CN114628755B - Mixed flow battery of solid nickel cobalt double hydroxide positive electrode prepared based on supercritical fluid method - Google Patents
Mixed flow battery of solid nickel cobalt double hydroxide positive electrode prepared based on supercritical fluid method Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
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- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- C—CHEMISTRY; METALLURGY
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- C01P2006/40—Electric properties
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- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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- 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
- Y02E60/30—Hydrogen technology
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Abstract
The invention belongs to the field of new energy, and particularly relates to a solid nickel cobalt double hydroxide anode mixed flow battery prepared based on a supercritical fluid method. The battery comprises a separator, a solid double-metal hydroxide positive electrode, a soluble organic negative electrode and an alkaline electrolyte solution. The double metal hydroxide is prepared by a supercritical fluid method to serve as a positive electrode, and anthraquinone and naphthoquinone derivatives with multiple hydrophilic functional groups on a mother ring are selected to serve as organic negative electrodes for improving solubility and energy density. The water system mixed flow battery integrates the advantages of the solid-state battery and the flow battery, has the advantages of simple manufacturing method, long cycle life, high energy density and the like, is low in cost, safe and environment-friendly, and has wide application prospects in the fields of large-scale electricity storage of wind energy and photovoltaic power generation and grid peak regulation.
Description
Technical Field
The invention belongs to the field of new energy, and particularly relates to a solid nickel cobalt double hydroxide anode mixed flow battery prepared based on a supercritical fluid method.
Background
Solar and wind energy are currently the mainstream renewable energy sources, but their regional and intermittent problems make it impossible to incorporate them widely into the national grid, high-performance battery systems need to be introduced to regulate the surplus and improve the efficiency, flow batteries store energy through liquid redox electrolytes instead of solid electrodes, and electroactive species circulate between storage tanks and battery systems via pumps, oxidizing or reducing in different areas, thus achieving charge and discharge. Because the electrochemical reaction place (electrode) and the energy storage species are spatially separated, the power output and the energy storage capacity are mutually independent, and therefore, the method has the advantages of high energy efficiency, long cycle life, mutual independence between energy and power, safety, environmental protection, low cost and the like.
Flow batteries are classified into aqueous and non-aqueous flow batteries according to the electrolyte. Compared with a non-aqueous flow battery, the aqueous flow battery uses water as a medium, does not use flammable and expensive organic solvents, has higher safety, and is more suitable for large-scale energy storage. According to different states of electroactive materials, flow batteries can be classified into full flow batteries and hybrid flow batteries, which have the advantages of higher energy density, lower cost, more compact size, and the like than full flow batteries.
The existing water system mixed flow battery mainly comprises vanadium-manganese, zinc-bromine, zinc-iron, iron-chromium batteries and the like, and the batteries have the advantages, but also have the defects that vanadium and bromine are high in price and high in toxicity, zinc is easy to generate dendrites, and potassium ferrocyanide is easy to decompose and the like. The key point of developing the water system mixed flow battery is to organically combine an anode and a cathode to obtain excellent performance, but the reported mixed flow batteries all adopt a soluble electroactive substance as an anode, solid metal as a cathode, and the energy density is limited by the anode of the battery.
Disclosure of Invention
The invention aims to provide an aqueous mixed flow battery with good electrochemical properties. Anthraquinone and naphthoquinone derivatives with multiple hydrophilic functional groups on a mother ring are selected as an organic negative electrode, bimetal hydroxide with high energy density is used as a solid positive electrode, and a water-based mixed flow battery with high energy density is assembled by a diaphragm and an alkaline electrolyte solution.
The invention adopts a simple and easy supercritical fluid method to prepare the double metal hydroxide. Compared with the single metal hydroxide, the double metal hydroxide has higher energy density, conductivity and stability in the alkaline electrolyte, and the invention is applied to the positive electrode of the flow battery, thereby breaking through the limitation that the existing positive electrode of the alkaline flow battery can only use the potassium ferrocyanide liquid electrolyte.
The metal ions in the solid-state positive electrode of the double-metal hydroxide with high positive potential in the water-based mixed flow battery are Ni and Co, and the molar ratio of the Ni to the Co is 1:4-4:1.
