CN107369565B - Magnesium ion hybrid supercapacitor and preparation method thereof - Google Patents

Magnesium ion hybrid supercapacitor and preparation method thereof Download PDF

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CN107369565B
CN107369565B CN201710584742.7A CN201710584742A CN107369565B CN 107369565 B CN107369565 B CN 107369565B CN 201710584742 A CN201710584742 A CN 201710584742A CN 107369565 B CN107369565 B CN 107369565B
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magnesium
active material
negative electrode
hybrid supercapacitor
ion hybrid
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CN107369565A (en
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唐永炳
吴石
张帆
陈光海
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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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
    • H01G11/22—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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • H01G11/40—Fibres
    • 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
    • H01G11/46—Metal oxides
    • 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

Abstract

The invention provides a magnesium ion mixed super capacitor and a preparation method thereof, relating to the technical field of super capacitors, wherein the magnesium ion mixed super capacitor comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are arranged between the positive electrode and the negative electrode; the negative electrode active material layer includes a negative electrode active material, and the negative electrode active material is a non-carbon material. The magnesium ion hybrid super capacitor solves the problems of low working voltage, low specific capacity and low energy density of the magnesium ion hybrid super capacitor in the prior art, and achieves the technical effects of improving the working voltage, the specific capacity and the energy density.

Description

Magnesium ion hybrid supercapacitor and preparation method thereof
Technical Field
The invention relates to the technical field of super capacitors, in particular to a magnesium ion hybrid super capacitor and a preparation method thereof.
Background
Supercapacitors, also called electrochemical capacitors, mainly consist of: positive electrode, negative electrode, electrolyte and diaphragm. The super capacitor is a novel energy storage system considered to be between a traditional capacitor and a lithium ion battery system, energy is stored mainly through rapid and reversible adsorption and desorption or oxidation reduction reaction (pseudo-capacitance) on a double electric layer or an electrode interface, compared with other energy storage systems, the super capacitor has the advantages of long cycle life, quick charging, high power density, environmental protection, wide working temperature range and the like, and is widely applied to the fields of transportation, electric power, communication, intelligent instruments, industrial control, national defense, consumer electronics, new energy automobiles and the like.
However, the supercapacitor has a low energy density because it stores energy by reversibly adsorbing/desorbing electrolyte ions through an electrode material. In recent years, in order to further improve the energy density of the super capacitor, researchers have successfully developed a new capacitor, an asymmetric capacitor, which is also called a hybrid super capacitor. In the super capacitor, one electrode uses an electric double layer electrode material to perform adsorption and desorption reaction energy storage, and the other electrode uses a traditional battery electrode so as to store energy through electrochemical oxidation-reduction reaction. This type of battery has a higher specific capacity and operating voltage, and therefore has a significantly higher energy density than an electric double layer capacitor. For the research and development of hybrid supercapacitors, a great deal of work is currently focused on lithium-ion hybrid supercapacitors based on lithium salt electrolyte, which achieve the adsorption (or storage) and desorption (or release) of charges through the migration of lithium ions. For example, the high-rise military et al (application number CN201020135552.0) invented a hybrid supercapacitor, in which the positive electrode active material is activated carbon, the negative electrode active material is lithium titanate, and the electrolyte is a lithium ion electrolyte, and the capacitor system can maintain high capacity, good cycling stability and long service life under the condition of large current. However, the lithium ion hybrid supercapacitor of the above type has the disadvantages of limited lithium resource storage and high cost. Finding low cost, high performance hybrid supercapacitors is becoming an increasing focus.
At present, the research on magnesium ion hybrid supercapacitors in the industry is not much, and the working voltage and energy density of the capacitor prepared by using the magnesium ions are low, the working voltage is generally 0.5-2.5V, and the energy density is about 10Wh/kg, so that the requirements of modern industrial equipment and traffic equipment cannot be met.
Disclosure of Invention
The invention aims to provide a magnesium ion hybrid supercapacitor to solve the technical problems that the magnesium ion capacitor in the prior art is low in working voltage, low in specific capacity and low in energy density and cannot meet the requirements of industrial equipment and traffic equipment.
The second purpose of the invention is to provide a preparation method of a magnesium ion hybrid supercapacitor, so as to alleviate the problems of low working voltage, low specific capacity and low energy density of the magnesium ion hybrid supercapacitor in the prior art.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a magnesium ion hybrid supercapacitor comprises a positive electrode, a negative electrode and a diaphragm and an electrolyte which are arranged between the positive electrode and the negative electrode, wherein the positive electrode comprises a positive electrode active material layer capable of adsorbing and desorbing magnesium salt anions, and the negative electrode comprises a negative electrode active material layer capable of embedding and extracting magnesium ions; the negative electrode active material layer includes a negative electrode active material that is a non-carbon material.
Further, the anode active material comprises one or a combination of at least two of a schiffer phase material, a mixed schiffer phase material, a transition metal sulfide, a transition metal selenide, a transition metal telluride or a transition metal oxide.
