CN114388274A - Ion and electron composite conduction electrode and in-situ preparation method thereof - Google Patents
Ion and electron composite conduction electrode and in-situ preparation method thereof Download PDFInfo
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- CN114388274A CN114388274A CN202111661962.8A CN202111661962A CN114388274A CN 114388274 A CN114388274 A CN 114388274A CN 202111661962 A CN202111661962 A CN 202111661962A CN 114388274 A CN114388274 A CN 114388274A
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- conductive material
- ion
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- electron
- electrode
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 239000004020 conductor Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000002243 precursor Substances 0.000 claims abstract description 43
- 150000002500 ions Chemical class 0.000 claims abstract description 42
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- 238000003756 stirring Methods 0.000 claims abstract description 22
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims abstract description 21
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
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- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- RMSOEGBYNWXXBG-UHFFFAOYSA-N 1-chloronaphthalen-2-ol Chemical compound C1=CC=CC2=C(Cl)C(O)=CC=C21 RMSOEGBYNWXXBG-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 2
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 2
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- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- UCYRAEIHXSVXPV-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)indiganyl trifluoromethanesulfonate Chemical compound [In+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F UCYRAEIHXSVXPV-UHFFFAOYSA-K 0.000 claims description 2
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention relates to an electrode which is conducted by combining ions and electrons and an in-situ preparation method thereof, comprising the following steps: and adding the additive precursor A and the active substance B into the mixing device, mixing for a set time, stirring the mixture of the additive precursor A and the active substance B in the mixing device by using the stirring device while mixing, and performing in-situ ion exchange on the additive precursor A and the active substance B in the stirring process to generate a product with electrolyte cation conductivity and uniformly disperse the product. The invention has the beneficial effects that: the invention also designs a three-dimensional conductive network constructed by zero-dimensional/one-dimensional/two-dimensional structural units in a targeted manner by the composite use of electronic conductive materials with different micro-morphologies. The material has low cost, simple and convenient method and easy large-scale expanded production, and is particularly suitable for preparing electrodes of water-system ion batteries and water-system super capacitors.
Description
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to an ion and electron composite conduction electrode and an in-situ preparation method thereof.
Background
With the development of economy and the progress of science and technology, the dependence of the current society on energy is increasing day by day. Electric energy is advocated and widely popularized by modern society as a clean and convenient secondary energy source at a use terminal. However, most of the current electric energy sources are fossil fuels such as coal, oil and natural gas, which are incompatible with the growing social demands in terms of resource abundance and bring serious consequences such as environmental pollution and aggravation of greenhouse effect. To address the drawbacks of fossil fuel power generation, renewable energy sources, such as: new energy systems such as solar energy, wind energy, tidal energy and the like are brought into the electric energy supply side of the power grid. In this process, the fluctuation and intermittency of the renewable electric energy are likely to impact the power grid, so that a large energy storage system with high efficiency needs to be developed. Among them, electrochemical energy storage is considered as an important candidate energy storage system due to its simple design and high industrialization degree.
At present, lithium ion batteries are the only candidates in the fields of 3C consumption and vehicle-mounted power batteries due to high energy density and long cycle life. However, lithium ion batteries based on flammable organic electrolyte systems still have a series of problems in terms of safety of use and abundance of metallic lithium resources. Therefore, a water system energy storage system which is more green, safe and low in cost is a better choice in a large-scale standing type energy storage system with loose requirements on energy density and a vehicle-mounted energy system used for a short distance.
In order to improve the energy density of the aqueous battery as much as possible, researchers and engineers have made many studies on metal-type negative electrode materials. At present, the bottleneck of performance and stability of the water-based battery is mainly the poor interface stability of the negative electrode and the water-based electrolyte, and the root of the bottleneck is that the negative electrode has poor performance on electron and ion transmission in the charge and discharge processes. Therefore, optimizing the material and structural design of the metal-type negative electrode to simultaneously improve the ionic and electronic conductivity is a key direction of research and development in the field.
