CN113036195B - Electrolyte of biomass flow fuel cell, preparation method of electrolyte and biomass flow fuel cell - Google Patents
Electrolyte of biomass flow fuel cell, preparation method of electrolyte and biomass flow fuel cell Download PDFInfo
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- CN113036195B CN113036195B CN202110246415.7A CN202110246415A CN113036195B CN 113036195 B CN113036195 B CN 113036195B CN 202110246415 A CN202110246415 A CN 202110246415A CN 113036195 B CN113036195 B CN 113036195B
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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
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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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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- 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
- Y02E60/50—Fuel cells
Abstract
The application belongs to the technical field of batteries, and particularly relates to an electrolyte of a biomass liquid flow fuel cell, a preparation method of the electrolyte and the biomass liquid flow fuel cell. The application provides an electrolyte of biomass liquid flow fuel cell, includes: biomass, a low-valence metal salt, a tetravalent titanium salt and a first acid solution; the low-valence metal salt is selected from a divalent copper salt and/or a trivalent iron salt. The application also provides a preparation method of the electrolyte, which comprises the following steps: mixing biomass, low-valence metal salt, tetravalent titanium salt and a first acid solution, heating to 50-100 ℃, and reacting for 0.5-10 h to obtain an anolyte; the low-valence metal salt is selected from a cupric salt or/and a ferric salt, and can effectively overcome the technical defects of generally low output power, current density, conversion efficiency, oxidative degradation efficiency, electron storage capacity and the like of the conventional biomass fuel cell.
Description
Technical Field
The application belongs to the technical field of batteries, and particularly relates to an electrolyte of a biomass liquid flow fuel cell, a preparation method of the electrolyte and the biomass liquid flow fuel cell.
Background
With the increasing energy crisis and environmental pollution, various countries have increased their attention on biomass application. The biomass is a renewable resource mainly containing a large amount of C, H, O, N and other elements, has the advantages of being rich in types, large in storage capacity, renewable and the like, and can be converted into other forms of energy through physical or chemical methods to be utilized by human beings. Therefore, the efficient utilization of biomass resources is of great significance.
Biomass fuel cells developed based on biomass can be divided into two broad categories: indirect biomass fuel cells (IDBFC) and Direct Biomass Fuel Cells (DBFC). IDBFC is a fuel cell technology that has been extensively studied in recent years and requires the prior conversion of biomass into usable fuels such as sugars (e.g., glucose and xylose), syngas, biogas or biochar for subsequent power generation by the fuel cell. IDBFCs include Solid Oxide Fuel Cells (SOFCs) and Direct Carbon Fuel Cells (DCFCs) operating at high temperatures, and Microbial Fuel Cells (MFCs) operating at low temperatures. DBFC is a new technology for generating electricity by directly using biomass as a fuel without performing complicated pretreatment on the fuel.
In the recently developed biomass fuel cell, the microorganisms in the MFC are influenced by conditions such as temperature, pH value and the like, and the power density is low, so that the requirements of practical application cannot be met; the SOFC has high operation temperature, high cost and large energy consumption. Most biomasses have complex chemical structures and a large number of stable chemical bonds, and the development and utilization of the biomasses need an efficient catalytic oxidation system and a low-cost process flow. And due to the influence of the homoionic effect, the concentration of the electrolyte cannot be infinitely increased, so that the improvement of the electrical performance of the battery is limited. In recent years, most catalytic oxidation systems for degrading biomass are biological enzymes, precious metals, heteropolyacids and the like, are high in cost and easy to inactivate, so that the conventional biomass fuel cell is high in output power, current density, conversion efficiency and oxidative degradation efficiency, low in electron storage capacity and not beneficial to large-scale development and utilization.
Therefore, it is necessary to develop a new biomass electrolyte with low cost and high performance to construct a new fuel cell.
Disclosure of Invention
In view of this, the application provides an electrolyte of a biomass liquid flow fuel cell, a preparation method thereof and the biomass liquid flow fuel cell, which can effectively solve the technical defects of generally low output power, current density, conversion efficiency, oxidative degradation efficiency, electron storage capacity and the like of the existing biomass fuel cell.
The application provides in a first aspect an electrolyte for a biomass liquid flow fuel cell, comprising:
biomass, a low-valence metal salt, a tetravalent titanium salt and a first acid solution; the low-valence metal salt is selected from a divalent copper salt and/or a trivalent iron salt.
In other embodiments, in the electrolyte of the biomass flow fuel cell, the biomass is selected from one or more of glucose, rice, bagasse, straw, fruit peel, grass, and leaves.
In other embodiments, the divalent copper salt is selected from one or more of copper chloride, copper sulfate, and copper nitrate.
In other embodiments, the ferric salt is selected from one or more of ferric chloride, ferric sulfate, and ferric nitrate.
In other embodiments, the tetravalent titanium salt is selected from titanyl sulfate or/and titanium sulfate.
In other embodiments, the first acid solution is selected from one or more of aqueous hydrochloric acid, aqueous oxalic acid, aqueous phosphoric acid, aqueous sulfuric acid, and aqueous nitric acid.
In other embodiments, the cupric salt is selected from cupric chloride; the ferric salt is selected from ferric chloride; the tetravalent titanium salt is selected from titanyl sulfate; the first acid solution is selected from aqueous hydrochloric acid.
