CN114277414A - Porous electrode and preparation method thereof - Google Patents
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- CN114277414A CN114277414A CN202110896046.6A CN202110896046A CN114277414A CN 114277414 A CN114277414 A CN 114277414A CN 202110896046 A CN202110896046 A CN 202110896046A CN 114277414 A CN114277414 A CN 114277414A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011812 mixed powder Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 27
- 238000006722 reduction reaction Methods 0.000 claims abstract description 26
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 21
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- 238000000034 method Methods 0.000 claims abstract description 16
- 239000013543 active substance Substances 0.000 claims abstract description 13
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- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 239000004332 silver Substances 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
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- 238000004519 manufacturing process Methods 0.000 claims description 12
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
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- 229910052744 lithium Inorganic materials 0.000 claims description 8
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- 239000010949 copper Substances 0.000 claims description 6
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- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
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- 229910052759 nickel Inorganic materials 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
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- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
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- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
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- 229910010420 TinO2n-1 Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 2
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a porous electrode and a preparation method thereof. The method comprises the following steps: mixing nano carbon powder, metal active precursor powder and polytetrafluoroethylene particles by a dry method to obtain mixed powder; compacting the mixed powder on a current collector to obtain a compact electrode; and immersing the compact electrode in electrolyte to carry out electrochemical reduction reaction, so that the precursor of the metal active substance is reduced into metal and is deposited on the surface of the conductive framework formed by the nano carbon in situ to obtain the porous electrode. The invention also provides the porous electrode obtained by the preparation method. The porous electrode obtained by the invention has the characteristics of large specific surface area of metal active substances, high activity utilization rate, small internal resistance and low consumption, and is a novel porous electrode with low cost, high performance and long service life.
Description
Technical Field
The invention relates to a porous electrode and a preparation method thereof, belonging to the field of electrochemical industry.
Background
The electrochemical industries such as electrolysis and electroplating, electrochemical water treatment, organic electrolytic synthesis, batteries, electrochemical sensors and the like can not separate electrodes, the preparation method, the structure and the performance of the electrode material have important influence on the electrochemical reaction process, and the continuous development of novel electrode materials with excellent performance is always widely concerned by various industries. The electrodes used in the electrochemical industry can be mainly divided into two types in terms of microstructure, wherein one type is a three-dimensional continuous compact non-porous or less-porous block electrode; the other is a porous electrode having an open pore structure in two or three dimensions. Compared with the former, the porous electrode has high specific surface area, a developed pore structure is favorable for electrolyte to go deep into the electrode, the diffusion resistance is small, and the utilization rate of active substances is high.
Many reports have been made on the present invention of porous electrodes. The chinese patent application No. 201810637398.8 discloses a method for preparing a porous electrode sheet, which includes mixing a conductive agent, a binder, activated carbon and a pore-forming agent to obtain a mixture, performing jet milling on the mixture, then performing roll-pressing to obtain a membrane, and performing thermal compounding after laminating the membrane with a current collector to obtain the porous electrode sheet; wherein the pore-forming agent is at least one selected from oxalic acid, citric acid and benzoic acid, and the pore-forming agent is decomposed when the thermal composite treatment is carried out, so that uniform pores are formed in the membrane. A Chinese patent application with application number 201910520862.X discloses a TinO2n-1Preparation method of porous electrode, TiH2And TiO2Mixing, ball milling, drying, sieving, sintering, dripping polyvinyl alcohol to obtain precursor mixture, adding the precursor mixture to foamed nickel, pressurizing to obtain compact, and sintering to obtain TinO2n-1A porous electrode; wherein polyvinyl alcohol exists as a binder, the polyvinyl alcohol is completely combusted under high-temperature sintering, and the obtained product is subjected to TinO2n-1Forming holes in the preform to obtain sintered TinO2n-1The preform has a porous structure. US patents 2015/0357626 a1 and US 2010/0015327 a1 describe processes in which an active material slurry is prepared in a so-called pulping process in which a particulate material is dispersed in a solution made of a polymer binder and a suitable solvent, and then the slurry is applied to a current collector in a coating process, the solvent is removed by drying, and a porous layer made of the particulate material and the binder is obtained on the surface of the current collector; wherein additionally a pore former is mixed into the active material slurry, which pore former dissolves out of the electrode in a subsequent step, thereby further increasing the porosity of the electrode. A method for preparing an electrode composition without solvent is described in US patent No. 2015/303481, on the basis of which chinese patent application No. 201980032800.2, further an electrode composition is applied to at least one surface of a substrate to obtain a dense electrode, the at least one particulate pore former is liquefied by heating the dense electrode; and/or makeThe dense electrode is contacted with at least one liquid electrolyte composition or at least one liquid component of an electrolyte composition for an electrochemical cell, which is capable of at least partially dissolving the at least one particulate pore-forming agent, to thereby obtain a porous electrode.
