CN116344885A - A rechargeable biomass battery - Google Patents

Abstract

The invention discloses a chargeable and dischargeable biomass battery. The battery is formed by sequentially assembling a negative current collector, a negative catalyst, a diaphragm, a positive electrode and a positive current collector, wherein a negative electrolyte and a positive electrolyte are respectively led into a negative chamber and a positive chamber by a liquid pump and are led into a negative storage tank and a positive storage tank for circulation. The system is characterized by Ni ²⁺ /Ni ³⁺ The redox energy storage mechanism is coupled with the electrocatalytic redox reaction of the biomass aldehyde in one device. During charging, the anode generates aldehyde to generate alcohol through electrocatalytic reduction reaction, and meanwhile, the anode Ni ²⁺ Oxidation to Ni ³⁺ The method comprises the steps of carrying out a first treatment on the surface of the During discharge, the anode generates aldehyde to generate acid through electrocatalytic oxidation reaction, and the anode Ni ³⁺ Reversible reduction to Ni ²⁺ . Compared with the traditional electrosynthesis system, the system effectively integrates the electrochemical energy storage characteristic, can be used for storing and releasing renewable electric energy, simultaneously realizes high-value conversion of cheap biomass, improves electronic economy, and reduces production energy consumption and cost.

Description

A rechargeable biomass battery

technical field

The invention belongs to the technical field of biomass electrocatalytic conversion and electrochemical energy storage, and specifically relates to a chargeable and dischargeable biomass battery. Composite systems for chemical energy storage.

Background technique

Renewable biomass resources can produce a wide range of fine chemicals, including polymers, surfactants, dyes, pharmaceuticals and pesticides, and are one of the effective means to solve energy depletion and environmental problems in modern society. The traditional biomass refining process often adopts thermal catalysis. This process requires the use of a large amount of redox agents, high temperature and high pressure, and consumes a large amount of fossil energy. It is difficult to meet the urgent needs of modern society for green and sustainable development. Using electric energy-driven electrochemical synthesis technology, the reaction conditions are mild (normal temperature and pressure), and active hydrogen and active oxygen in water can be used to participate in the reaction. It can be used as a green redox agent without generating carbon emissions, which is in line with the concept of green chemistry. Therefore, more and more attention has been paid to the directional high-value conversion of biomass molecules by means of electrocatalysis.

Biomass-derived aldehydes (such as furfural, 5-hydroxymethylfurfural, etc.) have abundant sources and low market prices, and high-value chemicals can be prepared by electrocatalytic redox. For example, furfural, the oxidation product of furfural, is an important raw material in the pharmaceutical, perfume and plastic industries, and its reduction product, furfuryl alcohol, also has wide application potential in furan resins, preservatives, lubricants and fuels. However, most of the current electrocatalytic synthesis only focuses on a single reaction process in the production process, and the other electrode is not effectively utilized, which reduces the electron economy of the whole system. Although the use of paired electrosynthesis can realize the simultaneous generation of chemicals at the two electrodes, due to the coupling relationship between the two electrodes, the production rate of the two chemicals will be limited to the slower half-reaction, and the entire electrolysis process still requires higher voltage drive. Such as the patent [CN 113430559 B] only realizes the reduction reaction of furfural or 5-hydroxymethylfurfural; the electrocatalytic reduction of 4-nitrobenzyl alcohol and the electrocatalytic oxidation of 5-hydroxymethylfurfural coupling system reported in the patent [CN 114164454 B] , although the simultaneous production of chemicals from the cathode and anode is achieved, a voltage driving force of ~1.4V is required.

Therefore, there is an urgent need to develop an electrochemical synthesis system with low energy consumption, high electron utilization and no mutual restriction of electrochemical production rates.