At present, the mainstream electrode design and preparation only focuses on improving the electronic conductivity of the electrode plate, and there are few documents and patents reporting the composite regulation and control of the ionic and electronic conductivity. In the aspect of improving the ionic conductivity independently, the document of Ultrafast-Ion-Conductor Interface heated High-Rate and Stable Voltage metals reports that the ionic conductivity type coating layer is used, and can protect the Metal electrode and simultaneously has better permeability to electrolyte ions. In the aspect of industrial research and development, the invention patent with the application number of CN202110725202.2 discloses oxygen-deficient TiO2-xThe coating anchored on the silica gel elastomer is beneficial to the uniform transmission of electrolyte ions. The invention patent with the patent number of CN202010818783.X discloses a metal electrode protective layer which is prepared by a short-circuit galvanic cell method and is beneficial to the transmission of electrolyte ions. The invention patent with patent number CN202010232631.1 takes the positive electrode as an exampleDisclosed is a Konkendall pore-forming effect formed by a hydrothermal reaction, which can effectively improve the diffusion of electrolyte ions. These results have good effects on maintaining and even improving the ionic conductivity. However, these efforts have not been made to comprehensively design ionic conductivity and electronic conductivity from the viewpoint of material and structure. Moreover, most of the reported methods have poor compatibility with large-scale production modes, and the surface coating type material has high process difficulty, so that the requirements of large-scale preparation cannot be met.
Therefore, the development of an electrode which can be produced in a large scale and has ionic and electronic conductivity as a metal type cathode has important research and industrialization significance for improving the performance of a water system energy storage device.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an electrode which is conducted by combining ions and electrons and an in-situ preparation method thereof.
The ion and electron recombination conducting electrode comprises: a point-like conductive material, a linear conductive material, a planar conductive material, and a current collecting base material; the point-shaped conductive material, the linear conductive material and the planar conductive material are all attached to the current collecting base material; the three-dimensional porous framework is constructed by the point-shaped conductive material, the linear conductive material and the planar conductive material.
Preferably, the point-like conductive material is a point-like electronic conductive material or a point-like ion-electron composite conductive material, the linear conductive material is a linear electronic conductive material or a linear ion-electron composite conductive material, and the planar conductive material is a planar electronic conductive material or a planar ion-electron composite conductive material.
The in-situ preparation method of the ion and electron combined conducting electrode comprises the following steps:
step 1, adding an additive precursor A and an active substance B into a mixing device, mixing for a set time, stirring a mixture of the additive precursor A and the active substance B in the mixing device by using a stirring device while mixing, and generating in-situ ion exchange in the stirring process of the additive precursor A and the active substance B to generate a product with electrolyte cation conductivity and uniformly dispersing the product;
step 2, after the mixing device in the step 1 is cooled, adding a dispersing binder C into the mixture obtained in the step 1, continuously mixing and stirring for a set time, and then adding a conductive network D into the mixing device; under the action of the dispersing binder C, performing secondary uniform dispersion on the conductive network D and the uniformly dispersed product in the step 1 to obtain a powder mixture directly used for preparing an electrode;
step 3, transferring the powder mixture prepared in the step 2 to a afflux substrate, and heating and drying; and rolling and cutting the afflux substrate with the powder mixture to obtain the pole piece with the set size.
Preferably, the mass ratio of the additive precursor A, the active substance B, the dispersing binder C and the conductive network D added in the step 1 and the step 2 is (1-10): 60-90): 1-10): 5-20); in the step 1, spontaneous in-situ electric replacement reaction also occurs in the stirring process of the additive precursor A and the active substance B.
Preferably, the additive precursor a in step 1 is an ionic conduction precursor a1, and after the ionic conduction precursor a1 reacts with the active material B, the electrolyte precursor has the transport capability of electrolyte cations; the ion conductive precursor A1 is at least one of metal phosphate, metal hydrogen phosphate, metal fluoride, organic ligand of metal organic framework compound and silicate, the ion conductive precursor A1 has electrolyte cation transmission capability and is powder with the particle size of less than 100 micrometers, or 0.01-50% of aqueous solution or dispersion liquid; the active substance B is metal simple substance powder or metal simple substance alloy with reducibility before hydrogen element and capable of safely and slowly generating hydrogen evolution reaction in a water system in the process of preparing the pole piece without generating deflagration, the particle size of the active substance B is less than 100 microns, and the active substance B is at least one of metal simple substance magnesium, aluminum, zinc, tin and lead and the metal simple substance alloy; the dispersion binder C is at least one of an aqueous solution and an emulsion dispersed in a water system, and the dispersion binder C is at least one of polytetrafluoroethylene, polyvinylidene fluoride, cellulose and a functional group modifier thereof, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, sodium polyacrylate and water-soluble rubber.
