CN114122569A - Hydride/air battery for synchronously treating waste acid and waste alkali and generating electricity - Google Patents
Hydride/air battery for synchronously treating waste acid and waste alkali and generating electricity Download PDFInfo
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- CN114122569A CN114122569A CN202111412386.3A CN202111412386A CN114122569A CN 114122569 A CN114122569 A CN 114122569A CN 202111412386 A CN202111412386 A CN 202111412386A CN 114122569 A CN114122569 A CN 114122569A
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- 239000002699 waste material Substances 0.000 title claims abstract description 96
- 239000002253 acid Substances 0.000 title claims abstract description 57
- 239000003513 alkali Substances 0.000 title claims abstract description 43
- 150000004678 hydrides Chemical class 0.000 title claims abstract description 21
- 230000005611 electricity Effects 0.000 title claims description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 45
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 35
- 150000004681 metal hydrides Chemical class 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000009792 diffusion process Methods 0.000 claims abstract description 16
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 229910000831 Steel Inorganic materials 0.000 claims description 21
- 239000010959 steel Substances 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 239000013543 active substance Substances 0.000 claims description 16
- -1 hydrogen ions Chemical class 0.000 claims description 16
- 238000006386 neutralization reaction Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003518 caustics Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000001994 activation Methods 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 229910002335 LaNi5 Inorganic materials 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 20
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 20
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000003929 acidic solution Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000003011 anion exchange membrane Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000001360 synchronised effect Effects 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
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- 239000012528 membrane Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
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- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
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- 229910011006 Ti(SO4)2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
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- 239000010802 sludge Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Images
Classifications
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/4608—Treatment of water, waste water, or sewage by electrochemical methods using electrical discharges
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
Abstract
A metal hydride/air electrochemical cell device for simultaneously processing waste acid and waste alkali and generating electric energy. The method comprises the following steps: an air diffusion electrode as a positive electrode, a hydride electrode as a negative electrode that stores hydrogen in advance, and an ion exchange membrane, wherein: the positive electrode and the negative electrode are respectively placed in the waste acid solution and the waste alkali solution, the positive electrode and the negative electrode are connected with an external circuit, and the ion exchange membrane is arranged between the acid electrolyte and the alkali electrolyte and is used as a diaphragm material; when the battery discharges or waste acid and waste alkali treatment is carried out, the reaction of the negative electrode is to separate out hydrogen and the hydrogen reacts with OH in the waste alkali‑The ions are oxidized to generate water and generate electrons; meanwhile, electrons are led out from an external circuit and flow to the anode, so that oxygen in the air and H in the waste acid+The ions are reduced to produce water. The invention relates to the environmental pollution problem caused by waste acid and waste alkali generated in industrial productionThe problem is to provide a 'harmless, quantitative reduction and resource' treatment technical path, which has practical significance and good application prospect.
Description
Technical Field
The invention relates to a technology in the fields of chemical industry, environment and energy, in particular to a device and a method for a hydride/air battery for synchronously treating waste acid, waste alkali and generating electricity based on safety.
Background
The waste acid and the waste alkali discharged in industrial production have great influence on the water environment, and are a prominent problem for restricting the sustainable development of China. The traditional technology for treating the waste acid and the waste alkali comprises the technologies of directly mixing the waste acid and the waste alkali for neutralization, biotechnology, cement kiln high-temperature incineration, air floatation precipitation and impurity removal, iron-carbon micro-electrolysis and wet oxidation method treatment. However, these conventional techniques have low resource utilization and lack economic efficiency. For example, the direct mixing neutralization treatment technique is to mix and neutralize acidic wastewater and alkaline wastewater with each other or directly neutralize acidic wastewater with solid caustic sludge. However, the waste heat energy generated in the chemical neutralization process of the technology is not converted and utilized, so that the total utilization rate and the economic benefit are low.