In other embodiments, the amount of biomass added is 40-200 g/L.
In other embodiments, the initial concentration of the cupric salt is 0.1-3 mol/L.
In other embodiments, the initial concentration of the ferric salt is 0.1-3 mol/L.
In other embodiments, the initial concentration of the tetravalent titanium salt is 80-200 g/L.
In other embodiments, the concentration of the first acid solution is 1-10.0 mol/L.
The second aspect of the application provides a preparation method of the electrolyte of the biomass liquid flow fuel cell, which comprises the following steps:
mixing biomass, low-valence metal salt, tetravalent titanium salt and a first acid solution, heating to 50-100 ℃, and reacting for 0.5-10 h to obtain an anolyte; the low-valence metal salt is selected from a divalent copper salt and/or a trivalent iron salt.
The application of the electrolyte of the biomass flow fuel cell or the electrolyte of the biomass flow fuel cell prepared by the preparation method in the biomass flow fuel cell is provided in a third aspect of the application.
The application provides a biomass liquid flow fuel cell, which comprises the electrolyte of the biomass liquid flow fuel cell or the electrolyte, the catholyte, the anolyte tank, the catholyte tank, the pump, the anode, the cathode, the exchange membrane and the load of the biomass liquid flow fuel cell prepared by the preparation method.
Specifically, the catholyte can be selected from high-potential vanadium salts and other suitable catholyte for the biomass flow fuel cell.
In other embodiments, the catholyte comprises a pentavalent vanadium salt, a second acid solution, and a cathodic regeneration oxidant.
In other embodiments, the pentavalent vanadium salt in the catholyte is selected from one or more of vanadium pentoxide, vanadyl sulfate, and vanadyl nitrate.
In other embodiments, the second acid solution is selected from one or more of aqueous hydrochloric acid, aqueous sulfuric acid, and aqueous nitric acid.
In other embodiments, the cathode regenerating oxidant is selected from one or more of nitric acid, oxygen, hydrogen peroxide, or potassium permanganate.
In other embodiments, the concentration of the pentavalent vanadium salt in the catholyte is 0.05 to 1 mol/L.
In other embodiments, the concentration of the second acid solution is selected from 0.05-8.0 mol/L.
In other embodiments, in the cathode regeneration oxidant, the concentration of the nitric acid is 0.01-8 mol/L, and the flow rate of the introduced oxygen is 30-100 mL/min.
The application provides a preparation method of the catholyte, which comprises the following steps: and mixing pentavalent vanadium salt, a second acid solution and a cathode regeneration oxidant to prepare the cathode electrolyte.
In other embodiments, the biomass flow fuel cell specifically includes the electrolyte of the biomass flow fuel cell or the electrolyte of the biomass flow fuel cell prepared by the preparation method, a catholyte, an anolyte tank, a catholyte tank, a pump, an anode, a cathode, an exchange membrane, and a load;
electrolyte of the biomass flow fuel cell is arranged in the anode electrolyte tank, and the cathode electrolyte is arranged in the cathode electrolyte tank;
the anode electrolyte tank is connected with the anode through the pump, and the cathode electrolyte tank is connected with the cathode through the pump;
the anode is connected with the first surface of the exchange membrane, and the cathode is connected with the second surface of the exchange membrane;
one end of the load is connected with the anode, and the other end of the load is connected with the cathode.
In other embodiments, the biomass flow fuel cell further comprises an anode fixed end plate and a cathode fixed end plate, wherein the anode is fixed on the anode fixed end plate; the cathode is fixed on the cathode fixing end plate.
Specifically, the cell structure used in the application is similar to that of the conventional flow cell, and the main components of the cell structure comprise an anode liquid storage tank, a cathode liquid storage tank, an anode electrolyte tank, a cathode electrolyte tank, a pump pipe, a snake-shaped runner graphite plate, a load, a lead, a fixed end plate and the like, which are assembled in a certain order to form the biomass flow fuel cell.
When the biomass liquid flow fuel cell is used, the electrolyte of the biomass liquid flow fuel cell is stored in the anode liquid storage tank, the cathode electrolyte is stored in the cathode liquid storage tank, and the biomass liquid flow fuel cell is constructed according to the method to perform biomass power generation. The specific operation process is as follows: the pump is used for conveying the catholyte and the anolyte to the cathode and the anode of the battery from the liquid storage tanks respectively, the catholyte and the anolyte are conveyed to the corresponding anolyte tank and the catholyte tank for oxidation-reduction reaction and regeneration after the electrochemical reaction of the cathode and the anode, and are continuously conveyed to the cathode and the anode of the battery through the pump in a circulating manner for power generation, so that the continuous and stable conversion of the biomass energy to the electric energy is realized. The schematic diagram of the cell power generation principle is shown in the attached figure 1. Specifically, fig. 1 is a schematic diagram of an operating principle of a biomass liquid flow fuel cell provided by the present application, and includes an anode electrolyte tank 3, a cathode electrolyte tank 14, a pump 4, a pump 13, a pump pipe, a fixed end plate (including an anode fixed end plate 5 and a cathode fixed end plate 11), an electrode (including an anode 6 and a cathode 9), a proton exchange membrane 7, a load 8, a battery 10, a cathode regenerated oxidant 12, a filtering catalytic device 2, a filtering catalytic device 15, a temperature control device 1, and a temperature control device 16. The anolyte is arranged in the anolyte tank 3, the catholyte is arranged in the catholyte tank 14, and the temperature of the electrolyte in the catholyte tank is controlled by the temperature control device 1 and the temperature control device 16; the anolyte is connected with an anode 6 (an anode fixed end plate 5) through a pump 4 by a filtering and catalyzing device 2, the catholyte is connected with a cathode 9 (a cathode fixed end plate 11) through a pump 13 by a catalyzing and filtering device 15, and the continuous supplement of the electrolyte is realized by the operation of the pump 4 and the pump 13, so that the continuous conversion of energy is realized; the anode 6 is separated from the cathode 9 by a proton exchange membrane 7; one end of a load 8 is connected with the anode 6 through a lead, and the other end of the load 8 is connected with the cathode 9; the anode 6 is fixed on the anode fixing end plate 5; the cathode 9 is fixed to a cathode-fixing end plate 11.