Preferably, the additive precursor a in step 1 is an ionic conduction precursor a1 and an electronic conduction precursor a 2; the ion conductive precursor a1 is at least one of hydroxyapatite, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, diammonium hydrogen phosphate, lithium fluoride, sodium fluoride, potassium fluoride, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-imidazolecarboxaldehyde, benzimidazole, montmorillonite, zircon, hydrotalcite, zeolite, kaolin, and clay; the electron-conductive precursor a2 is at least one of indium nitrate, indium acetate, indium sulfate, indium fluoride, indium chloride, indium bromide, indium iodide, indium trifluoromethanesulfonate, tin nitrate, tin acetate, tin sulfate, tin fluoride, tin chloride, tin bromide, tin iodide, tin trifluoromethanesulfonate, bismuth nitrate, bismuth acetate, bismuth fluoride, bismuth chloride, bismuth bromide, bismuth iodide, bismuth trifluoromethanesulfonate, and bismuth ammonium citrate; the electron conductive precursor A2 is a 0.01-50% aqueous solution of a metal salt having high electron conductivity and capable of suppressing hydrogen evolution reaction of the active material B in the electrode; the cation of the active ingredient of the electron-conductive precursor a2 is a metal element having a smaller reducibility than the active material B, and can react with the active material B to produce a simple metal substance having both electron conductivity and an ability to suppress a hydrogen evolution reaction.
Preferably, in the step 2, the conductive network D is a three-dimensional porous skeleton constructed by using point-type materials, line-type materials and surface-type materials as structural units, and the three-dimensional porous skeleton contains at least one of carbon and carbide materials; the dot material (zero dimension) is at least one of acetylene black, Ketjen black, activated carbon and carbon quantum dots; the linear material (one-dimensional) is at least one of carbon nano tube, carbon fiber and carbon nano belt; the surface material (two-dimensional) is at least one of natural graphite, artificial graphite, graphene, graphite alkyne and MXene material; the material source of the electron conductive material in the electrode in ion and electron composite conduction is mainly a conductive network D, and the rest material source can be extra electron conductive material generated through in-situ electric replacement reaction; the electronic conductive material covers three types of point conductive material, linear conductive material and planar conductive material; the ion conductive material does not necessarily cover all three types of the point conductive material, the linear conductive material and the planar conductive material, and the three-dimensional type of the ion conductive material is determined by the material and the process of the in-situ ion exchange.
Preferably, the active material B is at least one of zinc, lead, an alloy of zinc, and an alloy of lead.
Preferably, the mixing device in the step 1 comprises a planetary ball milling device, a shimmy ball milling device and a horizontal ball milling device; the stirring device is a double-planet stirring device; 3, transferring the powder mixture prepared in the step 2 to a afflux substrate in a single-sided coating, double-sided coating, slurry coating, screen printing or tabletting mode; the current collecting base material is a thin conductive material with the thickness of 5-100 micrometers, and comprises a carbon base material and a metal base material; the carbon substrate is graphite paper or carbon cloth, and the metal substrate is stainless steel foil, titanium foil, copper foil, nickel foil, zinc foil, stainless steel mesh, titanium mesh, copper mesh, nickel mesh, zinc mesh, copper foam, nickel foam or zinc foam.
Preferably, the electrode which conducts ions and electrons in a combined manner is used in an aqueous energy storage device as a metal-type negative electrode; the water-based energy storage device is a water-based ion battery or a water-based super capacitor.
Preferably, the mechanism of the in situ ion exchange reaction is: the active substance B generates hydrogen evolution reaction in the powder mixing process of the water system, thereby slowly releasing B on the surfacen+(n-1, 2,3) cations, which, upon contact with the ion-conducting precursor a1, undergo a spontaneous in situ cation exchange reaction, or which displace cations prior to dissociation and form a co-precipitated product; part or all of the anions in the additive precursor A can be mixed with the active material B when dispersed in an aqueous system containing the active material Bn+The (n-1, 2,3) cation bond substitutes the cation before dissolution and dissociation to form a precipitated salt and/or complex.
Preferably, the mechanism of the spontaneous in situ electro-displacement reaction is: when the active substance B contacts with electrons in the powder mixing processAfter the conductive precursor A2 is subjected to thermodynamic spontaneous in-situ electric displacement reaction with the electronic conductive precursor A2, a corresponding metal simple substance with high hydrogen evolution overpotential is generated; in the process of the electric replacement reaction, the surface of the active material B can slowly release B while replacing the metal simple substance with high hydrogen evolution overpotentialn+A (n ═ 1,2,3) cation, which can further promote the ion exchange reaction in situ. Part of cations in the additive precursor A can generate thermodynamic spontaneous in-situ electro-displacement reaction when dispersed in a water system containing an active substance B to generate a conductive metal simple substance with high hydrogen evolution overpotential.
