CN112599361B - Bismuth-based electrode-based wide-temperature-zone high-performance electrochemical energy storage device - Google Patents

Bismuth-based electrode-based wide-temperature-zone high-performance electrochemical energy storage device Download PDF

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CN112599361B
CN112599361B CN202011465518.4A CN202011465518A CN112599361B CN 112599361 B CN112599361 B CN 112599361B CN 202011465518 A CN202011465518 A CN 202011465518A CN 112599361 B CN112599361 B CN 112599361B
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bismuth
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potassium
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energy storage
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CN112599361A (en
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吴英鹏
黄璐
刘妙
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Hunan University
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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The invention provides a bismuth-based electrode-based wide-temperature-zone high-performance electrochemical energy storage device, which takes the prepared bismuth electrode as a cathode material of a potassium ion battery, and still has excellent cycling stability, high reversible capacity and long cycling life under the low-temperature condition. Further, by matching the prepared bismuth electrode with carbon, a bismuth-based potassium ion mixed supercapacitor with high energy and power density can be obtained at normal/low temperature. The bismuth-based electrode-based wide-temperature-zone high-performance electrochemical energy storage device has excellent electrochemical performance, can simultaneously solve the problems of low reversible capacity, short service life and high energy density and power density of a battery at normal/low temperature, is suitable for large-scale production, and is a novel green chemical power supply with wide application prospect.

Description

Bismuth-based electrode-based wide-temperature-zone high-performance electrochemical energy storage device
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to a wide-temperature-range high-performance electrochemical energy storage device based on a bismuth-based electrode.
Background
With the rapid development of the current society, the problems of the lack of traditional fossil fuel, the negative influence on the ecological environment and the like are increasingly prominent, so that the development of sustainable and renewable novel green energy storage devices becomes a hot spot of the current research. In the new regulations, the development trend of the global energy structure is accurately grasped, innovation and practical application of the low-carbon environment-friendly technology are focused, the application proportion of new energy in the automobile industry is greatly improved, and a new sustainable green development mode is finally constructed. The important point is to realize the scale application of the new energy automobile, and the whole quality and performance of the electric automobile are expected to be comprehensively improved in 2020. Thus, the development of new energy industries must develop electrochemical energy storage technologies and devices that are highly safe, long-lived, high energy density, and high power.
Recently, K/K has been developed due to the abundance and low cost of potassium resources, in particular + Is very close to Li/Li + Indicating potassium ion mixed superelectricityThe container has a very high operating voltage and a good energy density. The potassium ion hybrid supercapacitor consists of a faraday battery type negative electrode and an electric double layer capacitor positive electrode, can realize high energy and power density, and is considered as the most promising next-generation electrochemical energy storage device. Due to large K + The ionic radius (1.38 a) results in slow kinetics and volume expansion, and current research on potassium ion hybrid supercapacitors is in the primary stage. The low temperatures result in poor reaction kinetics and slow ion transport, resulting in severe capacity fade, but little research is currently done on wide temperature range potassium ion batteries. In particular, the development of a negative electrode material for a potassium ion battery and a potassium ion hybrid supercapacitor with rapid reaction kinetics in a wide temperature range has not been reported.
The electrode material, which is an important component of the battery, plays a critical role in improving the overall performance of the battery. Therefore, reasonably designing a negative electrode material with rapid reaction kinetics in a wide temperature range to match an electric double layer positive electrode material, and obtaining a high-performance potassium ion hybrid supercapacitor has become an important point of current research. Unfortunately, current research on this aspect is left blank.
Currently, an alloy-based electrode material such as Sb, bi, P, sn has attracted attention as a negative electrode material for a potassium ion battery because of its high capacity. Wherein bismuth (Bi) can be obtained by BiKBi 2 K 3 Bi 2 K 3 The reversible reaction of Bi provides a high theoretical capacity (386 mAh g -1 ) And a high volumetric capacity (3800 mAh L) -1 ) Therefore, they have been widely studied in potassium ion batteries. However, due to Bi to K 3 The alloying process of Bi will lead to a huge volume change, up to 411%, and during cycling will lead to severe agglomeration of Bi particles, leading to rapid capacity fade. Therefore, designing bismuth-based materials with stable structure and fast reaction kinetics has become a key for improving bismuth-based potassium ion batteries and bismuth-based hybrid supercapacitors.