When the anolyte is conveyed to an anode fixed end plate 5 through a filtering and catalyzing device 10 by a pump 4, biomass in the anolyte is oxidized by cupric salt (or ferric salt) and tetravalent titanium salt, correspondingly, an intermediate product, cuprous salt (or ferrous salt) and trivalent titanium salt are generated, the cuprous salt (or ferrous salt) and the trivalent titanium salt release electrons at an anode 6 to supply power to an external load 8, and simultaneously the cuprous salt (or ferric salt) and the tetravalent titanium salt are converted back to the cupric salt (or ferric salt) and the tetravalent titanium salt and conveyed back to an anolyte tank 3 to continuously oxidize the biomass or the intermediate product thereof; the released electrons move to the cathode 9 through an external circuit; the catholyte is conveyed to a cathode fixed end plate 11 through a pump 13, pentavalent vanadium ions in the catholyte are converted into tetravalent vanadium ions by receiving electrons conveyed by an external circuit at a cathode 9, and the tetravalent vanadium ions are conveyed back to a cathode electrolytic tank 14; oxygen with a certain speed is introduced into the catholyte, so that the tetravalent vanadium ions are rapidly converted back to the pentavalent vanadium ions under the action of the oxygen or the oxygen/nitric acid and the filtering and catalyzing device 15, the regeneration of the catholyte is realized, and the continuous and stable power generation of the battery system is realized.
The application discovers that the concentration of the catalyst can not be infinitely increased due to the influence of the same ion effect of the existing biomass fuel cell adopting the single water-soluble catalyst, the catalyst has selectivity, the single catalyst can not efficiently catalyze and degrade the biomass with a complex structure, and the electrical property of the biomass fuel cell adopting the single water-soluble catalyst is not ideal.
Aiming at the problems, by using the advantages of the biomass liquid flow fuel cell and using a cupric salt (or ferric salt) and a tetravalent titanium salt which are high in solubility and low in price as oxidants, the biomass is rapidly oxidized and degraded in a synergic manner, electrons of the biomass are stored in the cuprous (or ferrous salt) and the trivalent titanium, the electronic storage capacity of electrolytes is improved, the electrical property of the cell is further improved, the aim of directly and efficiently converting biomass energy into electric energy is fulfilled, and the efficient biomass liquid flow fuel cell based on the synergistic effect is developed.
On the one hand, based on the characteristics of the water system flow battery, a plurality of high-solubility electrolyte composite systems are adopted as catalytic oxidation systems for degrading biomass, so that the electronic storage capacity of electrolyte can be effectively improved, and the electrical property of the battery is further improved; on the other hand, cheap and high-solubility cupric salt (or trivalent ferric salt) and tetravalent titanium salt are used as a double-catalytic oxidation system, and the synergistic effect and high solubility of the double-catalytic oxidation system are utilized to deeply degrade the biomass and efficiently store and transport chemical energy from the biomass, so that the output power, current density and conversion efficiency of a battery system are greatly improved, and the double-catalytic oxidation system has the advantages of high oxidative degradation efficiency, strong electron storage capacity and the like.
The electrolyte of the biomass liquid flow fuel cell has the following advantages:
compared with the prior biomass fuel cell, the electrolyte of the biomass flow fuel cell adopts a low-price, high-solubility and low-potential cupric salt (or ferric salt) and tetravalent titanium salt to form a synergistic catalytic oxidation system, so that the biomass can be efficiently degraded, the efficiency of converting chemical energy in the biomass into electric energy and the energy density can be greatly improved, and the performance of the cell can be further improved; the catholyte adopts high-potential pentavalent vanadium, and forms a battery system together with low-potential anolyte. During the operation of the battery, monovalent copper salt (or divalent iron salt) and trivalent titanium salt generated in the anolyte rapidly release electrons at the anode plate of the battery and are transported to an external load, and are transported to the cathode plate of the battery through an external circuit to react with pentavalent vanadium ions in the catholyte to convert into tetravalent vanadium ions. The cathode regeneration oxidant is used for oxidizing tetravalent vanadium ions back to pentavalent vanadium ions, so that cyclic utilization is realized, the cost of the cathode electrolyte is greatly reduced, and the large-scale application of the biomass liquid flow fuel cell is promoted.
Drawings
In order to more clearly illustrate the embodiments of the present application 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.