The invention has the beneficial effects that:
the prepared electrode with the ion and electron composite conduction function has an ion conduction path and an electron conduction network at the same time, and is used for a metal type cathode of an aqueous energy storage device (an aqueous ion battery and an aqueous super capacitor). The invention is based on the industrialized powder dispersion technology, creatively integrates in-situ ion exchange and spontaneous in-situ electric replacement reaction, effectively improves the dispersibility of each component, and cancels the fussy post-treatment process of the electrode slice.
Meanwhile, compared with the published patent, the invention also designs a three-dimensional conductive network constructed by zero-dimensional/one-dimensional/two-dimensional structural units in a targeted manner through the composite use of electronic conductive materials with different micro-morphologies. The material has low cost, simple and convenient method and easy large-scale expanded production, and is particularly suitable for preparing electrodes of water-system ion batteries and water-system super capacitors.
Compared with the traditional feeding-stirring method, the scheme for preparing the electrode powder mixture through the precursor in-situ reaction provided by the invention can ensure the uniformity of each component in the mixing process and prevent the target product from agglomerating in the feeding process. Meanwhile, the method for preparing the electrode powder mixture is not changed in a complex way and exceeds the requirement of large-scale production, so that the method has the characteristics of simplicity and convenience and amplification, and can be directly compatible with the existing industrialized technology.
Drawings
Fig. 1 is a schematic three-dimensional structure diagram of an ion and electron composite conducting electrode according to the present invention.
Description of reference numerals: a dot-shaped conductive material 101, a linear conductive material 102, a planar conductive material 103, and a current collecting base 104.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that, for a person skilled in the art, several modifications can be made to the invention without departing from the principle of the invention, and these modifications and modifications also fall within the protection scope of the claims of the present invention.
Example 1
First, 3kg of brass powder and 10kg of zirconia balls were added to an agate jar mill. Immediately thereafter, 1kg of a nano-hydroxyapatite suspension with a solids content of 50% was added. And placing the ball milling tank with the powder on a planetary ball mill for ball milling and dispersing for 1 hour. In the process, the metallic zinc component in the brass powder and water slowly generate hydrogen evolution reaction, and Zn is slowly released from the surface2+. Zn produced2+Substitute Ca2+And then, the compound is subjected to cation exchange with hydroxyapatite in situ in the vicinity of the surface of the metal zinc to form zinc-hydroxyapatite which is a compound having cation conductivity. Compared with the zinc-hydroxyapatite powder directly added, the zinc-hydroxyapatite powder generated by the method can be dispersed more uniformly, the step of ion exchange by soaking in a zinc-containing solution is omitted, and the working procedures and the cost are saved.
After the ball milling tank is cooled, 1.25kg of polyethylene oxide (20% of solid content) and polyvinyl alcohol (20% of solid content) solutions are respectively added, and ball milling and dispersion are continued for 15 minutes. Subsequently, 0.25kg of acetylene black, 0.15kg of carbon nanotubes, and 0.6kg of artificial graphite were sequentially added to the ball mill pot, and ball milling was performed for 15 minutes after each charge to sufficiently disperse the mixture.
The obtained slurry can be directly used in a coating process, and a current collector is copper foil. After coating, the coil was dried by passing through a circulating constant temperature air-blast oven at 80 degrees. And finally, rolling and cutting to obtain the pole piece with a proper size. The pole piece does not need any post-treatment process, and can be directly used for assembling a water system battery or a super capacitor.
Example 2
First, 3.5kg of zinc powder and 10kg of zirconia balls were added to an agate jar mill. Immediately thereafter, 1.5kg of a 30% strength sodium dihydrogen phosphate solution were added. And placing the ball milling tank with the powder on a pendulum vibration type ball mill for ball milling and dispersing for 1 hour. In the process, the zinc powder and water slowly generate hydrogen evolution reaction, and Zn is slowly released from the surface2+And releasing OH in situ-. Zn produced2+At OH-With the aid of (3), replace Na+And H2PO4 -Combining on the surface of the metal zinc to generate Zn in situ3(PO4)2Such a compound having ion conductivity. Zn produced in this way3(PO4)2Compared with the direct addition of Zn3(PO4)2The powder can be uniformly dispersed on a molecular scale.