Double metal hydroxide Ni x Co 1-x (OH) 2 The specific preparation process comprises the following steps:
(1) Adding nickel nitrate, cobalt nitrate and urea into absolute ethyl alcohol together, and performing ultrasonic treatment for 1h to form a uniform mixed solution;
(2) Sealing the mixed solution in a stainless steel autoclaveThe autoclave temperature was raised to 30℃and CO was then charged into the autoclave 2 The pressure in the autoclave reaches 6MPa, the autoclave is stirred at the rotating speed of 300 rpm, the temperature of the autoclave is raised to 140 ℃ to enable the reaction system to reach a supercritical state, after the reaction lasts for 24 hours, the autoclave is cooled to room temperature, and CO is slowly released 2 Taking out the product;
(3) After washing and centrifuging for many times, vacuum drying the product at 80 ℃ to obtain the double metal hydroxide Ni with high energy density x Co 1-x (OH) 2 A solid state positive electrode.
Preferably, the molar ratio of nickel nitrate to cobalt nitrate is 1:4 to 4:1.
Preferably, the water-based mixed flow battery comprises anthraquinone and naphthoquinone derivatives with high solubility and multiple hydrophilic functional groups (amino, sulfonic acid groups, hydroxyl groups and the like) in a mother ring, and specifically comprises 2, 3-dichloro-5, 8-dihydroxy-1, 4-naphthoquinone, 6-methyl-1, 3, 8-trihydroxy anthraquinone, 1,2, 4-trihydroxy anthraquinone, 2-amino-3-methoxycarbonyl-1, 4-naphthoquinone, 1, 5-dihydroxyanthraquinone, 1H-naphthol [2,3-d ] imidazole-4, 9-dione (IMNQ), 3, 4-dihydroxy-9, 10-anthraquinone-2-sulfonic acid and 2,2' -bis (3-hydroxy-1, 4-naphthoquinone) (bisslawsone).
Preferably, the solubility of the soluble organic matter negative electrode in the alkaline water system mixed flow battery is in the range of 1-5 mol L -1 。
Preferably, the battery uses KOH electrolyte with the concentration of 1-2 mol L -1 。
The invention has the beneficial effects that:
the water system mixed flow battery provided by the invention integrates the advantages of a solid-state battery and a flow battery, has the advantages of simple manufacture, long cycle life, high specific energy and specific power and the like, is low in cost, safe and environment-friendly, and has wide application prospects in the fields of large-scale electricity storage of wind energy and photovoltaic power generation and grid peak regulation.
Description of the drawings:
FIG. 1 is a cyclic voltammogram of 2,2' -bis (3-hydroxy-1, 4-naphthoquinone) (bislaw) prepared in example 1;
FIG. 2 is an embodiment2 prepared double metal hydroxide (Ni 0.2 Co 0.8 (OH) 2 ) Is a cyclic voltammogram of (2);
FIG. 3 is an assembled Ni of example 3 0.2 Co 0.8 (OH) 2 Charge-discharge curve graph of the hybrid flow battery of// bislawsone;
FIG. 4 is an assembled Ni of example 3 0.2 Co 0.8 (OH) 2 Cycle life map of hybrid flow battery/bislaw;
FIG. 5 is an assembled Ni of example 3 0.2 Co 0.8 (OH) 2 Open circuit voltage-state of charge (SOC) dependence graph for a hybrid flow battery.