Fig. 1 is a schematic view of an operating principle of a biomass flow fuel cell provided by the present application.
Fig. 2 is a scanning electron microscope image of bagasse obtained by different electrolyte treatments as provided in example 1 of the present application. a is bagasse which is not processed by an electrolyte; b is bagasse degraded by a single cupric salt electrolyte; c is bagasse degraded by cooperating with divalent copper salt and tetravalent titanium salt electrolyte.
Fig. 3 provides a current density-voltage-output power graph for different biomass flow fuel cells in example 2 of the present application.
Fig. 4 provides a current density-voltage-output power graph for various biomass flow fuel cells in example 3 of the present application.
Fig. 5 provides a current density-voltage-output power graph for various biomass flow fuel cells in example 4 of the present application.
Fig. 6 provides a current density-voltage-output power graph for various biomass flow fuel cells in example 5 of the present application.
Fig. 7 provides a sustained discharge diagram of a different biomass flow fuel cell of comparative example 1 of the present application.
Fig. 8 provides a current density-voltage-output power plot for various biomass flow fuel cells of comparative example 2 of the present application.
The biomass liquid flow fuel cell shown in fig. 1 comprises an anode electrolyte tank 3, a cathode electrolyte tank 14, a pump 4, a pump 13, a pump pipe, a fixed end plate (comprising an anode fixed end plate 5 and a cathode fixed end plate 11), an electrode (comprising an anode 6 and a cathode 9), a proton exchange membrane 7, a load 8, a cell 10, a cathode regeneration oxidant 12, a filtering catalytic device 2, a filtering catalytic device 15, a temperature control device 1 and a temperature control device 16. The anolyte is arranged in the anolyte tank 3, the catholyte is arranged in the catholyte tank 14, and the temperature of the electrolyte in the catholyte tank is controlled by the temperature control device 1 and the temperature control device 16; the anolyte is connected with an anode 6 (anode plate) through a filtering and catalyzing device 2 and a pump 4, the catholyte is connected with a cathode 9 (cathode plate) through a catalyzing and filtering device 15 and a pump 13, and the operation of the pump 5 and the pump 13 realizes the continuous supplement of the electrolyte and the continuous conversion of energy; the anode 6 is separated from the cathode 9 by a proton exchange membrane 7; one end of a load 8 is connected with the anode 6 through a lead, and the other end of the load 8 is connected with the cathode 9; the anode 6 is fixed on the anode fixing end plate 5; the cathode 9 is fixed to a cathode-fixing end plate 11.
Detailed Description
The application provides an electrolyte of a biomass liquid flow fuel cell, a preparation method of the electrolyte and the biomass liquid flow fuel cell, which are used for overcoming the technical defects that the output power, the current density, the conversion efficiency, the oxidative degradation efficiency and the electron storage capacity of the biomass liquid flow fuel cell in the prior art are generally low.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. 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 application.
The reagents or raw materials used in the following examples are commercially available or self-made.
Example 1
The application provides different electrolyte solution degradation tests for biomass treatment, and the specific preparation method comprises the following steps:
1. 204.6g of copper chloride dihydrate and 100mL of concentrated hydrochloric acid are respectively dissolved in deionized water to prepare two 600mL mixed solutions, then 20g of bagasse and 150g of titanyl sulfate are added into one part, only 20g of bagasse is added into the other part, the mixture is uniformly stirred and heated to 95 ℃, the temperature is kept for reaction for 3h, and degraded liquid products and solid products are obtained by filtration, washing and low-temperature drying, and are respectively marked as bagasse b obtained by degrading single cupric salt and bagasse c obtained by synergistically degrading copper and titanium.
2. Dissolving 150g of titanyl sulfate and 100mL of concentrated hydrochloric acid in deionized water to prepare 600mL of mixed solution, then adding 20g of bagasse, uniformly stirring, heating to 95 ℃, preserving heat for reaction for 3h, filtering, washing and drying at low temperature to obtain a degraded liquid product and a solid product, wherein the product is marked as single tetravalent titanium degraded bagasse d.
3. SEM analysis: the morphology of bagasse a which is not subjected to electrolyte treatment, bagasse b which is degraded by divalent copper salt alone, bagasse c which is thermally degraded based on the synergistic effect of metal ions (namely, bagasse degraded by copper and titanium) and bagasse d which is degraded by tetravalent titanium alone is analyzed by a scanning electron microscope. The results are shown in fig. 2, and fig. 2 shows that the bagasse in a has smooth surface and compact structure as it is; b and d, the surfaces of the bagasse become rough after the thermal degradation of single divalent copper salt or single tetravalent titanium salt; c, after the synergistic thermal degradation of the divalent copper salt and the tetravalent titanium salt, the surface of the bagasse becomes rougher and looser. Therefore, the composite catalytic oxidant based on the synergistic effect has better oxidative degradation effect on the bagasse, and achieves the effect of 1+1> 2.
Example 2
The application provides a first biomass liquid flow fuel cell, which comprises the following specific preparation method:
1. preparing an anolyte: dissolving 61.4g of copper chloride dihydrate and 30mL of concentrated hydrochloric acid in deionized water, then adding 6g of straw and 45g of titanyl sulfate, adding water to a mixed solution with a constant volume of 180mL, uniformly stirring, heating to 90 ℃, and carrying out heat preservation reaction for 3 hours to obtain a copper-titanium synergistic degradation straw electrolyte; in addition, dissolving 61.4g of copper chloride dihydrate and 30mL of concentrated hydrochloric acid in deionized water, then only adding 6g of straws, adding water to a mixed solution with a constant volume of 180mL, uniformly stirring, heating to 90 ℃, and carrying out heat preservation reaction for 3 hours to obtain the single copper salt degradation straw electrolyte.