Further, the Scherfler phase material is Mo6T8Wherein T is S, Se or Te.
Further, the mixed Scherfield phase material is Mo6S8-ySeyAnd CuxMo6S8A mixture of (a); wherein: x is approximately equal to 1; y is 1 or 2.
Further, the negative active material layer comprises the following raw materials in percentage by weight: 60-95 wt% of positive electrode active material, 2-30 wt% of conductive agent and 3-10 wt% of binder.
Further, the negative active material layer comprises the following raw materials in percentage by weight: 75-85 wt% of negative electrode active material, 15-20 wt% of conductive agent and 5-10 wt% of binder.
Further, the negative electrode comprises a negative electrode current collector, and the negative electrode current collector is a metal foil.
Further, the metal is selected from any one or any one alloy of copper, chromium, magnesium, iron, nickel, tin, zinc, lithium, aluminum, calcium, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, beryllium, silver, gold or barium.
Further, the negative current collector is a copper foil.
Further, the positive active material layer comprises a positive active material, and the positive active material comprises one or a combination of at least two of activated carbon, porous carbon, graphene, carbon nanotubes or carbon fibers.
Further, the positive active material layer comprises the following raw materials in percentage by weight: 60-95 wt% of negative electrode active material, 2-30 wt% of conductive agent and 3-10 wt% of binder.
Further, the positive active material layer comprises the following raw materials in percentage by weight: 75-85 wt% of negative electrode active material, 15-20 wt% of conductive agent and 5-10 wt% of binder.
Further, the positive electrode comprises a positive electrode current collector, and the positive electrode current collector is a metal foil.
Further, the metal is selected from any one or any one alloy of aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium or manganese.
Further, the positive current collector is an aluminum foil.
Further, the electrolyte comprises an electrolyte and a solvent, and the electrolyte is a magnesium salt.
Further, the concentration range of the magnesium salt is 0.1-10 mol/L.
Further, the organic magnesium salt includes RMgX, pyrrolyl magnesium bromide, N-methylaniline magnesium bromide, N-bis (trimethylsilyl) amino magnesium chloride, Mg (SnPh)3)2Disodium magnesium ethylenediaminetetraacetate, Mg (BR)2R'2)2Or Mg (AZ)3-nRn'R'n”)2One or a combination of at least two of the type complexes;
wherein R is alkyl; x is halogen; a is Al, B, As, P, Sb, Ta or Fe; z is Cl or Br; r ' is aryl, and n ' + n ═ n, where 0< n ' + n "< 3.
Further, the inorganic magnesium salt includes Mg (ClO)4)2、Mg(BF4)2、Mg(PF6)2、MgCl2、MgBr2、MgF2、MgI2、Mg(NO3)2、MgSO4、Mg(SCN)2、MgCrO4Or Mg (CF)3SO3)2Or a combination of at least two thereof.
According to the preparation method of the magnesium ion hybrid supercapacitor, a positive electrode, a negative electrode, a diaphragm and electrolyte are assembled to obtain the magnesium ion hybrid supercapacitor.
Compared with the prior art, the invention has the following beneficial effects:
the magnesium ion hybrid supercapacitor provided by the invention is formed by adopting a positive electrode active material layer capable of adsorbing and desorbing magnesium salt anions and a negative electrode active material layer capable of embedding and desorbing magnesium ions, and the negative electrode active material is a non-carbon material. During charging, magnesium ions migrate to the negative electrode and are directly embedded into the negative electrode active material layer, and meanwhile, magnesium salt anions migrate to the positive electrode and are adsorbed on the surface of the positive electrode active material layer; in the discharging process, magnesium ions of the negative electrode are directly separated from the negative electrode active material layer and enter the electrolyte, and magnesium salt anions can be desorbed from the surface of the positive electrode active material layer and return to the electrolyte, so that reversible charging and discharging are realized. The working voltage of the magnesium ion hybrid super capacitor provided by the invention can reach more than 4.5V, the specific capacity can reach 95F/g, and the energy density can reach 45 Wh/kg.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural diagram of a magnesium ion hybrid supercapacitor provided in the invention.
Icon: 10-positive current collector; 20-a positive electrode active material layer; 30-an electrolyte; 40-a membrane; 50-a negative active material layer; 60-negative current collector.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the present invention provides a magnesium ion hybrid supercapacitor, including a positive electrode, a negative electrode, and a separator and an electrolyte interposed between the positive electrode and the negative electrode, the positive electrode including a positive active material layer capable of adsorbing and desorbing magnesium salt anions, the negative electrode including a negative active material layer capable of intercalating and deintercalating magnesium ions; the negative electrode active material layer includes a negative electrode active material that is a non-carbon material.