By combining the above methods, no matter dry electrode preparation or wet electrode preparation, additional pore-forming agent is required to be added into the original electrode components, so that the formed porous structure is difficult to control, the distribution uniformity is poor, and the formed pore channels are not most effective relative to the spatial distribution of active substances. Therefore, the development of new porous electrodes with low cost, high performance and long lifetime remains a key issue that is urgently needed to be solved by the electrochemical industry.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a porous electrode and a method for preparing the same, which do not require the addition of a pore-forming agent during the preparation process.
In order to achieve the above object, the present invention provides a method for preparing a porous electrode, comprising the steps of:
mixing nano carbon powder, metal active precursor powder and polytetrafluoroethylene particles by a dry method to obtain mixed powder;
compacting the mixed powder on a current collector to obtain a compact electrode;
and immersing the compact electrode in electrolyte to carry out electrochemical reduction reaction, so that the precursor of the metal active substance is reduced into metal and is deposited on the surface of the conductive framework formed by the nano carbon in situ to obtain the porous electrode.
In the above preparation method, preferably, the specific surface area of the nano carbon powder is not less than 10m2(ii)/g, more preferably 100-1000m2/g。
In the above preparation method, preferably, the nano carbon powder includes one or a combination of two or more of nano conductive carbon black, nano graphite, graphene, carbon nanotubes, nano carbon fibers, fullerene and graphene quantum dots.
In the above production method, preferably, the electrolyte is an aqueous system electrolyte or an organic system electrolyte. Wherein, the aqueous electrolyte can be inorganic salt aqueous solution, inorganic acid aqueous solution or inorganic base aqueous solution; preferably, the aqueous system electrolyte comprises one of an aqueous sodium chloride solution, an aqueous sodium sulfate solution, an aqueous sulfuric acid solution or an aqueous sodium hydroxide solution; the organic system electrolyte may include one of an organic carbonate electrolyte including lithium perchlorate, lithium hexafluorophosphate or lithium tetrafluoroborate.
In the above preparation method, preferably, the metal active material precursor is a powder having a particle size of 0.05 to 50 μm. When the metal active matter precursor is insoluble in the adopted electrolyte, the metal active matter precursor can be electrochemically reduced in the compact electrode to obtain the corresponding metal active matter in the electrolyte, and the electrolyte does not generate reduction reaction; when the metal active precursor is soluble in the electrolyte used, then, in order to avoid the dissolution of the metal active precursor in the dense electrode, the saturated metal active precursor should be contained in the electrolyte, and then the metal active precursor in the electrolyte can be subjected to electrochemical reduction reaction in the dense electrode to obtain the corresponding metal active.
In the above production method, preferably, the metal active precursor includes one or a combination of two or more of a metal salt, a metal oxide, and a metal hydroxide. The metal in the metal active material precursor may be selected from one or a combination of two or more of zinc, manganese, silver, lead, chromium, cadmium, nickel, copper, iron, tin, gold, indium, platinum, rhodium, palladium, lithium, sodium, and the like.
In the above production method, preferably, the polytetrafluoroethylene particles have a particle size of 0.1 to 100 μm.