Invention patent [ application publication No. CN104475133A]Discloses a preparation method of a Bi/BiOCl photocatalyst, which adopts a one-step combustion method to prepare bismuth nitrate and chloridizeAnd preparing the Bi/BiOCl composite photocatalyst by taking citric acid as a raw material. Invention patent [ application publication No. CN 108134090A ]]The invention discloses a nano bismuth/carbon composite material and a preparation method thereof, wherein various carbon materials are used as substrates, bismuth nitrate, bismuth chloride, bismuth sulfate, bismuth acetate, bismuth citrate and the like are used as bismuth sources, water, glycol, propylene glycol or a mixture thereof containing an organic complexing agent is used as a solvent, and sodium borohydride, potassium borohydride, hydrazine hydrate and the like are used as reducing agents. The nano bismuth and carbon compound is obtained by an adsorption-thermal decomposition-reduction method. Invention patent [ application publication No. CN 111224102A ]]The invention discloses a preparation method of a low-temperature battery, and the lithium ion battery can be used in a low-temperature environment of-30 ℃ on the premise of not using low-temperature electrolyte by changing the raw material ratio of a positive plate and a negative plate. Invention patent [ application publication No. CN 107732239A ]]Discloses a preparation method of a ferrous sulfide carbon coated anode material of a lithium-sodium ion low-temperature battery, wherein the current density of a sodium ion half battery is 0.05 Ag at the temperature of minus 25 DEG C -1 After 80 cycles, the capacity is kept at 311 mAh g -1 . As a negative electrode material of the lithium ion battery, the current density is 0.2 Ag at the temperature of minus 20 DEG C -1 After 80 cycles, the capacity is kept at 562 mAh g -1 。
In summary, there are many applications of bismuth-based materials as photocatalysts and hydrogen absorption reactions, and many studies on the wide temperature of lithium/sodium ion battery cathode materials, but studies on the wide temperature of potassium ion batteries and potassium ion hybrid supercapacitors are in a blank state, and particularly, studies on bismuth-based low-temperature potassium ion half batteries and bismuth-based low-temperature potassium ion hybrid supercapacitors have not been reported.
Disclosure of Invention
The invention provides a bismuth-based electrode-based wide-temperature-zone high-performance electrochemical energy storage device, which solves the problems that the bismuth-based electrode cannot be applied to a potassium ion battery and cannot be applied to the wide-temperature field at present.
The wide-temperature-zone high-performance electrochemical energy storage device comprises a bismuth-based potassium ion half cell and a bismuth-based potassium ion hybrid supercapacitor.
Preferably, the bismuth-based potassium ion half cell is used at the temperature of-20 ℃ to 60 ℃, wherein the potassium ion cell takes a bismuth-based electrode as a negative electrode, a potassium salt solution as an electrolyte and metallic potassium as a positive electrode.
The bismuth-based electrode is prepared from bismuth raw materials including at least one of bismuth citrate, bismuth acetate, bismuth carbonate, bismuth nitrate pentahydrate, bismuth trichloride, bismuth oxide or bismuth hydroxide; the concentration of the potassium salt solution is 0.1-8 mol L -1 The potassium salt is any one of potassium hexafluorophosphate, potassium chloride, potassium nitrate, potassium fluoride, potassium carbonate, potassium sulfate, potassium dodecylbenzenesulfonate or tripotassium citrate.
The preparation method of the bismuth raw material comprises the following steps:
(1) Respectively dissolving raw bismuth and a reducing agent in a solvent to prepare a bismuth solution and a reducing solution;
(2) Carrying out ultrasonic treatment on the bismuth solution, wherein the ultrasonic frequency is 10-40KHZ, the ultrasonic time is 10-200 minutes, then stirring for 10-100 minutes at-10-100 ︒ ℃, dripping the reduction solution into the bismuth solution after stirring, stirring again after dripping is finished, wherein the stirring time can be controlled to be 1-8 h, then washing with a solvent and centrifuging for multiple times, and drying the obtained solid in a vacuum drying oven at 30-120 ︒ ℃ for 3-15 h until the dried bismuth raw material is obtained.