After the ball milling tank is cooled, 1kg of sodium polyacrylate (15% of solid content) and polyvinylpyrrolidone (15% of solid content) solution are respectively added, and ball milling and dispersion are continued for 15 minutes. Subsequently, 0.1kg of ketjen black, 0.25kg of carbon fiber, and 0.4kg of natural graphite were sequentially added to the ball mill pot, and ball milling was performed for 15 minutes after each charge to sufficiently disperse the mixture. The obtained slurry can be directly used in a screen printing process, and the current collector is zinc foil.
After printing paste masses having an electrode shape with an appropriate thickness on the zinc foil, the material strip was dried by passing through a circulating constant temperature air-blowing oven at 80 ℃. And finally, rolling and cutting to obtain the pole piece with a proper size. The pole piece does not need any post-treatment process, and can be directly used for a water system battery or a super capacitor.
Example 3
First, 4kg of lead powder and 10kg of zirconia balls were added to an agate jar mill. Immediately thereafter, 2kg of a mixed solution of disodium hydrogenphosphate (solid content: 5%) and bismuth ammonium citrate (solid content: 5%) was further added.And placing the ball milling tank with the powder on a horizontal ball mill for ball milling and dispersing for 1 hour. In the process, lead powder and water slowly generate hydrogen evolution reaction to slowly release Pb from the surface2+And releasing OH in situ-. Produced Pb2+At OH-With the aid of (3), replace Na+With HPO4 2-Bonding on the surface of metallic lead to generate Pb in situ3(PO4)2Such a compound having ion conductivity. Meanwhile, lead can generate spontaneous in-situ electro-displacement reaction with bismuth ammonium citrate to generate Bi metal particles on the surface of lead and supplement Pb2+The concentration of the ions is favorable for the continuous occurrence of ion exchange. Compared with the direct addition of Pb3(PO4)2And Bi powder can be uniformly dispersed on a molecular scale.
After the ball milling tank is cooled, 0.3kg of water-soluble styrene-butadiene rubber emulsion (50% of solid content) and 1kg of carboxymethyl cellulose solution (15% of solid content) are respectively added, and ball milling and dispersion are continued for 15 minutes. Subsequently, 0.3kg of activated carbon, 0.18kg of carbon nanoribbons, and 0.2kg of graphene solution (10% solid content) were sequentially added to the ball mill pot, and ball milling was performed for 15 minutes after each charge to sufficiently disperse the mixture.
The obtained slurry can be directly used in a coating process, and the current collector is carbon cloth. After coating, the coil was dried by passing through a circulating constant temperature air-blast oven at 80 degrees. And finally, rolling and cutting to obtain the pole piece with a proper size. The pole piece does not need any post-treatment process, and can be directly used for assembling a water system battery or a super capacitor.
Example 4
First, 4kg of zinc powder and 0.5kg of tin powder were added to a stainless steel stirring tank. Immediately thereafter, 0.2kg of a nano-montmorillonite suspension having a solids content of 50% was added. The mixture was inserted into a double planetary mixer and dispersed for 1 hour under stirring. In the process, the zinc powder and water slowly generate hydrogen evolution reaction, and Zn is slowly released from the surface2+. Zn produced2+Substitute for Na+And Ca2+In-situ cation exchange with montmorillonite near the surface of metallic zinc to generate zinc-montmorillonite with cationAn ion-conductive compound. Compared with the method of directly adding zinc-montmorillonite powder, the zinc-montmorillonite generated by the method not only can be dispersed more uniformly, but also the step of carrying out ion exchange by soaking in a zinc-containing solution is omitted, and the working procedure and the cost are saved.
After the first-stage stirring, 0.5kg of sodium polyacrylate (15% solid content) and polyvinyl alcohol (15% solid content) solutions were added, and the ball milling dispersion was continued for 15 minutes. Subsequently, 0.5kg of a carbon quantum dot dispersion (10% solid content), 0.15kg of carbon nanotubes, and 0.5kg of an MXene solution (10% solid content) were sequentially added to the stirring tank.
The obtained slurry can be directly used in a slurry hanging procedure, and a current collector is foam copper. And after finishing the slurry coating, drying the material roll by a circulating constant-temperature air-blast oven at 80 ℃. And finally, rolling and cutting to obtain the pole piece with a proper size. The pole piece does not need any post-treatment process, and can be directly used for assembling a water system battery or a super capacitor.