Disclosure of Invention
The invention provides a metal hydride/air electrochemical cell device for synchronously treating waste acid, waste alkali and generating electric energy, aiming at the problem of the lack of the synchronous treatment technology of the waste acid, the waste alkali and the waste alkali with high safety and high resource utilization rate at present. The invention uses hydride with high safety to consume OH under alkaline condition-Oxidation reaction of ions as negative electrode reaction and high safety air diffusion electrode consuming H under acidic condition+The reduction reaction of the ions is used as the anode reaction, and the acid-base electrolyte is separated by an ion exchange membrane. In the process of discharging or performing electrochemical neutralization, namely when the waste acid and the waste alkali are treated, electric energy can be obtained from the treatment process of the waste acid and the waste alkali, and the electrochemical neutralization treatment with high efficiency, safety and resource utilization is realized. The invention does not discharge waste gas and waste liquid in the waste acid and waste alkali treatment process, and can continuously treat the waste acid and the waste alkali. The invention relates to the environmental pollution problem caused by waste acid and waste alkali generated in industrial productionThe problem is to provide a 'harmless, quantitative reduction and resource' treatment technical path, which has practical significance and good application prospect.
The invention is realized by the following technical scheme:
the invention relates to a metal hydride/air electrochemical cell device for synchronously treating waste acid and waste alkali and generating electric energy, which comprises: an air diffusion electrode as a positive electrode, a hydride electrode as a negative electrode that stores hydrogen in advance, and an ion exchange membrane, wherein: the positive electrode and the negative electrode are respectively placed in the waste acid solution and the waste alkali solution, the positive electrode and the negative electrode are connected with an external circuit, and the ion exchange membrane is arranged between the acid electrolyte and the alkali electrolyte and is used as a diaphragm material; when the battery discharges or waste acid and waste alkali treatment is carried out, the reaction of the negative electrode is to separate out hydrogen and the hydrogen reacts with OH in the waste alkali-The ions are oxidized to generate water and generate electrons; meanwhile, electrons are led out from an external circuit and flow to the anode, so that oxygen in the air and H in the waste acid+The ions are reduced to produce water.
During the above-mentioned entire discharge process of the device, H+Ions and OH-The ions are subjected to an effective electrochemical neutralization treatment and release electric energy through a corresponding electrochemical reaction.
The waste acid solution and the waste alkali solution can be taken from waste acid and waste alkali produced in industry and can be directly used as the electrolyte of the electrochemical cell device, and the electric energy can be obtained while the electrochemical neutralization treatment is obtained.
The air diffusion electrode is obtained by mixing and grinding a platinum-carbon catalyst, conductive carbon black and a binder solution, coating the mixture on the surface of hydrophobic carbon cloth and drying the mixture.
The hydride electrode for pre-storing hydrogen is obtained by the following steps:
firstly, the components in the nickel-metal hydride battery are LaNi5Mixing and grinding the Metal Hydride (MH), the conductive carbon black and the binder solution, and drying to obtain an active substance;
secondly, after the active substance is coated on the foamed nickel, the foamed nickel is folded in half and the nickel-plated steel strip is clamped in the middle to form a sandwich structure, and the part of the nickel-plated steel strip extends out of the foamed nickel.
Thirdly, the sandwich structure is dried and compacted and then is activated.
The component of the metal hydride is LaNi5Lanthanum nickel hydrogen storage alloy.
The activation treatment is as follows: charging and discharging with 20mA current (charging time is 2 hr, discharge cut-off voltage is 0.2V), circulating for four times, and finally performing one-time charging (cut-off voltage is 1.5V) to form hydride electrode for pre-storing hydrogen.
The pH value of the waste acid solution is preferably less than 1 before treatment, and the concentration of hydrogen ions in the waste acid is reduced after treatment, specifically, the reduction of the hydrogen ion concentration at least corresponds to 0.15-0.21M when electricity is output at 87.5 mAmp. The pH value of the treated waste acid solution is increased, which means that the acidity is obviously weakened.
The pH value of the waste alkali solution is preferably larger than 13 before treatment, and the concentration of hydroxide ions in the waste alkali is reduced after treatment, specifically, the electric quantity is reduced by at least 0.15-0.21M for every 87.5 mAmp output. The pH of the spent caustic solution after treatment decreases, meaning that the alkalinity is significantly reduced.
The battery discharges, the total reaction is 1 mol of oxygen, 4 mol of hydrogen ions, 4 mol of hydride of pre-stored hydrogen and 4 mol of hydroxide ions to generate 4 mol of hydride after releasing hydrogen and 6 mol of water, and no waste gas and liquid are generated in the reaction products.