Preferably, the bismuth material is composed of metal bismuth powder with nano/micron particle size
The solvent in the step (1) is at least one of water, methanol, ethanol, propanol, isopropanol, glycol, glycerol or polyethylene glycol, and the reducing agent is at least one of hydrazine hydrate, sodium borohydride, potassium borohydride or sodium hypophosphite; the concentration of the bismuth solution is 0.001-5mol/L, and the concentration of the reduction solution is 0.001-4.5mol/L.
The volume ratio of the bismuth solution to the reduction solution in the step (2) is (10-60): 1.
the invention also provides a bismuth-based potassium ion hybrid supercapacitor, which is formed by matching and assembling the prepared bismuth-based electrode and the carbon electrode, wherein electrolyte is potassium salt solution, the applicable temperature of the bismuth-based potassium ion hybrid supercapacitor is-20-60 ℃, the bismuth electrode provides Faraday capacitance, and the carbon electrode provides electric double layer capacitance.
The preparation of the bismuth-based electrode or the carbon electrode is as follows:
dissolving the binder in N-methyl pyrrolidone, stirring for 2-6 h, adding bismuth raw material or carbon material and conductive agent into the binder solution, stirring for 6-10 h, coating on copper foil or aluminum foil, drying for 6-15 h in a vacuum drying oven at 80-120 ︒ C, and slicing before battery assembly.
The bismuth or carbon material, the binder and the conductive agent meet the following mass ratio: 75-85% of bismuth or carbon material, 4-12% of binder and 2-21% of conductive agent.
And assembling the bismuth electrode, the anode, the electrolyte and the diaphragm to obtain the potassium ion mixed supercapacitor.
The carbon electrode comprises any one of activated carbon, graphitized carbon or biomass carbon, the particle size of the carbon material is 0.01-5 mu m, and the specific surface area is 300-4000 m 2 /g。
The energy density of the bismuth-based potassium ion super capacitor is 111.2 Wh kg at the temperature of minus 20 DEG C -1 The power density is 4153.8W kg -1 。
Preferably, the electrolyte adopts a nonaqueous solvent, and the nonaqueous solvent of the electrolyte is propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl formate, methyl acetate, triethylene glycol dimethyl ether, dimethyl sulfone and dimethyl ether.
Preferably, the bismuth electrode used in the present invention further comprises: pure bismuth electrode, bismuth carbon nano tube composite electrode, bismuth oxide and carbon composite electrode, bismuth tin and carbon composite electrode, bismuth tellurium electrode, bismuth tellurium and carbon composite electrodes, bismuth antimony and carbon composite electrodes, bismuth sulfur electrodes, bismuth selenium and carbon composite electrodes and are not limited to the bismuth-containing electrodes indicated above.
Preferably, the mass ratio between the positive electrode and the negative electrode in the supercapacitor is 1- (1:8).
The beneficial effects of the invention are as follows:
(1) The bismuth electrode prepared by the invention has excellent electrochemical performance under a wide temperature range, including excellent cycle stability, excellent rate performance and ultra-long cycle life. Particularly, the bismuth-based potassium ion battery at low temperature has not been reported at present, the performance of the low Wen Biji potassium ion battery prepared by the invention is superior to that of the low-temperature electrode material of the lithium ion battery and the low-temperature electrode material of the sodium ion battery reported by the prior art, and the study on the bismuth-based low temperature in the field of the potassium ion battery has not been reported.
(2) The bismuth-based potassium ion mixed super capacitor prepared by the invention has high energy density and power density in a wide temperature area. In particular, a potassium ion hybrid capacitor at low temperature has not been reported. The bismuth-based potassium ion half cell and the bismuth-based potassium ion mixed super capacitor prepared by the invention have excellent electrochemical performance, and can still reach excellent electrochemical performance at low temperature (-20 ︒ C), so that the device has wider applicable temperature and is a novel green chemical power supply with great prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an X-ray diffraction pattern of the bismuth powder material prepared in example 1.