The magnesium ion hybrid supercapacitor provided by the invention is formed by adopting a positive electrode active material layer capable of adsorbing and desorbing magnesium salt anions and a negative electrode active material layer capable of embedding and desorbing magnesium ions, and the negative electrode active material is a non-carbon material. During charging, magnesium ions migrate to the negative electrode and are directly embedded into the negative electrode active material, and meanwhile, magnesium salt anions migrate to the positive electrode and are adsorbed on the surface of the positive electrode active material; in the discharging process, magnesium ions of the negative electrode are directly separated from the negative electrode active material and enter the electrolyte, and magnesium salt anions are desorbed from the positive electrode active material and return to the electrolyte, so that reversible charging and discharging are realized. According to the cathode material, the cathode active material layer capable of embedding and extracting magnesium ions is innovatively used, so that the embedding and extracting reactions of the magnesium ions in the electrolyte are facilitated, the capacity of the capacitor is improved, and the energy density of the capacitor is further improved. The working voltage of the magnesium ion hybrid super capacitor provided by the invention can reach more than 4.5V, the specific capacity can reach 95F/g, and the energy density can reach 45 Wh/Kg.
As a preferred embodiment of the present invention, the anode active material includes one or a combination of at least two of scherrer phase material, mixed scherrer phase material, transition metal sulfide, transition metal selenide, transition metal telluride, or transition metal oxide.
The Scherfell phases (CPs for short) material is a typical mixed conductor with a layered structure, and when certain guest metals enter CPs crystal lattices, the material still retains the structural characteristics of the original compound, thereby well realizing the mutual conversion of electric energy and chemical energy. The Scherfler phase material herein refers to a single Scherfler phase material.
The mixed Scherfield phase material is a combination of at least two Scherfield phase compounds, and can provide more effective intercalation materials for magnesium ions by utilizing a mixed phase structure.
The cathode active material adopts a Scherfree phase material with a layered crystal structure, so that intercalation/de-intercalation reaction of cations in the electrolyte is facilitated, the capacity of the capacitor is improved, and further the energy density is improved. In the preferred embodiment, the cathode material is made of a cathode active material (scherrel phase material) layer capable of intercalating magnesium ions, so as to facilitate the intercalation/deintercalation reaction of magnesium ions in the electrolyte, thereby improving the capacity of the capacitor and further improving the energy density of the capacitor.
The transition metal sulfide is typically, but not limited to, selected from one or a combination of at least two of molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, iron disulfide, ferrous sulfide, nickel sulfide, zinc sulfide, cobalt sulfide, or manganese sulfide.
The transition metal selenide is typically, but not limited to, selected from one or a combination of at least two of tungsten diselenide, stannous selenide, molybdenum selenide, zinc selenide.
The transition metal telluride is typically, but not limited to, selected from one or a combination of at least two of molybdenum telluride, zinc telluride or bismuth telluride.
The transition metal oxide is typically, but not limited to, selected from one or a combination of at least two of vanadium pentoxide, manganese dioxide, molybdenum trioxide, lithium titanate, vanadium dioxide, nickel oxide, or tungsten trioxide.
The cathode active material adopts transition metal sulfide and other materials, participates in redox reaction with magnesium ions, has higher specific capacity, and further improves energy density.
In a preferred embodiment of the present invention, the Scherfree phase material is Mo6T8Wherein T is S, Se or Te.
In a preferred embodiment of the present invention, the mixed Scherfree phase material is Mo6S8-ySeyAnd CuxMo6S8A mixture of (a);
wherein: x is approximately equal to 1; y is 1 or 2.
Through the preferable composition of the Scherfield phase material, the deintercalation reaction of the negative active material layer and magnesium ions can be further optimized, so that the intercalation and deintercalation of the magnesium ions are facilitated, and the energy density of the capacitor is improved.
As a preferred embodiment of the present invention, the anode active material layer includes the following raw materials in percentage by weight: 60-95 wt% of a negative electrode active material, 2-30 wt% of a conductive agent and 3-10 wt% of a binder; preferably, the negative active material layer comprises the following raw materials in percentage by weight: 75-85 wt% of negative electrode active material, 15-20 wt% of conductive agent and 5-10 wt% of binder.
In the preferred embodiment described above, typical but non-limiting percentages of the negative electrode active material are, for example: 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt% or 95 wt%.
In the preferred embodiment described above, typical but non-limiting percentages of the conductive agent are, for example: 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%.
In the preferred embodiment described above, typical but non-limiting percentages of the binder are for example: 3, 4, 5, 6, 7, 8, 9 or 10 wt%.
The proportion of the negative active material, the conductive agent and the binder in the negative active material layer is optimized, so that the negative active material and the conductive agent form an optimal matching relationship to promote the insertion and extraction movement of magnesium ions.
As a preferred embodiment of the present invention, the negative electrode includes a negative electrode current collector, which is a metal foil; preferably, the metal is selected from any one or an alloy of any one of copper, chromium, magnesium, iron, nickel, tin, zinc, lithium, aluminum, calcium, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, beryllium, silver, gold or barium; further preferably, the negative electrode current collector is a copper foil.
By optimizing the metal composition of the negative current collector, the negative current collector has higher stability on the premise of meeting the conductivity.