45g of titanyl sulfate and 30mL of concentrated hydrochloric acid are dissolved in deionized water, 6g of bagasse is added, the volume is fixed to 180mL, the mixture is heated to 90 ℃ after being uniformly stirred, and the reaction is carried out for 3 hours under the condition of heat preservation, so that the single tetravalent titanium salt degradation straw electrolyte is prepared.
2. Preparing a cathode electrolyte: weighing 20g of vanadium pentoxide powder, adding the vanadium pentoxide powder into a beaker filled with deionized water, stirring at room temperature, adding 100mL of concentrated sulfuric acid into the solution, stirring for 12h to prepare 500mL of solution, adding 2 mL of nitric acid, continuously stirring until the solution is bright yellow, and standing for 24h to obtain the high-valence vanadium catholyte.
3. Battery system construction and electrical performance testing: independently adding the electrolyte prepared in the step 1 (a single copper salt degraded straw electrolyte, a single tetravalent titanium salt degraded straw electrolyte and a copper-titanium synergistic degraded straw electrolyte) into an 80 ℃ anode electrolyte tank, and storing the cathode electrolyte prepared in the step 2 into an 80 ℃ cathode electrolyte tank. The anode electrolyte tank is connected with the anode inlet and the cathode outlet of the battery by a pipe, and the cathode tank is connected with the cathode inlet and the cathode outlet of the battery. Meanwhile, high-purity oxygen is introduced into the cathode electrolyte tank at a certain flow rate, and the tetravalent vanadium is reduced by the oxygen, so that the regeneration of the cathode electrolyte is realized. The electrical properties of the cells were tested by the scanning current method, and the results are shown in fig. 3.
From FIG. 3, it can be seen thatCompared with the cupric salt or single tetravalent titanium salt as the catalytic oxidant, the synergistic cupric salt and tetravalent titanium salt based on the ion synergistic effect as the composite catalytic oxidant obviously improves the electrical property of the constructed fuel cell, the maximum voltage of the fuel cell is 0.56V, and the maximum current density is 830.2mA/cm 2 Maximum power density of 131mW/cm 2 (ii) a And the maximum voltage of the fuel cell with the single cupric salt as the catalytic oxidant is 0.53V, and the maximum current density is 668.3mA/cm 2 Maximum power density of 89mA/cm 2 . In contrast, the fuel cell using the tetravalent titanium salt alone as the catalytic oxidant had lower maximum current density and lower maximum power density, which was about 128mA/cm 2 Maximum power density of about 26.8mA/cm 2 . It can be seen that the tetravalent titanium salt alone has the worst degradation effect as a catalytic oxidant. In a word, when the copper-titanium synergistic degradation straw electrolyte is used as the anode electrolyte, the constructed fuel cell has more excellent electrical property which reaches 1+1>2.
Example 3
The application provides a second biomass liquid flow fuel cell, which comprises the following specific preparation method:
1. preparing an anolyte: dissolving 76.7g of copper chloride dihydrate and 36mL of concentrated hydrochloric acid in deionized water, adding 16.2g of glucose and 36g of titanyl sulfate, adding water to a mixed solution with a constant volume of 180mL, uniformly stirring, heating to 90 ℃, and carrying out heat preservation reaction for 1h to obtain a copper-titanium synergetic degraded glucose electrolyte; ② 76.7g of copper chloride dihydrate and 36mL of concentrated hydrochloric acid are dissolved in deionized water, then only 16.2g of glucose is added, water is added to the mixed solution with a constant volume of 180mL, the mixed solution is heated to 90 ℃ after being stirred uniformly, and the temperature is kept for reaction for 1h, thus preparing the glucose electrolyte with single copper salt degradation.
Dissolving 36g of titanyl sulfate and 36mL of concentrated hydrochloric acid in deionized water, then adding 16.2g of glucose, adding water to a mixed solution with a constant volume of 180mL, uniformly stirring, heating to 90 ℃, and carrying out heat preservation reaction for 3 hours to obtain the single tetravalent titanium salt degraded glucose electrolyte.
2. Preparing a cathode electrolyte: weighing 20g of vanadium pentoxide powder, adding the vanadium pentoxide powder into a beaker filled with deionized water, stirring at room temperature, adding 100mL of concentrated sulfuric acid into the solution, stirring for 12h to prepare 500mL of solution, adding 2 mL of nitric acid, continuously stirring until the solution is bright yellow, and standing for 24h to obtain the high-valence vanadium catholyte.
