CN114094210A - Three-dimensional positive electrode and aqueous zinc-manganese battery - Google Patents
Three-dimensional positive electrode and aqueous zinc-manganese battery Download PDFInfo
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- CN114094210A CN114094210A CN202111217221.0A CN202111217221A CN114094210A CN 114094210 A CN114094210 A CN 114094210A CN 202111217221 A CN202111217221 A CN 202111217221A CN 114094210 A CN114094210 A CN 114094210A
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- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 51
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000013543 active substance Substances 0.000 claims abstract description 24
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- 150000002500 ions Chemical class 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
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- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
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- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 claims description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 238000007599 discharging Methods 0.000 abstract description 10
- 238000007600 charging Methods 0.000 abstract description 6
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- 239000010410 layer Substances 0.000 description 49
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
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Images
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a three-dimensional structure anode and a water system zinc-manganese battery, wherein the three-dimensional structure anode comprises: the active material layer is formed on the first positive current collector; the composite resin layer is arranged on the active substance layer, wherein the active substance layer is a carbon fiber deposition layer loaded with manganese dioxide or an electrode pole piece containing manganese oxide. Therefore, the three-dimensional structure positive electrode has less positive electrode active substance dissolution in the charging and discharging processes, can adsorb partial protons, reduces negative electrode hydrogen evolution, and can improve the stability, cycle life and safety of the water-based zinc-manganese battery by applying the three-dimensional structure positive electrode to the water-based zinc-manganese battery.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a three-dimensional structure positive electrode and a water system zinc-manganese battery.
Background
Manganese-based (e.g. LiMn) 2 O 4 、MnO 2 ) With zinc or zinc alloy as negative electrodeThe batteries mostly adopt an aqueous electrolyte, namely H 2 O is used as a solvent, and a metal salt electrolyte is added. The water system electrolyte has the advantages of no toxicity, no harm, no combustibility, low cost, low requirement on production environment and the like. However, in an aqueous solution system, the positive electrode active material is gradually dissolved in the electrolyte during the charging and discharging processes, and the structure is damaged, so that a series of influences are caused on the stability of the battery; the cathode has severe corrosion and hydrogen evolution reaction, which reduces the stability of the battery.
Therefore, the conventional aqueous battery is in need of improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a three-dimensional positive electrode and an aqueous zinc-manganese battery, in which a positive electrode active material is less dissolved during charge and discharge, and a part of protons are adsorbed to reduce negative electrode hydrogen evolution, and which can improve stability, cycle life, and safety of the aqueous zinc-manganese battery when applied to the aqueous zinc-manganese battery.
In one aspect of the invention, a three-dimensional structure anode is provided. According to an embodiment of the present invention, the three-dimensional structure positive electrode includes:
a first positive current collector;
an active material layer formed on the first positive electrode current collector;
a composite resin layer provided on the active material layer,
the active substance layer is a carbon fiber deposition layer loaded with manganese dioxide or an electrode pole piece containing manganese oxide.
According to the three-dimensional structure anode provided by the embodiment of the invention, the active substance layer is formed on the first anode current collector, the active substance layer is a carbon fiber deposition layer loaded with manganese dioxide or an electrode pole piece containing manganese oxide, and then the composite resin layer is arranged on the active substance layer, wherein the three-dimensional carbon fiber framework or the electrode pole piece can provide an effective conductive framework structure, the integral conductivity in the anode is improved, the utilization rate of active substances is improved, a good deposition template and more sites are provided for the dissolution and deposition of manganese ions, the generation of deposition hardened substances is effectively slowed down, the utilization efficiency of the active substances is improved, the cycle life of the active substances is prolonged, the capacity attenuation in the cycle process is delayed or prevented to a certain extent, in addition, the composite resin layer formed on the active substance layer can form a buffer layer, the manganese ions and protons dissolved out from the active substance layer in the charge-discharge process are absorbed, the electric performance is improved, and the occurrence of a hydrogen evolution reaction of a negative electrode can be reduced. Therefore, the three-dimensional structure positive electrode has less positive electrode active substance dissolved in the charging and discharging process, can adsorb partial protons, reduces negative electrode hydrogen evolution, and can improve the stability, cycle life and safety of the water-based zinc-manganese battery when being applied to the water-based zinc-manganese battery.