In the above-mentioned production method, the dry mixing means that the mixed powder is subjected to a uniform dispersion treatment in a dry state by a stirrer, a ball mill, a grinder, a pulverizer or a crusher which provides a shearing force, wherein polytetrafluoroethylene particles as a binder are sheared into a radial fiber shape which has an adhesive aggregation action on the mixed powder.
In the above-described manufacturing method, the process of compacting the mixed powder on the current collector may be performed in the following manner: the operation is to directly compact the formable mixed powder onto a current collector through an extruder and/or a calender, or to form the mixed powder into a stable independent block and then compact the stable independent block onto the current collector, wherein the adopted current collector can be one of flaky, meshed or foamed copper, aluminum, nickel, titanium, stainless steel, silver or porous carbon. Preferably, the bulk conductivity of the dense electrode is not less than 0.01S/cm, more preferably 0.1-100S/cm.
In the above preparation method, the electrochemical reduction reaction means that the dense electrode is used as a cathode in an electrolyte solution, so that the metal active material precursor in the dense electrode is reduced into a corresponding metal or alloy by electrons.
In the above preparation method, the electrochemical reduction reaction is specifically performed in the following manner: immersing the compact electrode in electrolyte solution (or electrolyte solution saturated with corresponding metal active substance precursor) as cathode, platinum electrode as auxiliary anode, saturated calomel electrode as reference electrode, and applying 0.1-500mA/cm2The cathode reduction current of (2) is subjected to electrochemical reduction reaction to reduce the metal active material precursor into a corresponding metal active material.
In the preparation method, the metal in-situ deposition on the surface of the conductive framework formed by the nanocarbon means that the metal active substance precursor in the compact electrode obtains electrons from the conductive framework formed by the adjacent and closely contacted nanocarbon to be reduced into corresponding metal or alloy, and the metal active substance precursor is deposited on the conductive framework formed by the adjacent and closely contacted nanocarbon to further form a three-dimensional pore structure, and the compact electrode is converted into a porous electrode after electrochemical reduction.
According to the specific embodiment of the invention, the preparation method of the porous electrode can be carried out in the following way, and the technical scheme is that dry mixing treatment is carried out on at least one nano carbon powder used as a conductive agent, at least one metal salt used as a metal active precursor, powder of metal oxide or metal hydroxide and polytetrafluoroethylene particles to obtain uniformly dispersed mixed powder; kneading the mixed powder into a molding material, and further compacting the molding material on a current collector to obtain a compact electrode; and finally, immersing the compact electrode in an electrolyte, reducing the metal salt, the metal oxide or the metal hydroxide into metal through electrochemical reduction reaction, and depositing the metal salt, the metal oxide or the metal hydroxide on the surface of the conductive framework formed by the nano carbon in situ to obtain the porous electrode.
According to the specific embodiment of the invention, pore-forming agents and pore-forming agents are not used in the preparation method of the porous electrode provided by the invention.
The invention also provides a porous electrode prepared by the preparation method.
According to a specific embodiment of the present invention, preferably, the porous electrode has a conductive skeleton composed of nanocarbons bonded by polytetrafluoroethylene particles, and the surface of the conductive skeleton has a metal deposition layer having a thickness of 1nm to 100 μm and a pore size of 1nm to 100 μm.
The method can obtain a dry powdery mixture by using a conductive agent, polytetrafluoroethylene particles and metal active substance precursor powder as raw materials under the condition of not using a solvent, wherein the polytetrafluoroethylene particles used as a binder are sheared into radial fibers, the radial fibers have an adhesion and aggregation effect on the mixed powder, and the mixed powder is easy to knead, mold and compact on a current collector to obtain a compact electrode with certain conductive performance; by carrying out electrochemical reduction on the metal active matter precursor of the compact electrode in a specific electrolyte, the required metal active matter can be directly obtained, and a three-dimensional pore structure can be formed at the same time without adding an additional pore-forming agent, so that the formed porous structure is beneficial to full utilization of the metal active matter, and the transmission resistance of electrochemical reaction is greatly reduced. In addition, the porous electrode has a relatively high porosity and can be arbitrarily modulated in a wide range. The porous electrode obtained by the invention has the characteristics of large specific surface area of metal active substances, high activity utilization rate, small internal resistance and low consumption, and is a novel porous electrode with low cost, high performance and long service life.