3. Battery system construction and electrical performance testing: independently adding the electrolytes (a single copper salt degraded glucose electrolyte, a single tetravalent titanium salt degraded glucose electrolyte and a copper-titanium synergic degraded glucose electrolyte) prepared in the step 1 into an 80-DEG C anode electrolyte tank, and storing the cathode electrolyte prepared in the step 2 into an 80-DEG C cathode electrolyte tank. The anode electrolyte tank is connected with the anode inlet and the cathode outlet of the battery by a pipe, and the cathode tank is connected with the cathode inlet and the cathode outlet of the battery. Meanwhile, high-purity oxygen is introduced into the cathode electrolyte tank at a certain flow rate, and the tetravalent vanadium is reduced by the oxygen, so that the regeneration of the cathode electrolyte is realized. The electrical properties of the cells were tested using the scanning current method and are shown in fig. 4. The maximum voltage of the fuel cell based on the copper-titanium synergistic effect is 0.63V, and the maximum current density is 1030mA/cm 2 The maximum power density is 145.7mW/cm 2 (ii) a And the maximum voltage of the fuel cell with the single cupric salt as the catalytic oxidant is 0.58V, and the maximum current density is 858mA/cm 2 Maximum power density of 117.8mW/cm 2 . In contrast, the fuel cell using the tetravalent titanium salt alone as the catalytic oxidant has a maximum voltage of 0.69V, but has very low maximum current density and maximum power density of about 118mA/cm 2 Maximum power density of about 23.3mA/cm 2 . Therefore, when the copper-titanium synergetic degradation glucose electrolyte is used as the anode electrolyte, the constructed fuel cell has more excellent electrical property which reaches 1+1>2.
Example 4
The application provides a third biomass liquid flow fuel cell, which comprises the following specific preparation method:
1. preparing an anolyte: 72.981g of ferric chloride hexahydrate and 50mL of concentrated hydrochloric acid are dissolved in deionized water, then 16.2g of glucose and 36g of titanyl sulfate are added, the volume is constant, 180mL of mixed solution is prepared, the mixed solution is uniformly stirred and heated to 90 ℃, the temperature is kept for reaction for 1h, and the ferrotitanium synergetic degraded glucose electrolyte is prepared; dissolving 72.981g of ferric chloride hexahydrate and 50mL of concentrated hydrochloric acid in deionized water, then adding only 16.2g of glucose, fixing the volume to prepare 180mL of mixed solution, stirring uniformly, heating to 90 ℃, and keeping the temperature for reaction for 1h to prepare the single iron salt degraded glucose electrolyte.
2. Preparing a cathode electrolyte: 10g of vanadium pentoxide powder was weighed into a beaker containing deionized water and stirred at room temperature. 50mL of concentrated sulfuric acid was added to the solution. And then stirring the solution for 12h, adding 2 ml of nitric acid, continuously stirring until the solution is bright yellow, and standing for 24h to obtain the catholyte of high-valence vanadium.
3. And (3) testing electrical properties: respectively adding the electrolytes (Fe-Ti synergistic degradation glucose electrolyte and single Fe salt degradation glucose electrolyte) prepared in the step 1 into an 80 ℃ anode electrolyte tank, and storing the cathode electrolyte prepared in the step 2 into an 80 ℃ cathode electrolyte tank. The anode electrolyte tank was connected to the anode inlet and outlet of the cell and the cathode electrolyte tank was connected to the cathode inlet and outlet of the cell by pipes, and then the corresponding electrical performance test was performed, the results of which are shown in fig. 5. Compared with the single ferric salt as the catalytic oxidant, the electrical property of the fuel cell based on the iron-titanium synergistic effect is also obviously improved, which shows that the ferric iron and the tetravalent titanium also have the synergistic effect. Wherein, the maximum voltage of the fuel cell taking the trivalent ferric salt and the titanyl sulfate as the composite catalytic oxidant is 0.6V, and the maximum current density is 553mA/cm 2 Maximum power density of 81.6mW/cm 2 (ii) a Fuel cell with single ferric salt as catalytic oxidant and with maximum voltage of 0.54V and maximum current density of 418mA/cm 2 Maximum power density of 56.6W/cm 2 . However, by comparison with example 3, it was found that the synergistic effect of trivalent iron with tetravalent titanium is significantly lower than that of divalent copper with tetravalent titanium.
Example 5
The application provides a fourth biomass liquid flow fuel cell, which comprises the following specific preparation method:
1. 121.635g of ferric chloride hexahydrate and 50mL of concentrated hydrochloric acid are dissolved in deionized water, then 16.2g of glucose and 36g of titanyl sulfate are added, the volume is constant, 180mL of mixed solution is prepared, the mixed solution is uniformly stirred and heated to 90 ℃, the temperature is kept for reaction for 1h, and the ferrotitanium synergetic degraded glucose electrolyte is prepared; dissolving 121.635g of ferric chloride hexahydrate and 50mL of concentrated hydrochloric acid in deionized water, adding 16.2g of glucose, fixing the volume to prepare 180mL of mixed solution, uniformly stirring, heating to 90 ℃, and carrying out heat preservation reaction for 1h to prepare the single iron salt degraded glucose electrolyte.
2. Preparing a cathode electrolyte: 10g of vanadium pentoxide powder was weighed into a beaker containing deionized water and stirred at room temperature. 50mL of concentrated sulfuric acid was added slowly to the solution. And continuously stirring the solution for 12h, adding 2 ml of nitric acid, continuously stirring until the solution is bright yellow, and standing for 24h to obtain the catholyte of high-valence vanadium.