Contents of the invention

The purpose of the present invention is to provide a coupling system of electrocatalytic redox and electrochemical energy storage of biomass-derived aldehyde, which is characterized in that the Ni ²⁺ /Ni ³⁺ redox energy storage mechanism and the electrocatalysis of biomass aldehyde The redox reactions are coupled in one device. When charging, the electrocatalytic reduction reaction of aldehyde occurs at the negative electrode to generate alcohol, and at the same time, Ni ²⁺ at the positive electrode is oxidized to Ni ^{3 +} ; during discharge, the electrocatalytic oxidation reaction of aldehyde occurs at the negative electrode to generate acid, and Ni ³⁺ at the positive electrode is reversibly reduced to Ni ²⁺ . The system realizes the effective recovery of renewable electric energy and external energy supply, and at the same time solves the problems of insufficient half-reaction utilization, low electron economy, low chemical production rate, and high energy consumption in the existing electrosynthesis system during the charging and discharging process , to improve the efficiency of electrosynthesis.

The rechargeable and dischargeable biomass battery is sequentially assembled from a negative electrode collector, a negative electrode catalyst, a diaphragm, a positive electrode, and a positive electrode collector. The negative electrode electrolyte and the positive electrode electrolyte are respectively introduced into the negative electrode chamber and the positive electrode chamber by a liquid pump, and Introduce the negative electrode storage tank and the positive electrode storage tank for circulation.

working principle:

Charge positive reaction: reduced state –e ^– → oxidized state

Charge negative reaction: biomass-derived aldehyde + e ^– → bio-alcohol

Discharge positive reaction: oxidation state + e ^– → reduction state

Discharge negative electrode reaction: biomass-derived aldehyde –e ^– → biomass acid

During the charging and discharging process of the battery, the redox reactions of biomass-derived aldehydes were carried out separately on the negative electrode catalyst.

In the above technical solution, the current collector is one of copper foam, copper mesh, copper sheet, nickel foam, nickel mesh, nickel sheet, titanium mesh, titanium sheet, stainless steel mesh, stainless steel sheet, carbon cloth and carbon paper species or several.

In the above technical scheme, the negative electrode catalyst is one of copper, silver, gold, copper silver, copper gold, copper platinum, copper rhodium, copper palladium, copper ruthenium, copper nickel, copper cobalt, copper iridium catalyst or Several kinds. Preferably, the negative electrode catalyst is copper, copper rhodium and copper ruthenium catalysts.

The positive electrode is any one of nickel hydroxide, cobalt hydroxide, and cobalt-doped nickel hydroxide. Preferably, the positive electrode material is cobalt-doped nickel hydroxide.

In the above technical scheme, the negative electrode electrolyte is any aqueous electrolyte solution in sodium hydroxide, potassium hydroxide, sulfuric acid, perchloric acid, sodium sulfate, potassium bicarbonate, potassium carbonate, sodium bicarbonate, and sodium carbonate. Mixtures with biomass-derived aldehydes.

The positive electrode electrolyte is any aqueous electrolyte solution in sodium hydroxide, potassium hydroxide, sulfuric acid, perchloric acid, sodium sulfate, potassium bicarbonate, potassium carbonate, sodium bicarbonate, and sodium carbonate. Preferably, the negative electrode electrolyte is sodium hydroxide and potassium hydroxide.

In the above technical scheme, the biomass-derived aldehyde is furfural, 5-hydroxymethylfurfural, p-methylfurfural, m-methylfurfural, o-methylfurfural, benzaldehyde, aceguvaldehyde, glycolaldehyde, acetaldehyde, Any one or more of formaldehyde. Preferably, the biomass-derived aldehydes are furfural and 5-hydroxymethylfurfural.

In the above technical solution, the concentration of the aqueous electrolyte solution is 0.01-10M, and the concentration of the biomass-derived aldehyde is 0.005-0.5M. Preferably, the concentration of the aqueous electrolyte solution is 0.1-2M, and the concentration of the biomass-derived aldehyde is 0.01-0.2M.

In the above technical solution, the positive and negative catalysts are supported on the current collector by one or more methods of electrodeposition, hydrothermal method, spray coating method, spin coating method and impregnation method.

In the above technical solution, the diaphragm is any one of FAA-3-20, Nafion 212, and Nafion 117.

The premise that this type of battery can be successfully constructed is that the aldehyde group has both oxidation and reduction properties, and the oxidation potential and reduction potential of the aldehyde group are close to -0.83V relative to the standard hydrogen electrode scale in alkaline solution (pH=14), so as long as A rechargeable and dischargeable electrocatalytic-battery composite system can be constructed by selecting a suitable combination of reversible redox pairs.