The hydride/air battery discharge reaction mechanism for synchronously treating waste acid and waste alkali and generating electricity specifically comprises the following steps:
and (3) positive pole reaction:
and (3) cathode reaction:
and (3) total reaction:
technical effects
The invention utilizes hydride hydrogen storage material with high safety to consume OH under alkaline condition-Oxidation reaction of ions as negative electrode reaction and high safety air diffusion electrode consuming H under acidic condition+The reduction reaction of the ions is used as the positive pole reaction, and the acid-base electrolyte is separated by an ion exchange membrane to prevent direct mixed chemical neutralization reaction, so that the total electrochemical reaction of the formed electrochemical cell device can electrochemically neutralize H+Ions and OH-Ions and water and electricity are produced. Compared with the prior art, the cathode adopts the high-safety normal-temperature metal hydride hydrogen storage material, so that the safety of the actual industrial production operation is greatly improved; the liquid product is only water, and no waste gas or waste liquid is discharged, so that the environment is protected; the battery structure design improvement based on the pairing of the two chambers and the acid-base electrode can solve the problem of waste liquid treatment with different pH values; the synchronous electrochemical neutralization treatment of the waste acid and the waste alkali and the electricity generation are realized by a novel electrochemical reaction mode, and the resource utilization rate is improved.
Based on the standard electrode potentials of the positive and negative electrodes, the cell of the invention could theoretically produce a voltage of 2.03 volts under standard conditions when the hydrogen and hydroxide ion concentrations were each 1M. The electrochemical cell devices formed in accordance with the present invention have an actual open circuit voltage measurement of greater than 1.6 volts. In addition, hydrogen ions in waste acid and hydroxide ions in waste alkali are effectively neutralized in the discharging process, and electric quantity is generated. Therefore, the battery device has the advantages and characteristics of efficiently and synchronously treating the waste acid and the waste alkali and utilizing the electric quantity generated in the treatment process. The typical technical effect is as follows: the electrochemical cell device can synchronously process hydrogen ion concentration and hydroxyl ion of 0.15-0.21M respectively, and the acidity and alkalinity of the two waste liquids are obviously weakened when the generated electric quantity is 87.5 milliamperes.
Drawings
FIG. 1 is a diagram of the discharge reaction mechanism of a hydride/air cell;
FIG. 2 is a graph comparing the voltage change with time in the current test of the batteries of example 1 and example 2;
FIG. 3 is a plot of the 5-100mA current test polarization for the battery of example 3;
FIG. 4 is a plot of the 5-70mA current test polarization for the battery of example 4;
FIG. 5 is a diagram of a hydride/air cell configuration for simultaneous processing of spent acid and spent caustic and generation of electricity;
in the figure: an air diffusion electrode 1, a gas diffusion layer 101, a catalyst layer 102, an ion exchange membrane 2, a metal hydride 3, and an external circuit 4;
FIG. 6 is a diagram of an actual working apparatus of the embodiment;
in the figure: the air diffusion electrode comprises an air diffusion electrode 1, a gas diffusion layer 101, a catalyst layer 102, an ion exchange membrane 2, a metal hydride electrode 3 which is a nickel-plated steel strip and is soaked in an alkaline solution, a teflon cavity 4 filled with an acidic solution which is in contact with the catalyst layer of the air diffusion electrode, a teflon cavity 5 which allows air to be in contact with the gas diffusion layer of the air diffusion electrode, and a stainless steel strip current collector 6 which is in contact with the catalyst layer of the air diffusion electrode and is conductive.
Detailed Description
Example 1
The present example includes the following process and test steps:
1) preparing an electrolyte: 35mL of 0.5M sulfuric acid was prepared as a simulated spent acid positive electrolyte. 35mL of 1M KOH solution was prepared as a simulated spent alkaline negative electrolyte.
2) Preparing a positive electrode: 30mg of platinum-carbon catalyst and 0.4mL of 50 wt% Polytetrafluoroethylene (PTFE) adhesive solution are mixed and ground, then the mixture is coated on the surface of hydrophobic carbon cloth, and the hydrophobic carbon cloth is placed in an oven at 80 ℃ for 2 hours.
