and the positive electrode material has a positive electrode activity with a mass fraction of 85-95% by weight percentage Material, 0-5% conductive agent and 5-10% binder.
  3. 根据权利要求1-2所述的混合型超级电容器，其特征在于：所述组成正极活性材料的石墨为天然石墨和人造石墨中的一种或两种的组合。The hybrid supercapacitor according to claims 1-2, wherein the graphite constituting the positive electrode active material is one or a combination of natural graphite and artificial graphite.
  4. 根据权利要求1所述的混合型超级电容器，其特征在于：所述负极活性材料为锌片、锌箔、锌粉、锌合金中的一种或多种。The hybrid supercapacitor according to claim 1, wherein the negative electrode active material is one or more of zinc flake, zinc foil, zinc powder, and zinc alloy.
  5. 根据权利要求1所述的超级电容器，其特征在于：所述粘结剂为聚偏氟乙烯、聚四氟乙烯、羧甲基纤维素、丁苯橡胶中的一种或多种的组合。The supercapacitor according to claim 1, wherein the binder is one or a combination of polyvinylidene fluoride, polytetrafluoroethylene, carboxymethyl cellulose, and styrene-butadiene rubber.
  6. 根据权利要求1所述的混合型超级电容器，其特征在于：所述锌盐电解质为ZnSO 4、Zn(NO 3) 2、ZnCl 2、Zn(CH 3COO) 2、Zn(ClO 4) 2、Zn(BF 4) 2、Zn(CF 3SO 3) 2、Zn[N(CF 3SO 2) 2] 2、Zn(PF 6) 2一种或两种以上按一定比例混合而成。 The hybrid supercapacitor according to claim 1, wherein the zinc salt electrolyte is ZnSO 4 , Zn(NO 3 ) 2 , ZnCl 2 , Zn(CH 3 COO) 2 , Zn(ClO 4 ) 2 , Zn(BF 4 ) 2 , Zn(CF 3 SO 3 ) 2 , Zn[N(CF 3 SO 2 ) 2 ] 2 , Zn(PF 6 ) 2 are mixed by a certain proportion or more.
  7. 根据权利要求6所述的混合型超级电容器，其特征在于：所述电解液中锌离子的浓度范围为0.1-5mol/L。The hybrid supercapacitor according to claim 6, wherein the concentration of zinc ions in the electrolyte is in the range of 0.1-5mol/L.
  8. 根据权利要求1所述的混合型超级电容器，其特征在于：所述溶剂为介电常数大于20的有机溶剂，包括乙腈、碳酸丙烯酯、碳酸乙烯酯中的一种或两种以上按一定比例混合而成。The hybrid supercapacitor according to claim 1, wherein the solvent is an organic solvent having a dielectric constant greater than 20, including one or more of acetonitrile, propylene carbonate, and ethylene carbonate in a certain proportion Mixed.
  9. 一种混合型超级电容器的制备方法，其特征在于：将正极、负极、隔膜和电解液进行组装，得到所述基于石墨正极和锌负极的混合型超级电容器。A method for preparing a hybrid supercapacitor is characterized by assembling a positive electrode, a negative electrode, a separator and an electrolyte to obtain the hybrid supercapacitor based on graphite positive electrode and zinc negative electrode.
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