As a preferred embodiment of the present invention, the positive electrode active material includes one or a combination of at least two of activated carbon, porous carbon, graphene, carbon nanotubes, or carbon fibers.
Active carbon, porous carbon, graphene, carbon nanotubes or carbon fibers are used as the anode of the magnesium ion hybrid supercapacitor, more anions can be accumulated on the surface of the anode, and the energy density of the capacitor is improved.
As a preferred embodiment of the present invention, the positive electrode active material layer comprises the following raw materials in percentage by weight: 60-95 wt% of positive electrode active material, 2-30 wt% of conductive agent and 3-10 wt% of binder; preferably, the positive active material layer comprises the following raw materials in percentage by weight: 75-85 wt% of positive electrode active material, 15-20 wt% of conductive agent and 5-10 wt% of binder.
In the preferred embodiment described above, typical but non-limiting percentages of the positive electrode active material are, for example: 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt% or 95 wt%.
In the preferred embodiment described above, typical but non-limiting percentages of the conductive agent are, for example: 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt%.
In the preferred embodiment described above, typical but non-limiting percentages of the binder are for example: 3, 4, 5, 6, 7, 8, 9 or 10 wt%.
By optimizing the proportion of the positive active material, the conductive agent and the binder in the positive active material layer, the optimal matching relationship between the positive active material and the conductive agent is formed, so as to promote magnesium salt anions on the surface of the positive active material layer.
The conductive agent is one or the combination of at least two of conductive graphite, conductive acetylene black, conductive carbon spheres, graphene and carbon nanotubes; the binder is one or the combination of at least two of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, polyvinyl alcohol, carboxymethyl cellulose or polyolefin.
As a preferred embodiment of the present invention, the positive electrode includes a positive electrode current collector, and the positive electrode current collector is a metal foil; preferably, the metal is selected from any one or an alloy of any one of aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium or manganese; further preferably, the positive electrode current collector is an aluminum foil.
The metal composition of the positive current collector is optimized, so that the positive current collector has higher stability on the premise of meeting the conductivity.
As a preferred embodiment of the present invention, the electrolyte comprises an electrolyte and a solvent, the electrolyte is a magnesium salt; preferably, the concentration of the magnesium salt is in the range of 0.1-10 mol/L.
The concentration range of the magnesium salt is optimized to be beneficial to the movement of ions in the electrolyte, so that the charge and discharge performance of the capacitor is improved.
As a preferred embodiment of the present invention, the magnesium salt includes an organic magnesium salt or an inorganic magnesium salt; preferably, the organic magnesium salt comprises RMgX, pyrrolyl magnesium bromide, N-methylaniline magnesium bromide, N-bis (trimethylsilyl) amino magnesium chloride, Mg (SnPh)3)2Disodium magnesium ethylene diamine tetraacetate (EDTA-Mg) and Mg (BR)2R'2)2、Mg(AZ3-nRn'R'n”)2One or a combination of at least two of the type complexes; wherein R is alkyl; x is halogen; a is Al, B, As, P, Sb, Ta or Fe; z is Cl or Br; r 'is aryl, and n' + n ═ n. Preferably, the inorganic magnesium salt includes Mg (ClO)4)2、Mg(BF4)2、Mg(PF6)2、MgCl2、MgBr2、MgF2、MgI2、Mg(NO3)2、MgSO4、Mg(SCN)2Or MgCrO4、Mg(CF3SO3)2Or a combination of at least two thereof.
The charge and discharge performance of the capacitor is improved by optimizing the components of the magnesium salt.
As a preferred embodiment of the present invention, the solvent includes one or a combination of at least two of esters, sulfones, ethers, nitrile organic solvents, imidazoles, piperidines, pyrroles, quaternary amines and amide ionic liquids; alternatively, the solvent is selected from the group consisting of methylisopropyl carbonate, methyl ester, methyl formate, methyl acetate, propylene carbonate, ethylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylethyl carbonate, methylpropyl carbonate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, dibutyl carbonate, methylbutyl carbonate, N-dimethylacetamide, fluoroethylene carbonate, methyl propionate, ethyl acetate 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, dimethylsulfone, acetonitrile, dimethyl ether, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, dimethyl ether, dimethyl sulfite, dimethyl sulfate, diethyl sulfite, dimethyl sulfate, dimethyl, Crown ethers, 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, N-methyl, one or a combination of at least two of propylpiperidine-bistrifluoromethylsulfonyl imide salt, N-methyl, butylpiperidinbistrifluoromethylsulfonyl imide salt, N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl-N-propylpyrrolidine-bistrifluoromethylsulfonyl imide salt. Further preferably, the ethereal solvent includes one or a combination of at least two of Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2Me-THF), 1, 3-Dioxolane (DN), 1, 4-dioxane, ethylene glycol dimethyl ether (DME), diethyl ether (DEE), or tetraethylene glycol dimethyl ether.
In a preferred embodiment of the present invention, the separator includes an insulating porous polymer film or an inorganic porous film; preferably, the separator includes one or a combination of at least two of a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, a non-woven fabric, a glass fiber paper, or a porous ceramic separator.