In addition, the three-dimensional structure positive electrode according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the deposited layer of carbon fiber carrying manganese dioxide is obtained by electrodeposition, and the manganese dioxide is electrolytic manganese dioxide.
In some embodiments of the invention, a method of making the manganese oxide electrode sheet comprises: (1) Mixing manganese oxide, a conductive agent, a binder and a solvent to obtain slurry; (2) And attaching the slurry to a second positive current collector to obtain the manganese oxide electrode pole piece. Therefore, the whole conductivity in the positive electrode can be improved, the utilization rate of active substances is improved, a good deposition template and more sites are provided for the dissolution and deposition of manganese ions, and the generation of deposition hardening substances is effectively slowed down.
In some embodiments of the present invention, in the step (1), the mass ratio of the manganese oxide, the conductive agent and the binder is (60-80): (20-5): (20-15). Thereby, formation of a uniform slurry is facilitated.
In some embodiments of the invention, the slurry has a solids content of 40 to 60wt%. Thereby, formation of a uniform slurry is facilitated.
In some embodiments of the invention, in step (1), the manganese oxide comprises at least one of manganous oxide, manganese dioxide, manganomanganic oxide and lithium manganate.
In some embodiments of the present invention, the conductive agent includes at least one of a graphite-based conductive agent and a carbon black-based conductive agent.
In some embodiments of the invention, the adhesive comprises at least one of styrene butadiene rubber, sodium carboxymethyl cellulose, and an acrylate polymer.
In some embodiments of the present invention, the composite resin layer includes a carbon fiber skeleton and a resin supported on the carbon fiber skeleton. Therefore, a buffer layer can be formed to absorb manganese ions and protons dissolved out in the charge and discharge processes of the active material layer, so that the electric property is improved, and the occurrence of hydrogen evolution reaction of the negative electrode can be reduced.
In some embodiments of the invention, the resin comprises at least one of a sodium-type resin, a hydrogen-type resin, a zinc-type resin, and a manganese-type resin. This effectively inhibits the dissolution of ions in the positive electrode active material, and adsorbs a part of protons, thereby reducing hydrogen evolution in the negative electrode.
In a second aspect of the invention, an aqueous zinc-manganese battery is provided. According to an embodiment of the invention, the water-based zinc-manganese battery comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm, wherein the positive electrode adopts the three-dimensional structure positive electrode. This improves the stability, cycle life, and safety of the aqueous zinc-manganese battery.
In addition, the water-based zinc-manganese dioxide battery according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the invention, the separator comprises at least one of a glass fiber separator, a PP separator, a dust free paper separator, and a cellulose separator.
In some embodiments of the invention, the negative electrode comprises at least one of zinc and an alloy of zinc.
In some embodiments of the present invention, the electrolyte is a mixed aqueous solution of zinc sulfate and manganese sulfate.
In some embodiments of the invention, the ionic concentration of the mixed aqueous solution is 0.1 to 5mol/L.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic structural view of a three-dimensional structure positive electrode according to an embodiment of the present invention;
FIG. 2 is a schematic flow diagram of a method of making a manganese oxide electrode sheet according to one embodiment of the present invention;
FIG. 3 is a schematic diagram of the structure of an aqueous zinc-manganese battery according to one embodiment of the invention;
FIG. 4 is a graph of the electrical properties of the aqueous zinc-manganese battery of example 1;
fig. 5 is a graph of the electrical properties of the aqueous zinc-manganese battery of example 2.
Detailed Description
The embodiments described below with reference to the accompanying drawings are illustrative and intended to explain the present invention and should not be construed as limiting the present invention.
In one aspect of the invention, a three-dimensional structure anode is provided. According to an embodiment of the present invention, referring to fig. 1, the three-dimensional structure positive electrode includes: a first positive electrode collector 101, an active material layer 102, and a composite resin layer 103.