Drawings
FIG. 1a is a Scanning Electron Microscope (SEM) photograph of a compact electrode formed by kneading a mixed powder of silver chloride, carbon nanotubes and polytetrafluoroethylene.
Fig. 1b is a Scanning Electron Microscope (SEM) photograph of the porous silver electrode obtained after electrochemical reduction of the dense electrode in a sodium chloride solution.
FIG. 2 is a constant current reduction chronopotentiometric curve of a dense electrode and a porous silver electrode.
Fig. 3 is an X-ray diffraction (XRD) pattern of the dense electrode and the porous silver electrode.
Fig. 4a is a distribution diagram of the surface C, F, Cl of the dense electrode and Ag element.
Fig. 4b is a distribution diagram of the surface C, F, Cl of the porous silver electrode and the Ag element.
Fig. 5 is a comparison graph of chronopotentiometric potentials of a porous silver electrode and a commercial silver wire as a quasi-reference electrode applied in seawater.
FIG. 6 is a linear polarization curve of AgCl/Ag/CNT porous electrode and comparative silver wire in 1mol/L NaCl solution.
FIG. 7 is a graph showing the potential distribution of 28 AgCl/Ag/CNT porous electrodes prepared in different batches after soaking in seawater for 1 month.
FIG. 8 is a range potential curve of a pair of AgCl/Ag/CNT porous electrodes as an ocean electric field detection probe soaked in seawater for a long time.
FIG. 9 is a frequency response characteristic diagram of electric field signals of different frequencies in seawater using a pair of AgCl/Ag/CNT porous electrodes as an ocean electric field detection probe.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a preparation method of a porous electrode, which comprises the following steps:
97g of silver chloride with the average particle size of 20 mu m, 6g of polytetrafluoroethylene particles with the average particle size of 50 mu m and 220m of specific surface area2Adding 3 g/g of carbon nano tube into a ball mill for dry grinding to obtain uniformly dispersed mixed powder;
kneading and molding the mixed powder by a double-screw extruder, pressing the mixed powder on a silver mesh current collector with 100 meshes to obtain an SEM photo of a compact electrode, wherein the SEM photo is shown in figure 1a, polytetrafluoroethylene particles are in a radial fiber shape under the action of high shearing force, and the carbon nano tube and silver chloride powder are adhered and kneaded to form the compact electrode (except for a plurality of pores formed by cracks);
the dense electrode was immersed in a 3.5 wt% aqueous sodium chloride solution as a cathode, a platinum electrode as an auxiliary anode, a saturated calomel electrode as a reference electrode, and a cathodic reduction current of-5 mA was applied, and a constant-current reduction chronopotentiometric curve is shown in fig. 2, as can be seen from fig. 2: 12370s, the reduction termination potential reaches-0.6V, and the silver chloride in the compact electrode is almost completely reduced into silver, thus obtaining the porous silver electrode. This is also confirmed by the XRD pattern of fig. 3, where (a) is the XRD curve of the dense electrode, which is in full agreement with the standard diffraction peak position of silver chloride; fig. 3 (b) is an XRD curve of the porous silver electrode obtained after the dense electrode is subjected to the cathode reduction, which is completely consistent with the standard diffraction peak position of silver, and the SEM photograph of fig. 1b further shows that the porous silver electrode is obtained through the above preparation process.