FIG. 6 is Ni assembled in comparative example 1 0.2 Co 0.8 (OH) 2 Charge-discharge curve graph of the hybrid flow battery of// bislawsone;
FIG. 7 is Ni assembled in comparative example 1 0.2 Co 0.8 (OH) 2 Cycle life map of hybrid flow battery/bislaw;
FIG. 8 is Ni assembled in comparative example 1 0.2 Co 0.8 (OH) 2 Open circuit voltage-state of charge (SOC) dependence graph for the hybrid flow battery;
FIG. 9 is a charge and discharge plot of the assembled potassium ferricyanide// bislaw flow battery of comparative example 2;
FIG. 10 is a cycle life graph of the assembled potassium ferricyanide// bislaw flow battery of comparative example 2;
fig. 11 is a graph of open circuit voltage versus state of charge (SOC) dependence of the assembled potassium ferricyanide// bisla wsone flow battery of comparative example 2.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Preparation of 2,2' -bis (3-hydroxy-1, 4-naphthoquinone) (bislawsone) negative electrode electrolyte
1.058g of 2-hydroxy-1, 4-naphthoquinone and 2.77g of ammonium persulfate are uniformly mixed in 40mL of water and acetonitrile (volume ratio of 1:1), heated in a water bath at 80 ℃, stirred and refluxed for 3 hours, cooled, added with acetic acid, filtered, washed with distilled water and dried in vacuum to obtain the product. 2,2' -bis (3-hydroxy-1, 4-naphthoquinone) (bislaw) was dissolved in 2M KOH to prepare a negative electrode electrolyte having good solubility.
FIG. 1 is 1mmol L of the preparation -1 CV diagram of bislaw circulating 100 circles in 2M KOH solution at a sweeping speed of 100mV s -1 . As shown in the figure, the bislaw electrode has a pair of good oxidation-reduction peaks in KOH electrolyte, the potential of the balance electrode is about-0.586V, the positions of the oxidation peak and the reduction peak are basically unchanged after 100 times of circulation, and the peak current is reduced by about 10 percent, so that the prepared bislaw electrode has good circulation performance.
Example 2: double metal hydroxide (Ni) 0.2 Co 0.8 (OH) 2 ) Preparation of the Positive electrode
(1) Preparation of electrode materials
1g of nickel nitrate hexahydrate, 4g of cobalt nitrate hexahydrate and 4.2g of urea were added together to 100mL of absolute ethanol, and the mixture was sonicated for 1 hour to form a uniform mixed solution. The mixed solution was then sealed in a 0.5L stainless steel autoclave, the autoclave temperature was steadily increased to 30℃and CO was then charged into the autoclave 2 The pressure in the kettle reaches 6MPa. The autoclave was slowly warmed to 140℃with stirring at a rotational speed of 300 rpm, so that the reaction system reached a supercritical state. After the reaction was continued for 24 hours, the autoclave was cooled to room temperature and CO was slowly released 2 The product was removed. After multiple washes and centrifugation, the product was dried in vacuo at 80 ℃.
(2) Preparation of electrodes
Weighing 60mg of Ni prepared above 0.2 Co 0.8 (OH) 2 The electrode material and 17mg of carbon black were placed in a mixed solvent of 600. Mu.L of water and 600. Mu.L of isopropyl alcohol, sonicated for 0.5h, and 184. Mu.L of 5% Nafion solution was added thereto, followed by further sonicating for 1h. Then Ni prepared 0.2 Co 0.8 (OH) 2 The uniform solution of the electrode material is dripped on the surface of the glassy carbon electrode, and the electrode material is dried for 8 hours at 60 ℃. The glassy carbon electrode is used as a working electrode, the mercury/mercury oxide electrode is used as a reference electrode, the platinum sheet electrode is used as a counter electrode, and Ni is tested in a three-electrode system 0.2 Co 0.8 (OH) 2 The electrochemical performance of the positive electrode is tested in the whole process of nitrogen protection. Electric powerThe solution is 2mol L -1 Is a KOH solution, an alkaline electrolyte solution. FIG. 2 is Ni 0.2 Co 0.8 (OH) 2 CV diagram of electrode in 2M KOH solution for 100 circles with sweeping speed of 100mV s -1 。
Example 3: ni of water system mixed flow battery 0.2 Co 0.8 (OH) 2 Assembly of/(bislawsone)
An aqueous hybrid flow battery based on a bimetallic hydroxide positive electrode and a water-soluble anthraquinone derivative negative electrode was constructed. 1mmol L as used in example 1 -1 bislawsone is the negative electrode, and the double metal hydroxide (Ni in example 2 0.2 Co 0.8 (OH) 2 ) The solid-state anode is prepared by taking a pretreated Nafion membrane as an ion exchange membrane of a flow battery, and the concentration of the Nafion membrane is 2mol L -1 The aqueous mixed flow battery was subjected to charge and discharge tests using a new battery test system as an electrolyte.