The invention also provides a preparation method of the magnesium ion hybrid supercapacitor, which is characterized in that a positive electrode, a negative electrode, a diaphragm and electrolyte are assembled to obtain the magnesium ion hybrid supercapacitor.
As a preferred embodiment of the present invention, the above preparation method comprises the steps of:
step a): preparing a positive electrode: firstly, weighing a proper amount of positive active material, a proper amount of binder and a proper amount of conductive agent according to a certain proportion, uniformly mixing, adding a proper amount of solvent, fully grinding into uniform slurry to prepare a positive active material layer; then, taking a metal, metal alloy or metal compound conductive material as a positive current collector, uniformly coating the positive active material layer on the surface of the positive current collector, placing the positive active material layer in a vacuum drying box at a certain temperature for drying, and blanking the positive active material layer into a positive electrode with a required size after the positive active material layer is completely dried;
step b): preparing a negative electrode: firstly, weighing a proper amount of negative active material, a binder and a conductive agent according to a certain proportion, uniformly mixing, adding a proper amount of solvent, fully grinding into uniform slurry to prepare a negative active material layer; then, taking a metal, metal alloy or metal compound conductive material as a negative current collector, uniformly coating the negative active material layer on the surface of the negative current collector, placing the negative current collector in a vacuum drying box at a certain temperature for drying, and blanking into a negative electrode with a required size after the negative active material layer is completely dried;
step c): preparing a diaphragm: punching a porous polymer film or an inorganic porous film or an organic/inorganic composite diaphragm into a required size to be used as a diaphragm for later use;
step d): preparing an electrolyte: adding a certain amount of magnesium salt electrolyte into a corresponding solvent and an additive, and fully stirring and dissolving;
step e): and assembling the anode, the cathode, the diaphragm and the electrolyte prepared in the steps to obtain the magnesium ion mixed super capacitor.
The shape of the magnesium ion hybrid supercapacitor prepared by the above preparation method provided by the present invention is not particularly limited, and is, for example, a button type, a flat plate type or a cylindrical type.
It should be noted that although the steps described above describe the operations of the preparation method of the present invention in a particular order, this does not require or imply that these operations must be performed in this particular order. The preparation of steps a), b), c) and d) can be carried out simultaneously or in any sequence.
The invention is further illustrated by the following specific examples and comparative examples, but it should be understood that these examples are for purposes of illustration only and are not to be construed as limiting the invention in any way.
Example 1
A magnesium ion hybrid supercapacitor is structurally shown in figure 1 and comprises a positive electrode current collector 10, a positive electrode active material layer 20, an electrolyte 30, a diaphragm 40, a negative electrode active material layer 50 and a negative electrode current collector 60.
The positive electrode consists of an aluminum foil and a positive active material layer 20 of the following composition: activated carbon (specific surface area 2500 m)2Per g)80 wt%, 10 wt% of conductive graphite and 10 wt% of polytetrafluoroethylene.
The electrolyte 30 is Mg (PF)6)2And ethylene carbonate: dimethyl carbonate: and (3) methyl ethyl carbonate (in a volume ratio of 1:1:1) is mixed to prepare a solution.
The separator 40 is a porous polypropylene film.
The negative electrode composition includes a copper foil and a negative electrode active material layer 50 of the following composition: MoS280 wt%, conductive graphite 10 wt% and polyvinylidene fluoride 10 wt%.
The preparation method of the magnesium ion hybrid supercapacitor comprises the following steps:
step a): preparing a negative electrode: adding 0.8g of molybdenum disulfide, 0.1g of conductive graphite and 0.1g of polyvinylidene fluoride into 2mL of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; then uniformly coating the slurry on the surface of the copper foil, carrying out vacuum drying, cutting the dried electrode slice into a wafer with the diameter of 12mm, and compacting the wafer to be used as a negative electrode for later use;
step b): preparing an electrolyte: weighing 1.256g of magnesium hexafluorophosphate, adding the weighed magnesium hexafluorophosphate into 5mL of a mixed solvent (volume ratio is 1:1:1) of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, stirring until the magnesium hexafluorophosphate is completely dissolved, and fully stirring uniformly to serve as an electrolyte for standby (the concentration of the electrolyte is 0.8M);
step c): preparing a positive electrode: 0.8g of porous carbon (specific surface area 2500 m)2Adding 0.1g of conductive carbon black and 0.1g of polytetrafluoroethylene into 10mL of ethanol, and fully grinding to obtain uniform slurry; then uniformly coating the slurry on the surface of the carbon-coated aluminum foil, carrying out vacuum drying, cutting the dried electrode slice into a wafer with the diameter of 12mm, and compacting the wafer to be used as a positive electrode for later use;
step d): preparing a diaphragm: cutting the glass fiber diaphragm into a wafer with the diameter of 16mm, and drying the wafer to be used as the diaphragm for later use;
step e): assembling: and in a glove box protected by inert gas, tightly stacking the prepared positive electrode, the diaphragm and the negative electrode in sequence, dripping electrolyte to completely soak the diaphragm, and packaging the stacked part into a button type shell to finish the assembly of the magnesium ion mixed super capacitor.