In order to further analyze the obtained porous electrode structure, fig. 4a and 4b are distribution charts of the surface C, F, Cl of the compact electrode and the porous electrode and the distribution pattern of the Ag element obtained through an EDX (enhanced dispersive X-ray) energy spectrum, the large-area and light-gray-scale particle appearance on the compact electrode scanning photo in fig. 4a is similar to the distribution appearance of the Ag element and the Cl element, which indicates that the composition of the Ag element and the F element is AgCl, and the C element and the F element are distributed in the whole scanning area in combination, the local high-distribution area is similar to the dark-gray-scale particle appearance on the compact electrode scanning photo, which indicates that the carbon nanotubes are uniformly dispersed on the whole surface and the polytetrafluoroethylene particles are dispersed in radial fiber shape, thereby ensuring that the compact electrodes are all uniformly distributedUniform conductivity and structural stability; the porous electrode in fig. 4b has a large area, porous, and light-gray particle profile similar to the distribution profile of Ag element, and the distribution brightness of the corresponding Cl element is low, which indicates that the residual AgCl is very little and most of the AgCl has been reduced, and the distribution brightness of the C element also becomes low, which indicates that the Ag generated by AgCl reduction is coated on the surface of the carbon nanotube, and the distribution of the F element is still similar to the deep-gray particle profile of the porous electrode scan photograph, which indicates that the ptfe particles still remain dispersed in radial fiber form; further through the four-probe test, the volume conductivity of the compact electrode is about 2S cm-1And the volume conductivity of the porous electrode obtained after cathode reduction is more than 5000S-cm-1The reason for the improvement of the conductivity order is that the compact electrode depends on the carbon nano tube to form a conductive network, and the porous electrode obtained after the cathode reduction depends on the silver-coated carbon nano tube to form the conductive network. By combining the above analysis, it can be clearly shown that a novel porous silver electrode is obtained by the preparation method of this example.
To further illustrate the great potential of the novel porous electrode in application, the present invention exemplifies the application of the porous silver electrode prepared as described above in seawater as a reference electrode. After the porous silver electrode of example 1 was immersed in an aqueous solution of sodium chloride having a concentration of 3.5 wt% for 12 hours, it was found that silver chloride having an electric quantity of about 1 coulomb was generated on the surface of the porous silver, since the porous silver electrode of example 1 was constructed with carbon nanotubes as a skeleton, which can be represented by symbols as an Ag/CNT porous electrode, which formed a pair of galvanic couples with the porous silver, oxygen reduction reaction occurred on the carbon nanotubes by dissolving oxygen in the solution, and the resulting electrons originated from anodic reaction of the porous silver to generate silver chloride, which can be represented by symbols as AgCl/Ag/CNT porous electrode, which was directly used as a quasi-reference electrode in seawater and compared with a high-purity silver wire quasi-reference electrode for one month stability experiment, as shown in the time-potential comparison curve of fig. 5 (with respect to a commercial saturated potassium chloride AgCl/Ag reference electrode SSCE), as can be seen from FIG. 5, the potential of the AgCl/Ag/CNT porous electrode is always stabilized at 48 + -2 mV, while the potential of the Ag wire is stabilized in seawater for a longer time, the potential fluctuation is large,in particular, the steady potential is constantly moving negatively after the replacement of fresh seawater and is not recoverable. FIG. 6 is a linear polarization curve of AgCl/Ag/CNT porous electrode and comparative silver wire in NaCl solution with concentration of 1mol/L, from which the exchange current density of AgCl/Ag/CNT porous electrode of 3.7mA/cm can be obtained2It is nearly 100 times that of silver wire, which is the root cause of its good polarization resistance and stability. FIG. 7 is a potential distribution diagram of 28 AgCl/Ag/CNT porous electrodes prepared from different batches after being soaked in seawater for 1 month, and the potential distribution range is narrow (49.1 +/-0.3 mVvs. SSCE), which shows that the preparation method has good parallelism and can be commercialized. In addition, the AgCl/Ag/CNT porous electrode can be also applied to a marine electric field detection sensor probe as a non-polarized electrode, the range deviation of the AgCl/Ag/CNT porous electrode is less than 100 muV/24 h required by the standard, the AgCl/Ag/CNT porous electrode can be stabilized within 36.3 muV/24 h even after 10 days of work (see figure 8), and the electrode noise is only
Fig. 9 is a frequency response characteristic diagram of electric field signals of different frequencies in seawater, and it can be seen from the results shown in fig. 9 that: the AgCl/Ag/CNT porous electrode can completely meet the use requirement. Thus, the AgCl/Ag/CNT porous electrode of the invention, both in principle and in practice, shows to be a low cost, high stability, long life and full depth marine quasi-reference or non-polarized electrode.