Example 5
First, 3.5kg of zinc powder and 10kg of zirconia balls were added to an agate jar mill. Immediately thereafter, 0.6kg of a mixed solution of 2-methylimidazole (20% in terms of solid content) and tin chloride (5% in terms of solid content) was further added. And placing the ball milling tank with the powder on a planetary ball mill for ball milling and dispersing for 1 hour. In the process, the zinc powder and water slowly generate hydrogen evolution reaction, and Zn is slowly released from the surface2+. Zn produced2+Forming coordination compounds with 2-methylimidazole organic ligands, i.e. Zn (2-MI)2Also known as ZIF-8, a compound having ion transport channels. Meanwhile, the zinc and tin chloride can generate spontaneous in-situ electro-displacement reaction to generate Sn metal particles on the surface of the zinc and supplement Zn2+The concentration of the ions is favorable for the continuous occurrence of ion exchange. Compared with the method of directly adding ZIF-8 and Sn powder, the method can realize uniform dispersion on a molecular scale.
After the ball milling tank is cooled, 1kg of polyethylene oxide (20% of solid content) and polyvinylpyrrolidone (15% of solid content) solutions are added respectively, and ball milling and dispersion are continued for 15 minutes. Subsequently, 0.2kg of acetylene black, 0.3kg of carbon fibers, and 0.5kg of artificial graphite were sequentially added to the ball mill pot, and ball milling was performed for 15 minutes after each charge to sufficiently disperse the mixture. The obtained slurry can be directly used for a silk-screen printing process, and the current collector is graphite paper. After printing a paste mass having an electrode shape with an appropriate thickness on graphite paper, the material tape was dried by passing through a circulating constant temperature air-blowing oven at 80 ℃.
And finally, rolling and cutting to obtain the pole piece with a proper size. The pole piece does not need any post-treatment process, and can be directly used for assembling a water system battery or a super capacitor.
With reference to the above examples 1 to 5, the present invention relates to a composite electrode having ion conductive paths and electron conductive networks, which has the potential for mass production as shown in fig. 1. Compared with the prior art, the method has the advantages that on the basis of being compatible with the existing large-scale production method, in-situ ion exchange and optional spontaneous in-situ electric replacement reaction are innovatively introduced, and the reducibility characteristic of electrode active substances is utilized, so that the precursor of the ion/electron conductive material and the active substances are subjected to uniform reaction and compounding in the preparation process. Meanwhile, the invention also defines the comprehensive use of the point-line-surface conductive framework, and is beneficial to the formation of a three-dimensional conductive network in the electrode plate.
Claims (10)
1. An electrode that conducts by combining ions and electrons, comprising: a point-like conductive material (101), a linear conductive material (102), a planar conductive material (103), and a current collecting base material (104); the point-shaped conductive material (101), the linear conductive material (102) and the planar conductive material (103) are all attached to the current collecting base material (104); the three-dimensional porous framework is constructed by the dot-shaped conductive material (101), the linear conductive material (102) and the planar conductive material (103).
2. The electrode of claim 1, wherein the ion and electron recombination conduction electrode comprises: the point-shaped conductive material (101) is a point-shaped electronic conductive material or a point-shaped ion-electron composite conductive material, the linear conductive material (102) is a linear electronic conductive material or a linear ion-electron composite conductive material, and the planar conductive material (103) is a planar electronic conductive material or a planar ion-electron composite conductive material.
3. An in-situ preparation method of an electrode in ionic and electronic recombination conduction according to claim 1 or 2, characterized by comprising the following steps:
step 1, adding an additive precursor A and an active substance B into a mixing device, mixing for a set time, stirring a mixture of the additive precursor A and the active substance B in the mixing device by a stirring device while mixing, and carrying out in-situ ion exchange on the additive precursor A and the active substance B in the stirring process and uniformly dispersing;
step 2, after the mixing device in the step 1 is cooled, adding a dispersing binder C into the mixture obtained in the step 1, continuously mixing and stirring for a set time, and then adding a conductive network D into the mixing device; under the action of the dispersing binder C, performing secondary uniform dispersion on the conductive network D and the uniformly dispersed product in the step 1 to obtain a powder mixture directly used for preparing an electrode;
step 3, transferring the powder mixture prepared in the step 2 to a afflux substrate, and heating and drying; and rolling and cutting the afflux substrate with the powder mixture to obtain the pole piece with the set size.