Fig. 2 is a scanning electron microscope image of the bismuth powder material prepared in example 1.
FIG. 3 shows that the bismuth electrode prepared in example 1 was prepared at room temperature for 0.1 mV s -1 Cyclic voltammograms at different periods.
FIG. 4 shows that the bismuth electrode prepared in example 1 was prepared at 30 Ag under normal temperature conditions -1 Cycle life plot at 5000 cycles.
Fig. 5 is a graph showing the rate performance of the bismuth electrode prepared in example 1 under normal temperature conditions.
Fig. 6 is a graph showing the rate performance of the bismuth electrode prepared in example 1 at-20 ︒ C.
Fig. 7 is a graph showing the rate performance of the bismuth/carbon potassium ion hybrid supercapacitor prepared in example 1 at normal temperature.
Fig. 8 is a graph showing the rate performance of the bismuth/carbon potassium ion hybrid supercapacitor prepared in example 1 at-20 ︒ C.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Weighing bismuth trichloride powder of 0.1 and g, dissolving in 50 ml methanol, wherein the ultrasonic frequency is 30 KHZ, the ultrasonic time is 60 minutes, and stirring time is 80 minutes under the action of magnetic stirring to form S1;
(2) Weighing 0.08g of sodium borohydride powder, dissolving the sodium borohydride powder in a methanol solution until the sodium borohydride powder is completely reacted, wherein the reaction time is 10 minutes, and forming S2;
(3) Under the stirring state at room temperature, S1 is poured into S2, stirring is continued for 30 minutes, the obtained product is washed with ethanol/methanol/deionized water for a plurality of times, and then the product is dried for 8 hours under the condition of 80- ︒ C of a vacuum drying oven, so that the bismuth material is prepared.
The prepared bismuth raw material was subjected to phase composition analysis by using an X-ray diffractometer manufactured by Bruker, germany.
As shown in FIG. 1, the results indicate that the peaks of the sample at specific locations correspond to standard cards (PDF-44-1246), respectively. Indicating that the synthesized product is the target product bismuth.
The morphology and size of the prepared material were tested by using an S-4800 scanning electron microscope, as shown in FIG. 2, and it was observed that the target product prepared by the present invention was nano-sized bismuth particles, which were uniformly distributed, uniform in size, and about 30-80% nm in size.
Bismuth electrode and preparation of carbon electrode
Dissolving the binder in N-methyl pyrrolidone, stirring for 6 h, adding bismuth or carbon material and conductive agent into the binder solution, stirring for 8h, coating on copper foil or aluminum foil, drying for 8h in a vacuum drying oven at 100 ︒ C, and slicing before battery loading.
The bismuth or carbon material, the binder and the conductive agent meet the following mass ratio: 80% of bismuth or carbon material, 10% of binder and 10% of conductive agent.
The bismuth electrode and the metal potassium are assembled into the potassium ion half battery, and the assembly sequence is as follows: and after the positive electrode shell, the gasket, the negative electrode bismuth, the electrolyte, the diaphragm, the gasket, the elastic piece and the negative electrode shell are assembled successfully, performing constant current charge and discharge test.
The assembled potassium ion half cell was subjected to cyclic voltammetry, as shown in FIG. 3, three pairs of redox peaks respectively correspond (BiKBi 2 K 3 Bi 2 K 3 Bi), after the first circle of test, the curves of other circles are well overlapped, which indicates that the electrode has good reversibility and stable electrochemical performance.
The assembled potassium ion battery was subjected to constant current charge and discharge test at room temperature using a New Wipe tester, the result of which is shown in FIG. 4, and the electrode was prepared at 30A g -1 After 5000 cycles, the reversible capacity can reach 212.9 mAh g -1 After the second cycle, the coulombic efficiency can reach 100%, and the electrode shows excellent electrochemical performance.