Example 2
A magnesium ion mixed super capacitor, wherein the negative electrode material active material adopts Mo6Se8Otherwise, the same as in example 1.
Example 3
A magnesium ion mixed super capacitor, wherein the negative electrode material active material adopts Mo6Te8Otherwise, the same as in example 1.
Example 4
A magnesium ion mixed super capacitor, wherein the negative electrode material active material adopts Mo6S6Se2Otherwise, the same as in example 1.
Example 5
A magnesium ion mixed super capacitor, wherein the cathode material active material adopts CuMo6S8Otherwise, the same as in example 1.
Example 6
A magnesium ion hybrid supercapacitor, wherein molybdenum disulfide is used as a negative electrode material active material, and the rest is the same as in example 1.
Example 7
A magnesium ion hybrid supercapacitor, in which ferrous sulfide is used as a negative electrode material active material, is otherwise the same as in example 1.
Example 8
The magnesium ion mixed super capacitor is characterized in that a negative electrode material active substance adopts stannous selenide, and the rest is the same as that in the embodiment 1.
Example 9
A magnesium ion hybrid supercapacitor, wherein zinc selenide is used as a negative electrode material active material, and the rest is the same as in example 1.
Example 10
A magnesium ion hybrid supercapacitor in which molybdenum telluride is used as a negative electrode material active material, and the rest is the same as in example 1.
Example 11
A magnesium ion mixed super capacitor is provided, wherein a negative electrode material active substance adopts zinc telluride, and the rest is the same as the embodiment 1.
Example 12
A magnesium ion hybrid supercapacitor, wherein vanadium pentoxide is used as a negative electrode material active material, and the rest is the same as in example 1.
Example 13
A magnesium ion hybrid supercapacitor in which manganese dioxide was used as a negative electrode material active material, and the other examples were the same as in example 1.
Example 14
A magnesium ion mixed super capacitor, wherein the active substance of the positive electrode material adopts porous carbon (the specific surface area is 2000 m)2In g), the rest is the same as in example 1.
Example 15
The magnesium ion hybrid supercapacitor is characterized in that graphene is used as a positive electrode material active substance, and the rest is the same as that in example 1.
Example 16
A magnesium ion mixed super capacitor, wherein the active material of the positive electrode material adopts carbon nano tubes, and the rest is the same as that of the embodiment 1.
Example 17
A magnesium ion hybrid supercapacitor, in which carbon fiber is used as the positive electrode material active material, was otherwise the same as in example 1.
Example 18
A magnesium ion mixed super capacitor is provided, wherein magnesium salt used in electrolyte is magnesium perchlorate, and the rest is the same as that in the embodiment 1.
Example 19
A magnesium ion mixed super capacitor is disclosed, wherein magnesium salt used in electrolyte is bis (trifluoromethylsulfonyl imide) magnesium, solvent is tetrahydrofuran, and the rest is the same as in example 1.
Example 20
A magnesium ion mixed super capacitor, wherein the magnesium salt used in the electrolyte is magnesium bis (trifluoromethanesulfonate), and the rest is the same as that in example 1.
Example 21
A magnesium ion mixed super capacitor is provided, wherein the magnesium salt used in the electrolyte is Mg (AlCl)2BuEt)2The solvent was tetrahydrofuran, and the rest was the same as in example 1.
Example 22
A magnesium ion mixed super capacitor is provided, wherein the magnesium salt used in the electrolyte is Mg (AlCl)3Bu)2The solvent was tetraglyme, the rest being the same as in example 1.
Example 23
A magnesium ion hybrid supercapacitor in which the electrolyte concentration is 0.4M, the other being the same as in example 1.
Example 24
A magnesium ion hybrid supercapacitor in which the electrolyte concentration is 0.6M, the other being the same as in example 1.
Example 25
A magnesium ion mixed super capacitor is provided, wherein the electrolyte uses ethylene carbonate and diethyl carbonate (volume ratio 1:1) as solvent, and the rest is the same as example 1.
Example 26
A magnesium ion mixed super capacitor is provided, wherein the electrolyte uses ethylene carbonate and ethyl methyl carbonate (volume ratio 1:1) as solvent, and the rest is the same as example 1.
Example 27
A magnesium ion mixed super capacitor is provided, wherein the electrolyte uses ethylene carbonate and dimethyl carbonate (volume ratio 1:1) as solvent, and the rest is the same as example 1.
Example 28
A magnesium ion hybrid supercapacitor is provided, in which a porous polypropylene film is used as a separator, and the rest is the same as in example 1.
Example 29
A magnesium ion hybrid supercapacitor is provided, in which a porous polyethylene film is used as a separator, and the rest is the same as in example 1.