4. The in-situ preparation method of the ion and electron combined conducting electrode according to claim 3, characterized in that: the mass ratio of the additive precursor A, the active substance B, the dispersing binder C and the conductive network D added in the step 1 and the step 2 is (1-10): 60-90): 1-10): 5-20); in the step 1, spontaneous in-situ electric replacement reaction also occurs in the stirring process of the additive precursor A and the active substance B.
5. The in-situ preparation method of the ion and electron combined conducting electrode according to claim 3, characterized in that: in the step 1, an additive precursor A is an ionic conduction precursor A1, an ionic conduction precursor A1 is at least one of metal phosphate, metal hydrogen phosphate, metal fluoride, an organic ligand of a metal organic framework compound and silicate, and an ionic conduction precursor A1 is powder with the particle size of less than 100 micrometers, or is 0.01-50% of aqueous solution or dispersion liquid; the particle size of the active substance B is less than 100 microns, and the active substance B is at least one of metal simple substances such as magnesium, aluminum, zinc, tin and lead and alloys of the metal simple substances; the dispersing binder C is at least one of polytetrafluoroethylene, polyvinylidene fluoride, cellulose and functional group modifier thereof, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, sodium polyacrylate and water-soluble rubber.
6. The in-situ preparation method of the ion and electron combined conducting electrode according to claim 3, characterized in that: in the step 1, the additive precursor A is an ionic conduction type precursor A1 and an electronic conduction type precursor A2; the ion conductive precursor a1 is at least one of hydroxyapatite, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, diammonium hydrogen phosphate, lithium fluoride, sodium fluoride, potassium fluoride, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-imidazolecarboxaldehyde, benzimidazole, montmorillonite, zircon, hydrotalcite, zeolite, kaolin, and clay; the electron-conductive precursor a2 is at least one of indium nitrate, indium acetate, indium sulfate, indium fluoride, indium chloride, indium bromide, indium iodide, indium trifluoromethanesulfonate, tin nitrate, tin acetate, tin sulfate, tin fluoride, tin chloride, tin bromide, tin iodide, tin trifluoromethanesulfonate, bismuth nitrate, bismuth acetate, bismuth fluoride, bismuth chloride, bismuth bromide, bismuth iodide, bismuth trifluoromethanesulfonate, and bismuth ammonium citrate; the electron-conductive precursor A2 is a metal salt that suppresses the hydrogen evolution reaction of the active material B in the electrode, and is a 0.01 to 50% aqueous solution.
7. The in-situ preparation method of the ion and electron combined conducting electrode according to claim 3, characterized in that: in the step 2, the conductive network D is a three-dimensional porous skeleton which is constructed by taking point materials, line materials and surface materials as structural units, and the three-dimensional porous skeleton is composed of at least one of carbon and carbide materials; the dot material is at least one of acetylene black, Ketjen black, active carbon and carbon quantum dots; the line material is at least one of carbon nano tube, carbon fiber and carbon nano belt; the surface material is at least one of natural graphite, artificial graphite, graphene, graphite alkyne and MXene material.
8. The in-situ preparation method of the ion and electron combined conducting electrode according to claim 3, characterized in that: the active material B is at least one of zinc, lead, zinc alloy and lead alloy.
9. The in-situ preparation method of the ion and electron combined conducting electrode according to claim 3, characterized in that: the mixing device in the step 1 comprises a planetary ball milling device, a shimmy ball milling device and a horizontal ball milling device; the stirring device is a double-planet stirring device; 3, transferring the powder mixture prepared in the step 2 to a afflux substrate in a single-sided coating, double-sided coating, slurry coating, screen printing or tabletting mode; the current collecting base material is a thin conductive material with the thickness of 5-100 micrometers, and comprises a carbon base material and a metal base material; the carbon substrate is graphite paper or carbon cloth, and the metal substrate is stainless steel foil, titanium foil, copper foil, nickel foil, zinc foil, stainless steel mesh, titanium mesh, copper mesh, nickel mesh, zinc mesh, copper foam, nickel foam or zinc foam.
10. A method of using an electrode prepared by the in situ preparation method according to any one of claims 3 to 9, wherein: the electrode which is conducted by combining ions and electrons is used as a metal type cathode in an aqueous energy storage device; the water-based energy storage device is a water-based ion battery or a water-based super capacitor.
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