In order to prevent positive and negative active materials from being oxidized by oxygen in air during charge and discharge, nitrogen is introduced into positive and negative electrolyte to isolate air, and then electrochemical performance of the assembled water-based mixed flow battery is studied.
FIG. 3 is a graph at 10mA cm -2 Constant current charge-discharge curve of flow battery. The voltage range of charge and discharge is 0-1.4V, and the flow rate of electrolyte is 60mL min -1 . The discharge capacity of the hybrid flow battery was 11.9Ah.
To further investigate the stability of the cell, the assembled flow battery was subjected to cyclic charge and discharge testing.
FIG. 4 is an assembled full-water flow battery at 10mA cm -2 At a current density of 60mL min -1 The capacity retention rate of the battery 200 cycles when charging and discharging is performed under the conditions of (a). From the graph, the charge and discharge capacity of the battery can still be kept at 97.6% after 200 cycles, which indicates that the water-based mixed flow battery is designed and assembled stably and practically.
FIG. 5 is an assembled Ni of example 3 0.2 Co 0.8 (OH) 2 Open circuit voltage-state of charge of a hybrid flow battery of// bislawsone(SOC) correlation diagram. When the SOC is 50%, the open circuit voltage is 0.96V.
Example 4: ni of water system mixed flow battery 0.8 Co 0.2 (OH) 2 Assembly of/(bislawsone)
4g of nickel nitrate hexahydrate, 1g of cobalt nitrate hexahydrate and 4.2g of urea were added together to 100mL of absolute ethanol, and the mixture was sonicated for 1 hour to form a uniform mixed solution. The mixed solution was then sealed in a 0.5L stainless steel autoclave, the autoclave temperature was steadily increased to 30℃and CO was then charged into the autoclave 2 The pressure in the kettle reaches 6MPa. The autoclave was slowly warmed to 140℃with stirring at a rotational speed of 300 rpm, and the reaction system was brought to a supercritical state. After the reaction was continued for 24 hours, the autoclave was cooled to room temperature and CO was slowly released 2 The product was removed. After multiple washes and centrifugation, the product was dried in vacuo at 80 ℃.
The electrode was prepared in the same manner as in example 2. Ni of water system mixed flow battery 0.8 Co 0.2 (OH) 2 The assembly process of// bislawsone is the same as in example 3. The discharge capacity of the hybrid flow battery was 10.6Ah. The battery charge and discharge capacity can still be maintained at 95.2% after 200 cycles. When the SOC is 50%, the open circuit voltage is 0.93V.
Example 5: ni of water system mixed flow battery 0.2 Co 0.8 (OH) 2 Assembly of/(2, 3-dichloro-5, 8-dihydroxy-1, 4-naphthoquinone)
The procedure of example 3 was repeated except that 2, 3-dichloro-5, 8-dihydroxy-1, 4-naphthoquinone was used as the negative electrode, and the remaining electrode was prepared and assembled. The discharge capacity of the hybrid flow battery was 11.2Ah. The battery charge and discharge capacity remained at 92.8% after 200 cycles. When the SOC is 50%, the open circuit voltage is 0.89V.
Example 6: ni of water system mixed flow battery 0.2 Co 0.8 (OH) 2 Assembly of/(6-methyl-1, 3, 8-trihydroxyanthraquinone)
The procedure of example 3 was repeated except that 6-methyl-1, 3, 8-trihydroxyanthraquinone was used as the negative electrode, and the remaining electrode preparation and battery assembly procedures were performed. The discharge capacity of the hybrid flow battery was 9.9Ah. The charge and discharge capacity of the battery remained at 89.8% after 200 cycles.
Example 7: ni of water system mixed flow battery 0.2 Co 0.8 (OH) 2 Assembly of/(1, 2, 4-trihydroxyanthraquinone)
The procedure of example 3 was repeated except that 1,2, 4-trihydroxyanthraquinone was used as the negative electrode, and the remaining electrode preparation and battery assembly procedures were performed. The discharge capacity of the hybrid flow battery was 10.6Ah. The charge and discharge capacity of the battery remained at 90.4% after 200 cycles.