Compared with the traditional electrochemical redox of biomass-derived aldehydes, the proposed electrocatalysis-energy storage coupling system can not only generate the corresponding reduction and oxidation chemicals, but also can be used as a rechargeable battery for renewable electric energy Storage and release, efficient use of half-reactions in electrosynthesis, and improved electron economy; in addition, since the electrocatalytic reduction and electrocatalytic oxidation processes of biomass-derived aldehydes are carried out in the charging and discharging process of the battery, the ratio of the two The rate is not restricted, and the efficiency of electrosynthesis is improved.

Description of drawings

Fig. 1 is the linear sweep voltammetry polarization curve of furfural electrocatalytic oxidation on copper rhodium catalyst in embodiment 2.

Fig. 2 is the linear sweep voltammetry polarization curve of furfural electrocatalytic reduction on copper rhodium catalyst in embodiment 3.

Fig. 3 is the I-V curve and the power density diagram of the biomass battery assembled with the copper-rhodium catalyst in Example 4, cobalt-doped nickel hydroxide as the positive electrode, and the furfural-containing negative electrode solution assembled.

Fig. 4 is the charging and discharging curves of the biomass battery assembled into the negative electrode solution containing furfural with the copper-rhodium catalyst as the negative electrode, the cobalt-doped nickel hydroxide as the positive electrode and the furfural-containing negative electrode solution under different current densities in Example 4.

Fig. 5 is the I-V curve and the power density diagram of the biomass battery assembled with the zinc sheet as the negative pole, the copper-rhodium catalyst as the positive pole, and the catholyte solution containing furfural in Example 5.

6 is a battery I-V curve and a power density diagram assembled with a copper-rhodium catalyst as the negative electrode, cobalt-doped nickel hydroxide as the positive electrode, and a furfural-free negative electrode solution in Example 6.

Fig. 7 is a structure and reaction schematic diagram of a rechargeable and dischargeable biomass battery designed in an embodiment of the present invention.

Detailed ways

Hereinafter, the present invention will be further described in conjunction with specific examples. The following examples are only used to illustrate the present invention, but not to limit the protection scope of the present invention.

Embodiment 1 prepares negative pole and positive pole

A. copper negative electrode catalyst preparation, specific method is:

Calcination: A piece of commercial copper foam (3cm×4cm) was put into a muffle furnace, and calcined at 350°C for 2h at a heating rate of 5°C/min.

Electrochemical reduction: In a two-electrode system, nickel foam (3cm×4cm) was used as the anode, and electrochemical reduction was performed at -3V for 30min in 1M KOH solution.

B. preparation of copper rhodium negative pole catalyst, concrete method is:

Calcination: A piece of commercial copper foam (3cm×4cm) was put into a muffle furnace, and calcined at 350°C for 2h at a heating rate of 5°C/min.

Electrochemical reduction: In a two-electrode system, nickel foam (3cm×4cm) was used as the anode, and electrochemical reduction was performed at -3V for 30min in 1M KOH solution.

Electrochemical displacement: A 3cm×4cm Cu electrocatalyst was soaked in 100mL aqueous solution containing 25μmol RhCl ₃ , the stirring speed was 500rpm, and the displacement reaction lasted 20min to prepare a copper-rhodium electrocatalyst.

C. Preparation of cobalt-doped nickel hydroxide positive electrode, the specific method is:

Clean the foamed nickel current collector: use 1M HCl solution, ethanol, and deionized water to ultrasonically clean it for 15 minutes, and dry it for later use.

Preparation of electrolyte solution: 50mL of Ni(NO ₃ ) ₂ ·6H ₂ O/Co(NO ₃ ) ₂ ·6H ₂ O mixed solution with a concentration of 0.1M was used as the deposition solution;

Electrodeposition: A three-electrode system was used for electrodeposition, the Ag/AgCl electrode was used as the reference electrode, and two nickel foams of equal size (2.5cm×4cm) were used as the working electrode and the counter electrode, and several consecutive electrodepositions were carried out. Electrodeposition was performed 4 times, each time lasting 3000s, and the current density was -10mA cm ^-2 . After finishing, rinse with deionized water to remove residual metal ions on the electrode.