3. The electrical property test is that the electrolyte prepared in the step 1 (ferrotitanium synergistic degradation glucose electrolyte; and iron salt degradation glucose electrolyte alone) is added into an 80 ℃ anode electrolyte tank, and the cathode electrolyte prepared in the step 2 is stored in an 80 ℃ cathode electrolyte tank. The anode electrolyte tank was connected to the anode inlet and outlet of the cell and the cathode electrolyte tank was connected to the cathode inlet and outlet of the cell by pipes, and then the corresponding electrical performance test was performed, the results of which are shown in fig. 6. In the embodiment, the ferric iron and the tetravalent titanium also have good synergistic effect, the maximum voltage of the fuel cell based on the iron-titanium synergistic effect is 0.54V, and the maximum current density is 613mA/cm 2 Maximum power density of 80.3mW/cm 2 (ii) a The maximum voltage of the fuel cell using the single ferric iron salt electrolyte as the catalytic oxidant is 0.44V, and the maximum current density is 563mA/cm 2 Maximum power density of 68.4mW/cm 2 . However, in comparison with example 4, it was found that increasing the concentration of ferric chloride alone in the electrolyte did not have a significant synergistic effect on increasing the tetravalent titanium and trivalent iron.
Comparative example 1
The application provides a contrast biomass liquid flow fuel cell, which comprises the following specific preparation method:
1. preparing an anolyte: dissolving 102.3g of copper chloride dihydrate and 50mL of concentrated hydrochloric acid in deionized water, adding 27g of glucose and 60g of titanyl sulfate to a constant volume to prepare a 300mL mixed solution, uniformly stirring, heating to 90 ℃, and carrying out heat preservation reaction for 1h to prepare a copper-titanium synergetic degraded glucose electrolyte; dissolving 102.3g of copper chloride dihydrate and 50mL of concentrated hydrochloric acid in deionized water, adding 27g of glucose only, diluting to a constant volume to prepare 300mL of mixed solution, stirring uniformly, heating to 90 ℃, preserving heat and reacting for 1h to prepare the glucose electrolyte degraded by the copper salt alone.
60g of titanyl sulfate and 50mL of concentrated hydrochloric acid are dissolved in deionized water, 27g of glucose is added, a mixed solution of 300mL is prepared by constant volume, the mixed solution is uniformly stirred and heated to 90 ℃, and the temperature is kept for reaction for 3 hours, so that the single tetravalent titanium salt degraded glucose electrolyte is prepared.
2. Preparing a cathode electrolyte: 10g of vanadium pentoxide powder was weighed into a beaker containing deionized water and stirred at room temperature. 50mL of concentrated sulfuric acid was added slowly to the solution. And continuously stirring the solution for 12h, adding 2 ml of nitric acid, continuously stirring until the solution is bright yellow, and standing for 24h to obtain the catholyte of high-valence vanadium.
3. And (3) testing electrical properties: and (2) independently adding the electrolytes (a single copper salt degraded glucose electrolyte, a single tetravalent titanium salt degraded glucose electrolyte and a copper-titanium synergetic degraded glucose electrolyte) prepared in the step (1) into an 80-DEG C anode electrolyte tank respectively, and storing the cathode electrolyte prepared in the step (2) into an 80-DEG C cathode electrolyte tank. The anode electrolyte tank is connected with the anode inlet and the cathode outlet of the battery by a pipe, and the cathode electrolyte tank is connected with the cathode inlet and the cathode outlet of the battery. Meanwhile, high-purity oxygen is introduced into the cathode electrolyte tank at a certain flow rate, and the tetravalent vanadium is reduced by the oxygen, so that the regeneration of the cathode electrolyte is realized. The sustain discharge test was performed at a voltage of 0.3V as shown in fig. 7.
As can be seen from FIG. 7, the sustained discharge current density was only 10mA/cm when the tetravalent titanium salt alone was used as the catalytic oxidizing agent 2 The output power density is only 3mW/cm 2 (ii) a When the cupric salt alone is taken as the catalytic oxidant, the continuous discharge current density is 323.6mA/cm 2 The output power density is 97.1mW/cm 2 (ii) a By using a synergistic effectWhen the cupric salt/tetravalent titanium salt is used as a double catalytic oxidation system, the continuous discharge current density is 372.3mA/cm 2 The output power density is 111.7mW/cm 2 . Therefore, when the tetravalent titanium salt and the cupric salt are mixed together to be used as the catalytic oxidant, the tetravalent titanium salt does not reduce the performance of the cupric salt, but plays a synergistic role, so the cupric salt/tetravalent titanium salt dual-catalytic oxidation system based on the ion synergistic effect has more efficient electron storage and transport capacity, and the fuel cell is endowed with more excellent performance.