Example 2
The embodiment provides a preparation method of a porous electrode, which comprises the following steps:
firstly 100g of lead sulfate with an average particle size of 2 μm, 12g of polytetrafluoroethylene particles with an average particle size of 10 μm and a specific surface area of 434m2Adding 1 g/g of reduced graphene oxide into a jet mill for dry mixing to obtain uniformly dispersed mixed powder;
then the mixed powder is directly pressed on a foamed titanium current collector (the titanium surface is modified with a titanium suboxide coating) through a double-roller rolling machine to prepare a compact electrode;
and immersing the compact electrode in a sulfuric acid aqueous solution with the concentration of 1mol/L to be used as a cathode, using a platinum electrode as an auxiliary anode, applying a cathodic reduction current of-20 mA, and reducing the lead sulfate in the compact electrode into lead to prepare the porous lead electrode taking the reduced graphene oxide as a framework.
The porous lead electrode can be used as a negative electrode and/or a positive electrode of a lead-acid battery after being subjected to reforming treatment, and the power density and the energy density of the lead-acid battery can be greatly improved at the same time.
Example 3
The embodiment provides a preparation method of a porous electrode, which comprises the following steps:
firstly 5g of platinum dioxide with the average particle size of 50nm, 5g of polytetrafluoroethylene particles with the average particle size of 5 mu m and the specific surface area of 400m2Adding 4 g/g of high-conductivity nano carbon black into a grinding machine for dry mixing to obtain uniformly dispersed mixed powder;
kneading and molding the mixed powder through a calender, and pressing the mixed powder on a porous carbon current collector to prepare a compact electrode;
immersing the compact electrode in a sulfuric acid aqueous solution with the concentration of 0.5mol/L to be used as a cathode, using a platinum electrode as an auxiliary anode, applying a cathodic reduction current of-1 mA, and reducing the platinum dioxide in the compact electrode into platinum to prepare the porous platinum electrode taking the highly conductive nano carbon black as a framework.
The porous platinum electrode can be used as a hydrogen electrode and/or an oxygen electrode of a proton exchange membrane fuel cell after nafion modification treatment, the platinum carrying capacity can be greatly reduced, and the power generation performance of the fuel cell is improved.
Example 4
The embodiment provides a preparation method of a porous electrode, which comprises the following steps:
firstly, 30g of cuprous hydroxide and zinc hydroxide with the average particle size of 500nm respectively, 18g of polytetrafluoroethylene particles with the average particle size of 20 mu m and 50m of specific surface area2Adding 20 g/g of carbon nanofibers into a ball mill for dry mixing to obtain uniformly dispersed mixed powder;
kneading and molding the mixed powder through a calender, and pressing the mixed powder on a 20-mesh copper mesh current collector to obtain a compact electrode;
immersing the compact electrode in a sodium sulfate aqueous solution with the concentration of 0.5mol/L to be used as a cathode, using a platinum electrode as an auxiliary anode, applying a cathode reduction current of-2 mA, and reducing cuprous hydroxide and zinc hydroxide in the compact electrode into a copper-zinc alloy to prepare the porous copper-zinc alloy electrode taking the carbon nanofibers as a framework.
The porous copper-zinc alloy electrode is subjected to dealloying treatment to further obtain a porous copper electrode with composite nanopores, and the porous copper electrode can be used as a high-sensitivity electrochemical sensor electrode.