Activation: The obtained cobalt-doped nickel hydroxide electrode is activated by constant current (100mA) charge and discharge, and the activation reaction is as follows:

Tabletting: Rinse the activated electrode further with deionized water, then clamp the electrode with two pieces of nickel foam of the same size and press it under a pressure of 10MPa to prevent the electrode material from falling off.

Example 2

Using copper rhodium as the working electrode with a geometric surface area of 1.5cm ^-2 , platinum as the counter electrode, and Hg/HgO as the reference electrode, the electrocatalytic oxidation of furfural was tested in H-cell three-electrode. The concentration of furfural was 30mM, and the linear sweep voltammetry polarization curves were recorded at 20mV s ^-1 with and without furfural. The constant potential electrolysis was carried out at different potentials for 1800s, and the products after the reaction were detected by high performance liquid chromatography. Fig. 1 is the linear sweep voltammetry polarization curve of carrying out furfural oxidation on the copper-rhodium catalyst, and the faradaic efficiency of furoic acid is 100%.

Example 3

Using copper rhodium as the working electrode with a geometric surface area of 1.5cm ^-2 , platinum as the counter electrode, and Hg/HgO as the reference electrode, the electrocatalytic reduction reaction of furfural was tested in the H-cell three-electrode. The concentration of furfural was 30mM, and the linear sweep voltammetry polarization curves were recorded at 20mV s ^-1 with and without furfural. The constant potential electrolysis was carried out for 1800s under different potentials, and the products after the reaction were detected by high performance liquid chromatography. Fig. 2 is the linear sweep voltammetry polarization curve of furfural reduction on the copper-rhodium catalyst, and the faradaic efficiency of furfuryl alcohol is 83%.

Example 4

Flow cell assembly: use copper-rhodium catalyst as the negative electrode, with an area of 1.5cm ^-2 , pressed on a 2cm×2cm foamed nickel substrate; use a cobalt-doped nickel hydroxide thick electrode as the positive electrode, with a size of 2cm×2cm, mass loading 50 mg cm ^-2 ; the copper-rhodium catalyst, Nafion 117, and cobalt-doped nickel hydroxide were stacked layer by layer and compacted. The flow field area is 4cm ^-2 ; a peristaltic pump is used to control the flow rate of the cathode solution and the anode solution. The catholyte was 1M KOH solution with a flow rate of 15 mL/min. The negative electrode solution is a mixed solution of 1M KOH and 0.1M furfural, and the flow rate is 30mL/min.

Battery performance results: Figure 3 is the IV curve and power density diagram of a biomass battery assembled with a copper-rhodium catalyst as the negative electrode, cobalt-doped nickel hydroxide as the positive electrode, and a furfural-containing negative electrode solution. The battery has an open circuit voltage of 1.29V and a maximum power density of 107mW cm ^-2 . Figure 4 shows the charge and discharge curves of the battery at different current densities. At a current density of 20mA cm ^-2 , the battery capacity is 19.8mWh cm ^-2 .

Example 5

Assembling the flow cell: use a zinc sheet as the negative electrode, with a size of 2cm×2cm; use a copper-rhodium catalyst as the positive electrode, with an area of 1.5cm ^-2 , and press it on a 2cm×2cm foamed nickel substrate; zinc sheet, Nafion 117, copper rhodium The catalysts are stacked and compacted layer by layer. The flow field area is 4cm ^-2 ; a peristaltic pump is used to control the flow rate of the cathode solution and the anode solution. The negative electrode solution is 1M KOH solution, and the flow rate is 15mL/min. The catholyte was a mixed solution of 1M KOH and 0.1M furfural, and the flow rate was 30mL/min.

Battery performance results: Figure 5 shows the IV curve and power density diagram of a biomass battery assembled with a zinc sheet as the negative electrode, a copper-rhodium catalyst as the positive electrode, and a catholyte containing furfural. The highest power density of the battery is 3.2mW cm ^-2 .