Example 8: ni of water system mixed flow battery 0.2 Co 0.8 (OH) 2 Assembly of/(2-amino-3-methoxycarbonyl-1, 4-naphthoquinone)
The procedure of example 3 was followed except that 2-amino-3-methoxycarbonyl-1, 4-naphthoquinone was used as the negative electrode, and the remaining electrode preparation and battery assembly procedures were performed. The discharge capacity of the hybrid flow battery was 8.5Ah. The battery charge and discharge capacity remained at 87.9% after 200 cycles.
Example 9: ni of water system mixed flow battery 0.2 Co 0.8 (OH) 2 Assembly of/(1, 5-dihydroxyanthraquinone)
The procedure of example 3 was repeated except that 1, 5-dihydroxyanthraquinone was used as the negative electrode and the remaining electrode preparation and battery assembly processes were performed. The discharge capacity of the hybrid flow battery was 10.5Ah. The charge and discharge capacity of the battery remained at 90.2% after 200 cycles.
Example 10: ni of water system mixed flow battery 0.2 Co 0.8 (OH) 2 1H-naphthol [2,3-d ]]Assembly of imidazole-4, 9-dione (IMNQ)
The procedure of example 3 was followed except that 1H-naphthol [2,3-d ] imidazole-4, 9-dione (IMNQ) was used as the negative electrode, and the remaining electrode preparation and battery assembly procedures were performed. The discharge capacity of the hybrid flow battery was 9.2Ah. The battery charge and discharge capacity remained at 87.7% after 200 cycles.
Example 11: ni of water system mixed flow battery 0.2 Co 0.8 (OH) 2 Assembly of/(3, 4-dihydroxy-9, 10-anthraquinone-2-sulfonic acid)
The procedure of example 3 was repeated except that 3, 4-dihydroxy-9, 10-anthraquinone-2-sulfonic acid was used as the negative electrode, and the remaining electrode preparation and battery assembly procedures were performed. The discharge capacity of the hybrid flow battery was 9.6Ah. The battery charge and discharge capacity remained at 88.3% after 200 cycles.
Comparative example 1: double metal hydroxide (Ni) prepared by coprecipitation method 0.2 Co 0.8 (OH) 2 ) Flow battery with anode and bislaw cathode assembled
(1) Preparation of electrode materials
1g of NiCl 2 ·6H 2 O and 4g of CoCl 2 ·6H 2 O was dissolved in 100mL deionized water and stirred for 30min to give a homogeneous mixture. Then, 100mL of a 1M NaOH solution was added to the mixture while maintaining the pH at 13. Then stirred at room temperature for 6 hours, aged at 60 ℃ for 12 hours, collected by centrifugation as brown precipitate, washed with deionized water for multiple times. Vacuum drying at 60deg.C to obtain Ni 0.2 Co 0.8 (OH) 2 And a positive electrode material.
(2) Preparation of electrodes
Weighing 60mg of Ni 0.2 Co 0.8 (OH) 2 The electrode material and 17mg of carbon black were placed in a mixed solvent of 600. Mu.L of water and 600. Mu.L of isopropyl alcohol, sonicated for 0.5h, and 184. Mu.L of 5% Nafion solution was added thereto, followed by further sonicating for 1h. Then Ni prepared 0.2 Co 0.8 (OH) 2 The electrode material uniform solution is dripped on the surface of the glassy carbon electrode, and is dried for 8 hours at 60 ℃.
(3) Assembly of aqueous hybrid flow battery
An aqueous hybrid flow battery based on a double metal hydroxide positive electrode and a bislaw negative electrode was constructed. The assembly process is the same as in example 3.
FIG. 6 is Ni assembled in comparative example 1 0.2 Co 0.8 (OH) 2 Charge-discharge curve of the hybrid flow battery of// bislawsone. The discharge capacity of the hybrid flow battery was 3.1Ah.
FIG. 7 is Ni assembled in comparative example 1 0.2 Co 0.8 (OH) 2 Cycle life graph of the hybrid flow battery of// bislawsone. As can be seen from the graph, the battery charge-discharge capacity retention rate after 200 cycles was about 82.2%.