Example 30
A magnesium ion hybrid supercapacitor, wherein a porous ceramic film is used as a separator, and the rest is the same as that of example 1.
Example 31
A magnesium ion hybrid supercapacitor in which the conductive agents used for the positive and negative electrodes are carbon nanotubes, the other steps being the same as in example 1.
Example 32
A magnesium ion mixed super capacitor is provided, wherein the conductive agent used by the positive electrode and the negative electrode is graphene, and the rest is the same as that in the embodiment 1.
Example 33
A magnesium ion mixed super capacitor, wherein the binder used by the positive electrode and the negative electrode is polyvinylidene fluoride, and the rest is the same as the embodiment 1.
Example 34
A magnesium ion mixed super capacitor, wherein the binder used by the positive electrode and the negative electrode is carboxymethyl cellulose, and the rest is the same as that in the embodiment 1.
Example 35
A magnesium ion mixed super capacitor, wherein the binder used by the positive electrode and the negative electrode is SBR rubber, and the rest is the same as the embodiment 1.
Comparative example 1
A lithium ion hybrid supercapacitor comprises a negative electrode, a diaphragm, electrolyte and a positive electrode. Wherein electrolyte is prepared: 0.76g of lithium hexafluorophosphate is weighed and added into 5mL of mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate (volume ratio is 4:3:2), stirred until the lithium hexafluorophosphate is completely dissolved, and fully and uniformly stirred to be used as electrolyte for standby. The rest is the same as in example 1.
Comparative example 2
A magnesium ion symmetric super capacitor comprises a negative electrode, a diaphragm, electrolyte and a positive electrode. The negative electrode and the positive electrode are completely the same and are both made of activated carbon materials. The rest is the same as in example 1.
Electrochemical performance and safety performance of the magnesium ion hybrid supercapacitors of examples 1-35 and the devices of comparative examples 1-2 were tested, and the test results are shown in table 1.
Electrochemical performance tests include specific capacitance, energy density and cycle number, using conventional capacitor test methods.
Table 1 electrochemical performance and safety performance test results of devices of examples and comparative examples
Figure BDA0001352616780000171
Figure BDA0001352616780000181
As can be seen from table 1, the magnesium ion hybrid supercapacitor of the present invention, which uses a non-carbon material into which magnesium ions can be inserted and extracted as a negative electrode active material and a porous carbon material as a positive electrode active material, has high specific capacity, high energy density, long cycle life, and good safety performance.
Examples 2-13 compared to example 1, the electrochemical performance of the resulting magnesium ion hybrid supercapacitor was slightly different with different negative electrode active materials.
Examples 14 to 17 are different from example 1 in the active material used for the positive electrode, and the electrochemical performance of the obtained magnesium ion hybrid supercapacitor is different, in which the specific capacity and energy density of the magnesium ion hybrid supercapacitor obtained by using the activated carbon having a large specific surface area as the positive electrode active material are higher than those of other magnesium ion hybrid supercapacitors obtained by using other carbon materials as the positive electrode active material.
In examples 18 to 22, the electrolyte used magnesium salt was different from that used in example 1, and the electrochemical performance of the obtained magnesium ion hybrid supercapacitor was slightly different.
In examples 23 to 24, the electrochemical performance of the obtained magnesium ion hybrid supercapacitor was different depending on the concentration of the electrolyte compared to example 1, and the specific capacity and energy density of the magnesium ion hybrid supercapacitor were the highest when the electrolyte was 0.8M.
In examples 25 to 27, compared with example 1, the electrolyte used different solvents, and the electrochemical performance of the obtained magnesium ion hybrid supercapacitor is different, it can be seen that the electrolyte solvent has certain influence on the specific capacity and energy density of the magnesium ion hybrid supercapacitor.
Examples 28-30 compared with example 1, the separators used were different, and the electrochemical performance of the resulting magnesium ion hybrid supercapacitor was not much different.
In examples 31 to 32, the types of the conductive agents used in the positive and negative electrode materials were different from those in example 1, and in examples 33 to 35, the types of the binders used in the positive and negative electrode materials were different from those in example 1, so that the electrochemical performance of the obtained magnesium ion hybrid supercapacitor was not greatly different, and it was found that the types of the conductive agents and the binders added to the positive and negative electrode materials had little influence on the electrochemical performance of the entire magnesium ion hybrid supercapacitor.
Comparative example 1 compared to example 1, comparative example 1 is a conventional lithium ion hybrid supercapacitor, which has a low energy density, a short service life, a limited lithium storage capacity, and a high cost, limiting the application of the lithium ion hybrid supercapacitor. Comparative example 2 compared to example 1, comparative example 2 is a conventional magnesium ion symmetric supercapacitor, which has a lower energy density and limits the application of supercapacitors.