3) Preparing a negative electrode: taking out Metal Hydride (MH) from a fully discharged rechargeable battery, mixing and grinding 1g of MH, 50mg of carbon black (Kabot) and 1mL of 50 wt% PTFE solution, putting the mixture into an oven to be dried to be in a cement state to obtain an active substance, coating the active substance on the upper half surface of foamed nickel with the thickness of 0.5mm and the length of 3 cm and the width of 0.15 mm, cutting a nickel-plated steel strip with the length of 6cm and the thickness of 8mm, folding the foamed nickel, clamping the active substance and the nickel-plated steel strip in the middle, and taking a part of the nickel-plated steel strip extending out of the foamed nickel as a lead current collector to obtain a negative electrode. The electrode was placed in an oven at 80 ℃ for 2h, removed and pressed with a press at 45KPa for 20 min.
4) Activation of the negative electrode: and (3) taking out the positive electrode (the nickel hydroxide is used as the component) from the fully discharged rechargeable battery, taking 1M KOH solution as electrolyte, and forming a secondary battery together with the negative electrode prepared in the step 3), performing charge-discharge with the current of 20mA for four times, and finally performing charge to 1.5V with the current of 20mA to obtain the activated and fully charged negative electrode.
5) Separator material handling and battery assembly: the cation exchange membrane soaked for over 12 hours is taken out of the 5 wt% NaCl solution and washed by deionized water. The positive electrode chamber is filled with positive electrode electrolyte; the negative electrode cavity is filled with negative electrode electrolyte and is in a static state; the two sides of the positive electrode cavity are respectively a negative electrode cavity and an air cavity. The electrolyte of the positive electrode and the electrolyte of the negative electrode are isolated by an ion exchange membrane, so that direct contact chemical neutralization is avoided. Assembling the key materials obtained in the steps 1), 2), 4) and 5) into a battery to be tested, wherein the current collectors of the positive electrode and the negative electrode are respectively a stainless steel strip and a nickel-plated steel strip.
And (3) current testing: the Wuhan blue battery test system is used for continuously discharging for 5min from 5mA to 35mA at constant current every 5mA, and the open-circuit voltage is measured at intervals of 10 s. And directly measuring the pH value of the tested electrolyte by using a digital display pH meter.
In this example, the pH changes are shown in table 1 below. The pH value is obviously changed, and the specific values are as follows: the pH of the acidic solution rose from 0.63 to 1.14, while the pH of the basic solution fell from 13.65 to 12.89, with pH changes of 0.51 and 0.76, respectively. Thus, there was some consumption of both hydrogen/hydroxide ions, indicating that the cell was able to discharge and neutralize a corresponding portion of the spent caustic solution. The electrochemical cell device in this example produces about 12 milliamp hours of electricity.
Example 2
The following process and test steps are included in this example:
1) preparing an electrolyte: 35mL of 1M sulfuric acid was prepared as a simulated spent acid positive electrolyte. 35mL of 1M KOH solution was prepared as a simulated spent alkaline negative electrolyte. This example, unlike example 1, uses a more acidic waste acid solution to further demonstrate the utility of the cell.
2) Preparing a positive electrode: 30mg of platinum-carbon catalyst and 0.4mL of 50 wt% PTFE adhesive solution are mixed and ground, then the mixture is coated on the surface of hydrophobic carbon cloth, and the hydrophobic carbon cloth is placed in an oven at 80 ℃ for 2 hours.
3) Preparing a negative electrode: taking out Metal Hydride (MH) from a fully discharged rechargeable battery, mixing and grinding 1g of MH, 50mg of carbon black (Kabot) and 1mL of 50 wt% PTFE solution, putting the mixture into an oven to be dried to be in a cement state to obtain an active substance, coating the active substance on the upper half surface of foamed nickel with the thickness of 0.5mm and the length of 3 cm and the width of 0.15 mm, cutting a nickel-plated steel strip with the length of 6cm and the thickness of 8mm, folding the foamed nickel, clamping the active substance and the nickel-plated steel strip in the middle, and extending the part of the nickel-plated steel strip out of the foamed nickel, thereby preparing a negative electrode as a lead current collector. The electrode is placed in an oven at 80 ℃ for 2h, and is pressed for 20min at the pressure of 45MPa by a press after being taken out. In contrast to example 1, this example used a higher pressure to prepare the electrode, thereby further improving the electrode performance.
4) Activation of the negative electrode: taking out the positive electrode (nickel hydroxide as the component) from the fully discharged rechargeable battery, taking 1M KOH solution as electrolyte, and forming a secondary battery together with the negative electrode prepared in the step 3), performing charge-discharge with 20mA current, circulating for four times, and finally performing charge to 1.5V with 20mA current to obtain an activated and fully charged negative electrode.