The assembled potassium ion battery was subjected to rate performance test at room temperature using a New Wipe tester, the results of which are shown in FIG. 5, and the electrode was at 20 Ag -1 Can obtain 321.2 mAh g at the current density of (2) -1 When the current density is increased to 20A g -1 When the reversible capacity is up to 254.5 mAh g -1 . Then when the current density is restored to 5A g -1 When the reversible capacity is 345.9 mAh g -1 Reversible recoveryThe recovery rate reaches 91.3 percent. The electrode exhibits excellent rate performance at room temperature, mainly due to the contribution of good reaction kinetics and capacitive behavior.
The assembled potassium ion battery was subjected to rate performance test at low temperature (-20 ︒ C) using a low temperature box (DW-40, cangzhou, hebei) with a New Williams tester, and the results are shown in FIG. 6, in which the electrode was used at low temperature at 1, 2, 5 and 8A g -1 The current of (2) was tested for rate capability with reversible capacities of 400.7, 402.6, 345.4 and 264.2 mAh g, respectively -1 When the current density increases to 10A g -1 When the reversible capacity is 202.8 mAh g -1 . Subsequently, when the current returns to 1A g -1 When the reversible capacity reaches 401.2 mAh g -1 。
The electrode has excellent rate capability at low temperatures, mainly due to its good reaction kinetics.
Matching bismuth-based electrode with carbon, assembling potassium ion mixed super capacitor, testing the assembled bismuth-carbon-potassium ion mixed super capacitor with a Xinwei tester at room temperature, and the results are shown in figure 7, wherein the devices are 0.2, 0.5, 1, 2, 5 and 10A g -1 111.8, 108, 98.8, 86.4, 59.7, 29 Wh kg can be obtained at a current density of (C) -1 Is 14461.7W kg -1 . The device can realize higher energy density and power density, and is a novel green chemical power supply with great prospect.
The assembled bismuth carbon potassium ion hybrid supercapacitor was subjected to rate performance test at low temperature (-20 ℃) using a low temperature box (DW-40, cangzhou, hebei) with a New Williams tester, and the result is shown in FIG. 8 that the device still could achieve an energy density of 111.2 Wh kg at low temperature -1 The power density is 4153.8W kg -1 . The invention reports the low Wen Bitan potassium ion mixed super capacitor for the first time, thereby promoting the development of the low-temperature ion mixed super capacitor.
Example 2
(1) Weighing bismuth nitrate pentahydrate powder of 0.2 and g, dissolving in 60 ml ethanol, wherein the ultrasonic frequency is 10 KHZ, the ultrasonic time is 10 minutes, and stirring time is 10 minutes by virtue of the magnetic stirring effect to form S1;
(2) Weighing 0.05g of potassium borohydride powder, dissolving the powder in an ethanol solution until the powder is completely reacted, wherein the reaction time is 30 minutes, and forming S2;
(3) Under the stirring state at room temperature, pouring S1 into S2, continuously stirring for 60 minutes, washing the obtained product with ethanol/methanol/deionized water for multiple times, and then drying for 3 hours under the condition of 30- ︒ ℃ in a vacuum drying oven to prepare the bismuth material.
The manufacturing process of the bismuth electrode comprises the following steps: dissolving the binder in N-methyl pyrrolidone, stirring for 2 h, adding bismuth raw material or carbon material and conductive agent into the binder solution, stirring for 6 h, coating on copper foil or aluminum foil, drying for 6 h in a vacuum drying oven at 80 ︒ C, and slicing before battery loading.
The bismuth or carbon material, the binder and the conductive agent meet the following mass ratio: 75% of bismuth or carbon material, 4% of binder and 21% of conductive agent.
The potassium ion half cell and the potassium ion hybrid supercapacitor were prepared as in example 1.