The magnesium ion hybrid supercapacitor realizes energy storage through the embedding and the releasing of magnesium ions on a non-carbon negative electrode material and the adsorption and the desorption of anions on a positive electrode material. The problems of limited lithium ion resources and high cost are solved, the obtained magnesium ion hybrid supercapacitor is better than lithium in electrochemical performance, the anode and cathode materials are simple, easy to obtain, environment-friendly and safe, the production process is simple and low in cost, and the magnesium ion hybrid supercapacitor is a hybrid supercapacitor with high energy density, high power density and high safety.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (18)

1. The magnesium ion hybrid supercapacitor is characterized by comprising a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the diaphragm and the electrolyte are arranged between the positive electrode and the negative electrode, the positive electrode comprises a positive electrode active material layer capable of adsorbing and desorbing magnesium salt anions, and the negative electrode comprises a negative electrode active material layer capable of embedding and extracting magnesium ions; the negative electrode active material layer includes a negative electrode active material that is a non-carbon material;
the anode active material comprises one or a combination of at least two of transition metal sulfide, transition metal selenide or transition metal telluride;
the negative active material is selected from MoS2、Mo6Se8、Mo6Te8、Mo6S6Se2、CuMo6S8、FeS、SnSe、ZnSe、MoTe2Or ZnTe or a combination of at least two thereof.
2. The magnesium ion hybrid supercapacitor according to claim 1, wherein the negative active material layer comprises the following raw materials in percentage by weight: 60-95 wt% of negative electrode active material, 2-30 wt% of conductive agent and 3-10 wt% of binder.
3. The magnesium ion hybrid supercapacitor according to claim 2,
the negative active material layer comprises the following raw materials in percentage by weight: 75-85 wt% of negative electrode active material, 15-20 wt% of conductive agent and 5-10 wt% of binder.
4. The magnesium ion hybrid supercapacitor according to any one of claims 1 to 3, wherein the negative electrode comprises a negative electrode current collector, and the negative electrode current collector is a metal foil.
5. The magnesium-ion hybrid supercapacitor according to claim 4, wherein the metal is selected from any one of copper, chromium, magnesium, iron, nickel, tin, zinc, lithium, aluminum, calcium, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, beryllium, silver, gold, or barium, or an alloy of any one of these.
6. The magnesium ion hybrid supercapacitor according to claim 4, wherein the negative current collector is a copper foil.
7. The magnesium-ion hybrid supercapacitor according to claim 1, wherein the positive active material layer comprises a positive active material comprising one of activated carbon, porous carbon, graphene, carbon nanotubes, carbon fibers or a combination of at least two thereof.
8. The magnesium ion hybrid supercapacitor according to claim 7, wherein the positive active material layer comprises the following raw materials in percentage by weight: 60-95 wt% of positive electrode active material, 2-30 wt% of conductive agent and 3-10 wt% of binder.
9. The magnesium ion hybrid supercapacitor according to claim 8, wherein the positive active material layer comprises the following raw materials in percentage by weight: 75-85 wt% of positive electrode active material, 15-20 wt% of conductive agent and 5-10 wt% of binder.
10. The magnesium-ion hybrid supercapacitor according to claim 1, wherein the positive electrode comprises a positive current collector, and the positive current collector is a metal foil.
11. The magnesium ion hybrid supercapacitor according to claim 10, wherein the metal is selected from any one of aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium or manganese or an alloy of any one of them.
12. The magnesium ion hybrid supercapacitor according to claim 10, wherein the positive current collector is aluminum foil.
13. The magnesium ion hybrid supercapacitor of claim 1, wherein the electrolyte comprises an electrolyte and a solvent, the electrolyte being a magnesium salt.
14. The magnesium ion hybrid supercapacitor according to claim 13, wherein the concentration of the magnesium salt is in the range of 0.1-10 mol/L.
15. The magnesium ion hybrid supercapacitor of claim 13, wherein the magnesium salt comprises an organic magnesium salt or an inorganic magnesium salt.
16. The magnesium-ion hybrid supercapacitor of claim 15, wherein the organic magnesium salt comprises RMgX, pyrrolyl magnesium bromide, N-methylaniline magnesium bromide, N-bis (trimethylsilyl) amino magnesium chloride, Mg (SnPh)3)2Disodium magnesium ethylenediaminetetraacetate, Mg (BR)2R'2)2Or Mg (AZ)3-nRn'R'n”)2One or a combination of at least two of the type complexes;
wherein R is alkyl; x is halogen; a is Al, B, As, P, Sb, Ta or Fe; z is Cl or Br; r ' is aryl, and n ' + n ═ n, where 0< n ' + n "< 3.
17. The magnesium-ion hybrid supercapacitor of claim 15, wherein the inorganic magnesium salt comprises Mg (ClO)4)2、Mg(BF4)2、Mg(PF6)2、MgCl2、MgBr2、MgF2、MgI2、Mg(NO3)2、MgSO4、Mg(SCN)2、MgCrO4Or Mg (CF)3SO3)2Or a combination of at least two thereof.
18. A method for preparing the magnesium ion hybrid supercapacitor according to any one of claims 1 to 17, wherein the magnesium ion hybrid supercapacitor is obtained by assembling a positive electrode, a negative electrode, a separator and an electrolyte.
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