5) Separator material handling and battery assembly: the cation exchange membrane soaked for over 12 hours is taken out of the 5 wt% NaCl solution and washed by deionized water. The positive electrode chamber is filled with positive electrode electrolyte; the negative electrode cavity is filled with negative electrode electrolyte and is in a static state; the two sides of the positive electrode cavity are respectively a negative electrode cavity and an air cavity. The electrolytes of the positive and negative electrodes are isolated by an ion exchange membrane to avoid direct contact. Assembling the key materials obtained in the steps 1), 2), 4) and 5) into a battery to be tested, wherein the current collectors of the positive electrode and the negative electrode are respectively a stainless steel strip and a nickel-plated steel strip.
And (3) current testing: the Wuhan blue battery test system is used for continuously discharging for 5min from 5mA to 35mA at constant current every 5mA, and the open-circuit voltage is measured at intervals of 10 s. And directly measuring the pH value of the tested electrolyte by using a digital display pH meter.
In this example, the pH change is shown in table 2 below. The pH value is obviously changed, and the specific values are as follows: the pH of the acidic solution rose from 0.34 to 0.73, while the pH of the basic solution fell from 13.46 to 12.89, with pH changes of 0.39 and 0.57, respectively. Thus, there is some depletion of both hydrogen/hydroxide ions, indicating that the cell is capable of discharging and neutralizing a corresponding portion of the acid-base solution. The electrochemical cell device in this example produces about 12 milliamp hours of electricity.
The Voltage profiles over time for examples 1 and 2 are shown in FIG. 2, where the experimental data for Voltage1 were obtained for example 1 and the experimental data for Voltage2 were obtained for example 2. After the pressure used for pressing the negative electrode is increased in the embodiment 2, the structure of the material is more compact, the material is not easy to fall off, and the performance of the battery is more stable, which is specifically shown in that the discharge platform of the battery is higher than 1.4V in the tested current range.
Example 3
The present example includes the following process and test steps:
1) preparing an electrolyte: 1M sulfuric acid (17 mL) is prepared as simulated waste acid anode electrolyte. 17mL of 1M KOH solution was prepared as a simulated spent alkaline negative electrolyte. The present embodiment uses less electrolyte, thereby exploring the utility of the battery device.
2) Preparing a positive electrode: 30mg of platinum-carbon catalyst and 0.4mL of 50 wt% PTFE adhesive solution are mixed and ground, then coated on the surface of carbon cloth, and the carbon cloth is placed in an oven at 80 ℃ for 2 hours.
3) Preparing a negative electrode: taking out Metal Hydride (MH) from a fully discharged rechargeable battery, mixing and grinding 1g of MH, 50mg of carbon black (Kabot) and 1mL of 50 wt% PTFE solution, putting the mixture into an oven to be dried to be in a cement state to obtain an active substance, coating the active substance on the upper half surface of foamed nickel with the thickness of 2mm and the length of 3 cm and the width of 0.15 mm, cutting a nickel-plated steel strip with the length of 6cm and the thickness of 8mm, folding the foamed nickel, clamping the active substance and the nickel-plated steel strip in the middle, and taking a part of the nickel-plated steel strip extending out of the foamed nickel as a lead current collector to obtain a negative electrode. The electrode is placed in an oven at 80 ℃ for 2h, and is pressed for 20min at the pressure of 45MPa by a press after being taken out. In contrast to examples 1 and 2, this example uses thicker nickel foam for electrode preparation, thereby further improving electrode performance.
4) Activation of the negative electrode: and (3) taking out the positive electrode (the nickel hydroxide is used as the component) from the fully discharged rechargeable battery, taking 1M KOH solution as electrolyte, and forming a secondary battery together with the negative electrode prepared in the step 3), performing charge-discharge with the current of 20mA for four times, and finally performing charge to 1.6V with the current of 20mA to obtain the activated and fully charged electrode negative electrode.