Example 6

Flow cell assembly: use copper-rhodium catalyst as the negative electrode, with an area of 1.5cm ^-2 , pressed on a 2cm×2cm foamed nickel substrate; use a cobalt-doped nickel hydroxide thick electrode as the positive electrode, with a size of 2cm×2cm, mass loading 50mg cm ^-2 ; the copper-rhodium catalyst, Nafion 117, and cobalt-doped nickel hydroxide were stacked layer by layer and compacted. The flow field area is 4cm ^-2 ; a peristaltic pump is used to control the flow rate of the cathode solution and the anode solution. Both the cathode solution and the anode solution were 1M KOH solution, and the flow rate was 15mL/min.

Battery performance results: Figure 6 shows the IV curve and power density diagram of a biomass battery assembled with a copper-rhodium catalyst as the negative electrode, cobalt-doped nickel hydroxide as the positive electrode, and a furfural-free anode solution. The highest power density of the battery is 17mW cm ^-2 .

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, and those skilled in the art should understand that any person skilled in the art should be aware of any disclosure in the present invention Within the technical scope, easily conceivable changes or substitutions all fall within the scope of protection and disclosure of the present invention.

Claims (10)

1. The chargeable and dischargeable biomass battery is characterized by being formed by sequentially assembling a negative electrode current collector, a negative electrode catalyst, a diaphragm, a positive electrode and a positive electrode current collector, wherein negative electrode electrolyte and positive electrode electrolyte are respectively led into a negative electrode chamber and a positive electrode chamber by a liquid pump and are led into a negative electrode storage tank and a positive electrode storage tank for circulation.

2. The chargeable and dischargeable biomass battery of claim 1, wherein: the current collector is one or more of foam copper, a copper net, a copper sheet, foam nickel, a nickel net, a nickel sheet, a titanium net, a titanium sheet, a stainless steel net, a stainless steel sheet, carbon cloth and carbon paper.

3. The chargeable and dischargeable biomass battery of claim 1, wherein: the negative electrode catalyst is one or more of copper, silver, gold, copper silver, copper gold, copper platinum, copper rhodium, copper palladium, copper ruthenium, copper nickel, copper cobalt and copper iridium catalysts.

4. The chargeable and dischargeable biomass battery of claim 1, wherein: the negative electrode electrolyte is a mixed solution of any electrolyte aqueous solution of sodium hydroxide, potassium hydroxide, sulfuric acid, perchloric acid, sodium sulfate, potassium bicarbonate, potassium carbonate, sodium bicarbonate and sodium carbonate and biomass-derived aldehyde.

5. The chargeable and dischargeable biomass battery of claim 4, wherein: the biomass derived aldehyde is any one or more of furfural, 5-hydroxymethyl furfural, p-methyl furfural, m-methyl furfural, o-methyl furfural, benzaldehyde, methylglyoxal, glycolaldehyde, acetaldehyde and formaldehyde.

6. The chargeable and dischargeable biomass battery of claim 4, wherein: the concentration of the electrolyte aqueous solution is 0.01-10M, and the concentration of the biomass-derived aldehyde is 0.005-0.5M.

7. The chargeable and dischargeable biomass battery of claim 1, wherein: the positive electrode is any one of nickel hydroxide, cobalt hydroxide and cobalt doped nickel hydroxide.

8. The chargeable and dischargeable biomass battery of claim 1, wherein: the positive electrolyte is any one electrolyte aqueous solution of sodium hydroxide, potassium hydroxide, sulfuric acid, perchloric acid, sodium sulfate, potassium bicarbonate, potassium carbonate, sodium bicarbonate and sodium carbonate.

9. The chargeable and dischargeable biomass battery of claim 1, wherein: the positive electrode and the negative electrode catalyst are loaded on the current collector by one or more methods of an electrodeposition method, a hydrothermal method, a spraying method, a spin-coating method and an impregnation method.

10. The chargeable and dischargeable biomass battery of claim 1, wherein: the diaphragm is any one of FAA-3-20, nafion 212 and Nafion 117.

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