Example 5
The embodiment provides a preparation method of a porous electrode, which comprises the following steps:
firstly 1000g of lithium hexafluorophosphate with an average particle size of 15 μm, 100g of polytetrafluoroethylene particles with an average particle size of 20 μm, and a specific surface area of 315m250 g/g carbon nanotube and a specific surface area of 150m2Adding 10 g/g of graphene into an airflow crusher for dry mixing to obtain uniformly dispersed mixed powder;
then the mixed powder is rolled in a glove box to prepare a diaphragm, and the diaphragm is pressed on a copper foil current collector to prepare a compact electrode;
immersing the compact electrode in organic carbonate electrolyte containing saturated lithium hexafluorophosphate to serve as a cathode, taking the lithium iron phosphate electrode as an anode, applying a cathode reduction current of-50 mA to reduce the lithium hexafluorophosphate in the compact electrode into metal lithium, and thus obtaining the porous lithium electrode taking the carbon nanotube composite graphene as a framework.
The porous lithium electrode can be used as a negative electrode of a lithium ion battery, can effectively inhibit the formation of lithium dendrites in the charge-discharge cycle process, can be charged and discharged under the condition that the discharge multiplying power is increased by 50 times compared with the conventional metal lithium negative electrode, can be circulated for 500 times without obvious lithium dendrites and pulverization phenomena, and greatly improves the cycle charge-discharge performance and safety of the lithium ion battery.
The above description is only a preferred embodiment of the present invention, and should not be construed as limiting the present invention in any way, and any technical equivalents of the modifications or variations of the present invention disclosed by the present invention may be substituted by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. A method of making a porous electrode comprising the steps of:
mixing nano carbon powder, metal active substance precursor powder and polytetrafluoroethylene particles by a dry method to obtain mixed powder, wherein the loose packing density ratio of the nano carbon powder to the metal active substance precursor powder is 0.001-0.1: 1, the mass ratio of the nano carbon powder to the polytetrafluoroethylene particles is 1: 1-10;
compacting the mixed powder on a current collector to obtain a compact electrode;
and immersing the compact electrode in electrolyte to carry out electrochemical reduction reaction, so that the precursor of the metal active substance is reduced into metal and is deposited on the surface of the conductive framework formed by the nano carbon in situ to obtain the porous electrode.
2. The preparation method according to claim 1, wherein the specific surface area of the nano-carbon powder is not less than 10m2Per g, preferably 100-2/g。
3. The method for preparing the carbon nanopowder according to claim 1, wherein the carbon nanopowder comprises one or more of carbon nanopowder, graphite nanopowder, graphene, carbon nanotubes, carbon nanofibers, fullerenes and graphene quantum dots in combination.
4. The production method according to claim 1, wherein the electrolyte is an aqueous system electrolyte or an organic system electrolyte;
preferably, the aqueous system electrolyte includes an aqueous inorganic salt solution, an aqueous inorganic acid solution, or an aqueous inorganic base solution; preferably, the aqueous system electrolyte comprises one of a sodium chloride aqueous solution, a sodium sulfate aqueous solution, a sulfuric acid aqueous solution and a sodium hydroxide aqueous solution;
preferably, the organic system electrolyte comprises one of lithium perchlorate, lithium hexafluorophosphate or a solution of lithium tetrafluoroborate in an organic carbonate.
5. The production method according to claim 1, wherein the metal active material precursor is a powder having a particle size of 0.05 to 50 μm.
6. The production method according to claim 1, wherein the metal active material precursor includes one or a combination of two or more of a metal salt, a metal oxide, and a metal hydroxide;
preferably, the metal is selected from one or a combination of two or more of zinc, manganese, silver, lead, chromium, cadmium, nickel, copper, iron, tin, gold, indium, platinum, rhodium, palladium, lithium and sodium.
7. The production method according to claim 1, wherein the polytetrafluoroethylene particles have a particle size of 0.1 to 100 μm.
8. The production method according to claim 1, wherein the bulk conductivity of the dense electrode is not less than 0.01S/cm, preferably 0.1 to 100S/cm.
9. A porous electrode produced by the production method according to any one of claims 1 to 8.
10. The porous electrode according to claim 9, wherein the porous electrode has a conductive skeleton composed of nanocarbons bonded by polytetrafluoroethylene, and the surface of the conductive skeleton has a metal deposition layer having a thickness of 1nm to 100 μm and a pore size of 1nm to 100 μm.
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