5) Separator material handling and battery assembly: the anion exchange membrane soaked for more than 12 hours is taken out of the 5 wt% NaCl solution and washed by deionized water. The positive electrode chamber is filled with positive electrode electrolyte; the negative electrode cavity is filled with negative electrode electrolyte and is in a static state; the two sides of the positive electrode cavity are respectively a negative electrode cavity and an air cavity. The electrolytes of the positive and negative electrodes are isolated by an ion exchange membrane to avoid direct contact. Assembling the key materials obtained in the steps 1), 2), 4) and 5) into a battery to be tested, wherein the current collectors of the positive electrode and the negative electrode are respectively a stainless steel strip and a nickel-plated steel strip. In contrast to examples 1 and 2, this example uses an anion exchange membrane as the separator material, slowing down H+And ions are diffused, so that the performance of the battery is further improved.
And (3) current testing: the Wuhan blue battery test system is used for continuously discharging for 5min at constant current every 5mA from 5mA to 100mA, and the open-circuit voltage is measured at intervals of 10 s. And respectively measuring the pH value and the conductivity of the tested electrolyte by using a digital display pH meter and a conductivity meter.
In this example, the resulting hydride/air cell was discharged stably. Wherein the pH of the acidic solution before discharging is 0.13, the conductivity S is 83.75mS/cm, the pH of the alkaline solution is 13.56, and the conductivity S is 42.26 mS/cm. After discharge, the pH of the acidic solution was 0.24, the conductivity S was 62.26mS/cm, the pH of the alkaline solution was 13.30, and the conductivity S was 22.61 mS/cm. The data show that the acid solution and the alkaline solution are subjected to corresponding electrochemical neutralization treatment, the acidity and the alkalinity are obviously weakened, and the electricity output is 87.5 mAmp hours.
According to the polarization curve of fig. 3, when the output current is stabilized at 90mA, the output power of the battery is maximum, and reaches 93 mW. The efficiency of the cell is up to 94% as calculated by Faraday's law. This means that 94% of the electrochemically neutralized spent acid spent caustic produced a corresponding amount of electricity in the process.
Example 4
The present example includes the following process and test steps:
1) preparing an electrolyte: preparing 17mL of waste acid simulation liquid as anode electrolyte, wherein the component of the waste acid simulation liquid is 17 wt% of H2SO4、5wt％FeSO4、1.5wt％Al2(SO4)3、1wt％Ti(SO4)2(ii) a Preparing 80mL of waste alkali simulation solution as negative electrode electrolyte, wherein the component of the waste alkali simulation solution is 3 wt% of Na2CO3、0.5wt％NaHCO3、0.1wt％NaOH、0.5wt％NaClO。
In distinction to examples 1, 2 and 3, this example demonstrates the continuous throughput and feasibility of quantitative processing of the present invention by a one-sided spent caustic flow-through cycle electrochemical neutralization test.
2) Preparing a positive electrode: 20mg of platinum-carbon catalyst, 0.15g of conductive carbon black (cabot) and 0.4mL of 50 wt% PTFE adhesive solution are mixed, ground and coated on the surface of carbon cloth, and the carbon cloth is placed in an oven at 80 ℃ for 2 hours.
3) Preparing a negative electrode: taking out Metal Hydride (MH) from a fully discharged rechargeable battery, mixing and grinding 1g of MH, 50mg of conductive carbon black (Kabot) and 1mL of 50 wt% PTFE solution, putting the mixture into an oven to be dried to be in a cement state to obtain an active substance, coating the active substance on the upper half surface of foamed nickel with the thickness of 3 x 6cm and the thickness of 2mm, shearing a nickel-plated steel strip with the length of 6cm and the thickness of 0.15 x 8mm, folding the foamed nickel, clamping the active substance and the nickel-plated steel strip in the middle, and taking the part of the nickel-plated steel strip extending out of the foamed nickel as a lead current collector to obtain a negative electrode. The electrode is placed in an oven at 80 ℃ for 2h, and is pressed for 20min at the pressure of 45MPa by a press after being taken out.
4) Activation of the negative electrode: and (3) taking out the positive electrode (the nickel hydroxide is used as the component) from the fully discharged rechargeable battery, taking 1M KOH solution as electrolyte, and forming a secondary battery together with the negative electrode prepared in the step 3), performing charge-discharge with the current of 20mA for four times, and finally performing charge to 1.5V with the current of 20mA to obtain the activated and fully charged negative electrode.