Example 3
(1) Weighing bismuth citrate powder of 0.5 and g, dissolving in 70 ml methanol, wherein the ultrasonic frequency is 40KHZ, the ultrasonic time is 200 minutes, and stirring time is 80 minutes by virtue of the magnetic stirring effect to form S1;
(2) Weighing 0.15g of potassium borohydride powder, dissolving the powder in a methanol solution until the powder is completely reacted, wherein the reaction time is 100 minutes, and forming S2;
(3) Under the stirring state at room temperature, pouring S1 into S2, continuously stirring for 100 minutes, washing the obtained product with ethanol/methanol/deionized water for multiple times, and then drying for 15 hours under the condition of 100 ︒ ℃ in a vacuum drying oven to prepare the bismuth material.
The manufacturing process of the bismuth electrode comprises the following steps: dissolving the binder in N-methyl pyrrolidone, stirring for 6 h, adding bismuth raw material or carbon material and conductive agent into the binder solution, stirring for 10 h, coating on copper foil or aluminum foil, drying for 15h in a vacuum drying oven at 120 ︒ C, and slicing before battery assembly.
The bismuth or carbon material, the binder and the conductive agent meet the following mass ratio: 85% of bismuth or carbon material, 12% of binder and 3% of conductive agent.
The potassium ion half cell and the potassium ion hybrid supercapacitor were prepared as in example 1.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (5)

1. The wide-temperature-zone high-performance electrochemical energy storage device based on the bismuth-based electrode is characterized in that: the electrochemical energy storage device is a bismuth-based potassium ion hybrid supercapacitor, and is assembled by matching a bismuth-based electrode and a carbon electrode, wherein electrolyte is potassium salt solution, the applicable temperature of the bismuth-based potassium ion supercapacitor is-20-60 ℃, and the bismuth-based electrode is a negative electrode;
the bismuth-based electrode is prepared from bismuth raw materials including at least one of bismuth citrate, bismuth acetate, bismuth carbonate, bismuth nitrate pentahydrate, bismuth trichloride, bismuth oxide or bismuth hydroxide; the concentration of the potassium salt solution is 0.1-8 mol L -1 The potassium salt is any one of potassium hexafluorophosphate, potassium chloride, potassium nitrate, potassium fluoride, potassium carbonate, potassium sulfate, potassium dodecylbenzenesulfonate or tripotassium citrate;
the preparation method of the bismuth raw material comprises the following steps:
(1) Respectively dissolving raw bismuth and a reducing agent in a solvent to prepare a bismuth solution and a reducing solution;
(2) Carrying out ultrasonic treatment on the bismuth solution, then stirring for 10-100min at-10-100 ︒ ℃, dripping the reduction solution into the bismuth solution after stirring, stirring again after dripping, and then washing with a solvent, centrifuging and drying to obtain a bismuth raw material;
the preparation of the bismuth-based electrode is as follows: dissolving the binder in N-methyl pyrrolidone, stirring for 2-6 h, adding bismuth raw material and conductive agent into the binder solution, stirring for 6-10 h, coating on copper foil or aluminum foil, and vacuum drying and slicing.
2. The bismuth-based electrode-based wide temperature range high performance electrochemical energy storage device of claim 1, wherein: the solvent in the step (1) is at least one of water, methanol, ethanol, propanol, isopropanol, glycol, glycerol or polyethylene glycol, and the reducing agent is at least one of hydrazine hydrate, sodium borohydride, potassium borohydride or sodium hypophosphite; the concentration of the bismuth solution is 0.001-5mol/L, and the concentration of the reduction solution is 0.001-4.5mol/L.
3. The bismuth-based electrode-based wide temperature range high performance electrochemical energy storage device of claim 1, wherein: the volume ratio of the bismuth solution to the reduction solution in the step (2) is (10-60): 1.
4. a wide temperature range high performance electrochemical energy storage device based on bismuth based electrodes as claimed in claim 3, characterized in that: the carbon electrode comprises any one of activated carbon, graphitized carbon or biomass carbon, the particle size of the carbon material is 0.01-5 mu m, and the specific surface area is 300-4000 m 2 /g。
5. The bismuth-based electrode-based wide temperature range high performance electrochemical energy storage device of claim 4, wherein: the energy density of the bismuth-based potassium ion super capacitor is 111.2 Wh kg at the temperature of minus 20 DEG C -1 The power density is 4153.8W kg -1 。
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