FIG. 8 is Ni assembled in comparative example 1 0.2 Co 0.8 (OH) 2 Open circuit voltage-state of charge (SOC) dependence of a hybrid flow batteryA drawing. When the SOC is 50%, the open circuit voltage of the battery is 0.87V.
Comparative example 2: by commercializing potassium ferricyanide (K) 3 [Fe(CN) 6 ]) Flow battery with anode and bislaw cathode assembled
Considering the factor of easy decomposition of potassium ferricyanide, the amount of potassium ferricyanide is 10 times in excess in the process of assembling the battery. We used 45mL 2mmol L -1 Potassium ferricyanide as positive electrode, 9mL of 1mmol L -1 bislawsone is used as a cathode, a pretreated Nafion membrane is used as an ion exchange membrane of a flow battery, and 2mol L -1 As an electrolyte, a flow battery was assembled. The assembly and testing procedure is the same as in example 3.
FIG. 9 is an assembled K of comparative example 2 3 [Fe(CN) 6 ]Charge-discharge curve of the hybrid flow battery of// bislawsone. The discharge capacity of the hybrid flow battery was 0.4Ah.
FIG. 10 is an assembled K of comparative example 2 3 [Fe(CN) 6 ]Cycle life graph of the hybrid flow battery of// bislawsone. As can be seen from the graph, the battery charge-discharge capacity retention rate after 200 cycles was about 49.7%.
FIG. 11 is an assembled K of comparative example 2 3 [Fe(CN) 6 ]Open circuit voltage-state of charge (SOC) dependence graph for a hybrid flow battery. When the SOC is 50%, the open circuit voltage of the battery is 0.79V.
Claims (4)
1. A mixed flow battery of solid nickel cobalt double hydroxide positive electrode based on supercritical fluid method is characterized in that: the mixed flow battery is prepared from double metal hydroxide Ni x Co 1-x (OH) 2 The solid positive electrode, the soluble quinone organic matter negative electrode, the diaphragm and the alkaline electrolyte solution are formed, wherein x=0.2-0.8; the double metal hydroxide Ni x Co 1-x (OH) 2 The preparation method adopts a supercritical fluid method, and comprises the following specific preparation process steps:
(1) Adding nickel nitrate, cobalt nitrate and urea into absolute ethyl alcohol together, and performing ultrasonic treatment on the mixture 1 and h to form a uniform mixed solution;
(2) Sealing the mixed solution in stainless steelIn an autoclave, the temperature of the autoclave was raised to 30℃and CO was charged into the autoclave 2 The pressure in the autoclave reaches 6MPa, the autoclave is stirred at the rotating speed of 300 rpm, the temperature of the autoclave is raised to 140 ℃ to enable the reaction system to reach a supercritical state, after the reaction lasts for 24h, the autoclave is cooled to the room temperature, and CO is slowly released 2 Taking out the product;
(3) After washing and centrifuging for many times, vacuum drying the product at 80 ℃ to obtain the double metal hydroxide Ni with high energy density x Co 1-x (OH) 2 A solid-state positive electrode;
the soluble quinone organic matter negative electrode is selected from 2, 3-dichloro-5, 8-dihydroxyl-1, 4-naphthoquinone, 6-methyl-1, 3, 8-trihydroxy anthraquinone, 1,2, 4-trihydroxy anthraquinone, 1, 5-dihydroxyl anthraquinone, 1H-naphthol [2,3-d ] imidazole-4, 9-dione, 3, 4-dihydroxyl-9, 10-anthraquinone-2-sulfonic acid or 2,2' -bis (3-hydroxy-1, 4-naphthoquinone).
2. The hybrid flow battery of claim 1, wherein: the molar ratio of the nickel nitrate to the cobalt nitrate is 1:4-4:1.
3. The hybrid flow battery of claim 1, wherein: the solubility of the soluble quinone organic matters is in the range of 1-5 mol L -1 。
4. The hybrid flow battery of claim 1, wherein: the concentration of the alkaline electrolyte solution is 1-2 mol L -1 Is not included in the KOH of (C).
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| CN114628755A (en) | 2022-06-14 |
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