5) Separator material handling and battery assembly: the anion exchange membrane soaked for more than 12 hours is taken out of the 5 wt% NaCl solution and washed by deionized water. The positive electrode chamber is filled with positive electrode electrolyte; the negative electrode cavity is internally provided with negative electrode electrolyte, and the peristaltic pump is communicated with an external beaker filled with the negative electrode electrolyte through a silicone tube pipeline connected with an inlet and an outlet of the negative electrode cavity of the battery, so that the negative electrode electrolyte is in a flowing circulation state; the two sides of the positive electrode cavity are respectively a negative electrode cavity and an air cavity. The electrolytes of the positive and negative electrodes are isolated by an ion exchange membrane to avoid direct contact. Assembling the key materials obtained in the steps 1), 2), 4) and 5) into a battery to be tested, wherein the current collectors of the positive electrode and the negative electrode are respectively a stainless steel strip and a nickel-plated steel strip.
And (3) current testing: the open circuit voltage was measured with a wuhan blue cell test system from 5mA to 70mA, with constant current discharge continuously for 10s every 5mA, and every 2 s.
In the embodiment, the formed battery system can stably treat waste acid and waste alkali solution simulating actual industrial production. As can be seen from the polarization curve of fig. 4, when the output current is stabilized at 40mA, the output power of the battery is maximum and reaches 22 mW.
| pH (before test) | pH (after test) | ΔpH | |
| 0.5M H2SO4 | 0.63 | 1.14 | 0.51 |
| 1M KOH | 13.65 | 12.89 | 0.76 |
TABLE 1
| pH (before test) | pH (after test) | ΔpH | |
| 1M H2SO4 | 0.34 | 0.73 | 0.39 |
| 1M KOH | 13.46 | 12.89 | 0.57 |
TABLE 2
The catalyst of the air electrode is a platinum-carbon mixture.
The negative electrode hydride active material is LaNi5 in an AB5 type lanthanum (La) nickel (Ni) alloy system.
The diaphragm material is an anion exchange membrane or a cation exchange membrane.
Through specific practical experiments, the actual open-circuit voltage measured value of the electrochemical battery device formed by the invention is higher than 1.6 volts. When the device produces electricity at 87.5 mAmp, the concentration of hydrogen ions or hydroxyl ions is reduced by at least 0.15-0.21M, and the pH value of the treated waste liquid is obviously reduced. Therefore, the method has the new functions of efficiently and synchronously treating the waste acid and the waste alkali and utilizing the electric quantity generated in the treatment process, and is favorable for improving the resource utilization rate. In addition, the electric quantity recovery rate of the acidic waste liquid and the alkaline waste liquid can reach 94 percent, and the voltage can still be maintained at about 1 volt when the maximum power is reached (namely 93 mW). No waste gas or waste liquid is generated in the reaction process, which shows that the selectivity of the target reaction is high, the method has the characteristics of environmental protection and no pollution, and the resource utilization rate is improved.
Compared with the prior art, the invention has the technical effects that: firstly, metal hydride is introduced as a negative electrode, so that the safety and the stability of the actual synchronous processing work of the battery are greatly improved. Second, the cell can achieve up to 94% recovery of electricity from the electrochemically neutralized spent acid spent caustic. And thirdly, based on the structural design improvement of the battery with two cavities and acid-base electrode matching, the battery device can be used for treating waste liquids with different pH values in a targeted manner, and provides a harmless, quantitative-reducing and recycling waste acid, waste alkali and synchronous treatment technical path.
The foregoing embodiments may be modified in many different ways by those skilled in the art without departing from the spirit and scope of the invention, which is defined by the appended claims and all changes that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. A metal hydride/air electrochemical cell device for simultaneously processing waste acid and waste alkali and generating electrical energy, comprising: an air diffusion electrode as a positive electrode, a hydride electrode as a negative electrode that stores hydrogen in advance, and an ion exchange membrane, wherein: the anode and the cathode are respectively placed in the waste acid solution and the waste alkali solution, and the anode and the cathode are connected with an external circuit phaseThe ion exchange membrane is arranged between the acid electrolyte and the alkali electrolyte and is used as a diaphragm material; when the battery discharges or waste acid and waste alkali treatment is carried out, the reaction of the negative electrode is to separate out hydrogen and the hydrogen reacts with OH in the waste alkali-The ions are oxidized to generate water and generate electrons; meanwhile, electrons are led out from an external circuit and flow to the anode, so that oxygen in the air and H in the waste acid+The ions are reduced to produce water.