Comparative example 2
The application provides a contrast biomass liquid flow fuel cell, which comprises the following specific preparation method:
1. preparing an anolyte: dissolving 76.7g of copper chloride dihydrate and 36mL of concentrated hydrochloric acid in deionized water, adding 16.2g of glucose, diluting to a constant volume to prepare 180mL of mixed solution, uniformly stirring, heating to 90 ℃, and carrying out heat preservation reaction for 1h to prepare the single cupric salt degraded glucose electrolyte (marked as CuCl in figure 8) 2 ) (ii) a ② 76.7g of copper chloride dihydrate and 36mL of concentrated hydrochloric acid are dissolved in deionized water, then 16.2g of glucose and 36g of sodium chloride are added, the volume is constant to prepare 180mL of mixed solution, the mixed solution is heated to 90 ℃ after being stirred uniformly, the temperature is kept and the reaction is carried out for 1h, thus obtaining the cupric salt and sodium chloride composite degraded glucose electrolyte (marked as CuCl in figure 8) 2 + NaCl); dissolving 76.7g of copper chloride dihydrate and 36mL of concentrated hydrochloric acid in deionized water, adding 16.2g of glucose and 36g of potassium chloride, diluting to a constant volume to prepare 180mL of mixed solution, stirring uniformly, heating to 90 ℃, preserving heat and reacting for 1h to prepare the cupric salt and potassium chloride composite degraded glucose electrolyte (marked as CuCl in figure 8) 2 + KCl); dissolving 16.2g of glucose and 36mL of concentrated hydrochloric acid in deionized water, adding 36g of titanyl sulfate, preparing 180mL of mixed solution by constant volume, uniformly stirring, heating to 90 ℃, and carrying out heat preservation reaction for 1h to prepare the single tetravalent titanium salt degraded glucose electrolyte (marked as TiOSO in figure 8) 4 ) (ii) a Fifthly, 16.2g of glucose and 36mL of concentrated hydrochloric acid are dissolved in deionized water, then 36g of titanyl sulfate and 36g of sodium chloride are added, the volume is constant, 180mL of mixed solution is prepared, the mixed solution is heated to 90 ℃ after being evenly stirred, the reaction is carried out for 1h under the condition of heat preservation, and the titanyl sulfate is preparedGlucose electrolyte compositely degraded by titanium and sodium chloride (marked as TiOSO in figure 8) 4 +NaCl)。
2. Preparing a cathode electrolyte: 10g of vanadium pentoxide powder was weighed into a beaker containing deionized water and stirred at room temperature. 50mL of concentrated sulfuric acid was added slowly to the solution. And continuously stirring the solution for 12h, adding 2 ml of nitric acid, continuously stirring until the solution is bright yellow, and standing for 24h to obtain the catholyte of high-valence vanadium.
3. And (3) testing electrical properties: the electrolyte (CuCl) prepared in the step 1 2 、CuCl 2 +NaCl、CuCl 2 +KCl、TiOSO 4 Or TiOSO 4 + NaCl) was added to the 80 ℃ anolyte tank and the catholyte prepared in step 2 was stored in the 80 ℃ catholyte tank. The anode electrolyte tank was connected to the anode inlet and outlet of the cell and the cathode electrolyte tank was connected to the cathode inlet and outlet of the cell by pipes, and then the corresponding electrical performance test was performed, the results of which are shown in fig. 8.
Fig. 8 shows that the addition of chloride salts (such as sodium chloride and potassium chloride) without synergistic effect to the electrical performance of the cell under the same test conditions does not effectively improve the electrical performance of the cell, and slightly decreases the electrical performance of the cell, which may be caused by the addition of chloride salts without synergistic effect as a catalyst, which increases the viscosity of the system but does not increase the capability of the system to store and transfer electrons, so that the electrical performance of the fuel cell decreases. It can be seen that the more kinds of metal salts are not the anolyte, the better, only specific metal salts can have synergistic effect with divalent copper salt or trivalent iron salt, and the anolyte of the application can only have synergistic effect with tetravalent titanium salt in specific divalent copper salt or trivalent iron salt.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.
Claims (8)
1. The electrolyte of the biomass flow fuel cell is characterized by consisting of biomass, low-valence metal salt, tetravalent titanium salt and a first acid solution;
the low-valence metal salt is selected from a divalent copper salt or/and a trivalent iron salt;
the cupric salt is selected from one or more of cupric chloride, cupric sulfate and cupric nitrate; the ferric salt is selected from one or more of ferric chloride, ferric sulfate and ferric nitrate;
the tetravalent titanium salt is selected from titanyl sulfate or/and titanium sulfate.
2. The electrolyte of claim 1, wherein the biomass is selected from one or more of glucose, rice, bagasse, straw, fruit peel, grass, and leaves.
3. The electrolyte of claim 1, wherein the first acid solution is selected from one or more of an aqueous hydrochloric acid solution, an aqueous oxalic acid solution, an aqueous phosphoric acid solution, an aqueous sulfuric acid solution, and an aqueous nitric acid solution; the concentration of the first acid solution is 1-10.0 mol/L.
4. The electrolyte according to claim 2, wherein the biomass is added in an amount of 40 to 200 g/L.
5. The electrolyte of claim 1, wherein the cupric salt has an initial concentration of 0.1-3 mol/L; the initial concentration of the trivalent ferric salt is 0.1-3 mol/L.
6. The electrolyte of claim 1, wherein the initial concentration of the tetravalent titanium salt is 80-200 g/L.
7. A method for preparing the electrolyte according to any one of claims 1 to 6, comprising the steps of:
mixing biomass, low-valence metal salt, tetravalent titanium salt and a first acid solution, heating to 50-100 ℃, and reacting for 0.5-10 h to obtain an anolyte; the low-valence metal salt is selected from a divalent copper salt and/or a trivalent iron salt.
8. A biomass flow fuel cell, characterized by comprising the electrolyte according to any one of claims 1 to 6 or the electrolyte prepared by the preparation method according to claim 7.
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