2. A metal hydride/air electrochemical cell device as claimed in claim 1, wherein the spent acid solution and spent caustic solution are obtained from industrial spent acid and spent caustic and are used directly as electrolyte to obtain electrical energy while undergoing electrochemical neutralization.
3. A metal hydride/air electrochemical cell device as claimed in claim 1, wherein the air diffusion electrode is obtained by mixing and grinding a platinum-carbon catalyst, conductive carbon black and a binder solution, coating the mixture on the surface of a hydrophobic carbon cloth, and drying the mixture.
4. A metal hydride/air electrochemical cell device as claimed in claim 1, wherein said hydride electrode for pre-storing hydrogen is obtained by the steps of:
mixing and grinding metal hydride, conductive carbon black and a binder solution in the nickel-metal hydride battery, and drying to obtain an active substance;
secondly, coating active substances on the foamed nickel, folding the foamed nickel in half, and clamping the nickel-plated steel strip in the middle to form a sandwich structure, wherein the part of the nickel-plated steel strip extends out of the foamed nickel;
thirdly, the sandwich structure is dried and compacted and then is activated.
5. A metal hydride/air electrochemical cell device as claimed in any one of claims 1 to 4, wherein the metal hydride is LaNi5Lanthanum nickel hydrogen storage alloy.
6. A metal hydride/air electrochemical cell device as claimed in claim 4, wherein the activation process is: and (3) charging and discharging with 20mA current, circulating for four times, and finally charging once to form the hydride electrode for pre-storing hydrogen.
7. A metal hydride/air electrochemical cell device as claimed in claim 1, wherein the spent acid solution and spent alkaline solution are separated by an ion exchange membrane disposed within the cell device.
8. A metal hydride/air electrochemical cell device as claimed in claim 1 or 2, wherein the pH of the spent acid solution before treatment is less than 1, and the concentration of hydrogen ions in the spent acid is reduced after treatment, in particular, at least corresponding to a hydrogen ion concentration reduction of 0.15-0.21M per 87.5 ma hour of electricity output; the pH value of the treated waste acid solution is increased;
the pH value of the waste alkali solution is more than 13 before treatment, the concentration of hydroxide ions in the waste alkali is reduced after treatment, specifically, the electric quantity is reduced at least corresponding to the concentration reduction of the hydroxide ions of 0.15-0.21M when the output is 87.5 milliampere; the pH value of the treated waste alkali solution is reduced.
9. A metal hydride/air electrochemical cell device as claimed in claim 1, wherein the cell discharges and the total reaction is 1 mole of oxygen, 4 moles of hydrogen ions, 4 moles of hydrogen pre-stored hydride and 4 moles of hydroxyl ions to produce 4 moles of hydrogen released hydride and 6 moles of water, and the reaction products are free of any waste effluent, and the specific reaction scheme comprises:
and (3) positive pole reaction:
and (3) cathode reaction:
and (3) total reaction:
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| US20050238959A1 (en) * | 2004-04-23 | 2005-10-27 | Kwo Young | Nickel metal hydride battery design |
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| CN103928716A (en) * | 2013-01-15 | 2014-07-16 | 中国科学院大连化学物理研究所 | Lead-acid battery with coexisting acid, alkali and salt electrolyte solutions |
| US20160248136A1 (en) * | 2014-03-06 | 2016-08-25 | California Institute Of Technology | Metal hydride-air (mh-air) battery for low cost storage applications |
| US20180287237A1 (en) * | 2015-12-10 | 2018-10-04 | Board Of Regents, The University Of Texas System | Metal-Air Battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050238959A1 (en) * | 2004-04-23 | 2005-10-27 | Kwo Young | Nickel metal hydride battery design |
| CN101083338A (en) * | 2007-07-12 | 2007-12-05 | 南开大学 | Flexible nickle/metal hydrides secondary batteries |
| CN103928716A (en) * | 2013-01-15 | 2014-07-16 | 中国科学院大连化学物理研究所 | Lead-acid battery with coexisting acid, alkali and salt electrolyte solutions |
| US20160248136A1 (en) * | 2014-03-06 | 2016-08-25 | California Institute Of Technology | Metal hydride-air (mh-air) battery for low cost storage applications |
| US20180287237A1 (en) * | 2015-12-10 | 2018-10-04 | Board Of Regents, The University Of Texas System | Metal-Air Battery |
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