According to an embodiment of the present invention, referring to fig. 1, the first positive electrode collector 101 is a positive electrode collector conventionally used in the field of batteries, for example, the first positive electrode collector 101 may employ a carbon material such as graphite foil, conductive PE, or stainless steel, titanium foil, etc.
According to an embodiment of the present invention, the active material layer 102 is formed on the first positive electrode collector 101, and the active material layer 102 is a carbon fiber deposited layer supporting manganese dioxide or a manganese oxide-containing electrode sheet. The inventor finds that a three-dimensional carbon fiber framework or an electrode pole piece is used as a framework in the active material layer 102, and can provide an effective conductive framework structure, improve the overall conductivity in the positive electrode and improve the utilization rate of the active material, provide a good deposition template and more sites for the dissolution and deposition of manganese ions in the active material of the positive electrode, effectively slow down the generation of a deposition hardening substance, improve the utilization rate of the active material, prolong the cycle life of the active material, and delay or prevent the capacity attenuation in the cycle process to a certain extent. Specifically, the active material layer 102 may be formed on the first positive current collector 101 through an adhesive layer, and a person skilled in the art may select a specific composition of the adhesive layer according to actual needs as long as the above functions can be achieved, and details are not described herein.
Further, the carbon fiber deposition layer carrying manganese dioxide is obtained by adopting an electrodeposition mode, and the manganese dioxide is electrolytic manganese dioxide. It should be noted that the technology for obtaining the deposited layer of carbon fiber loaded with manganese dioxide by electrodeposition is a conventional technology in the art, and is not described herein again.
Further, referring to fig. 2, the method for preparing the manganese oxide electrode sheet includes:
s100: mixing manganese oxide, conductive agent, adhesive and solvent
In the step, manganese oxide, a conductive agent, a binder and a solvent are mixed and uniformly mixed to obtain slurry. Furthermore, the mass ratio of the manganese oxide to the conductive agent to the binder is (60-80) to (20-5) to (20-15). The inventor finds that if the addition amount of the manganese oxide is too low, the capacity of the battery is influenced, so that the energy density of the battery is reduced, and if the addition amount of the manganese oxide is too high, the conductivity is insufficient, the internal resistance of an electrode plate is increased, and the performance of the gram capacity of a material is not facilitated; if the addition amount of the conductive agent is too high, the content of active substances can be reduced, the energy density of the battery is influenced, and if the addition amount of the conductive agent is too low, the conductivity of the electrode plate is insufficient, and the gram capacity exertion of the material is influenced; if the binder addition amount is too high, the content of the active material is reduced, which affects the energy density of the battery, and if the binder addition amount is too low, the adhesion between the particles of the positive electrode material and between the positive electrode material and the conductive agent is reduced, which is not favorable for the exertion of the electrical properties of the material.
Further, the solid content of the slurry is 40-60 wt%. The inventor finds that if the solid content of the slurry is too low, the slurry after homogenizing is too sparse, which is not beneficial to the coating process of the electrode plate, and if the solid content of the slurry is too high, which is not beneficial to the uniform dispersion of the anode material and the conductive agent, which influences the electrical performance of the electrode plate.
It should be noted that the specific types of the above-mentioned manganese oxide, conductive agent, binder and solvent are not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the manganese oxide includes but is not limited to at least one of manganous oxide, manganese dioxide, manganous oxide and lithium manganate; the conductive agent includes, but is not limited to, at least one of a graphite-based conductive agent and a carbon black-based conductive agent; the adhesive includes but is not limited to at least one of styrene-butadiene rubber, sodium carboxymethyl cellulose and acrylate polymer; the solvent is deionized water.
S200: attaching the slurry to a second positive current collector
In the step, the slurry is attached to a second positive current collector and then dried, so that the manganese oxide electrode plate can be obtained. It should be noted that the specific method for attaching the slurry to the second positive electrode collector is not particularly limited as long as the above function is achieved, for example, the slurry is attached to the second positive electrode collector by coating or slurry drawing. And the second positive current collector is a positive current collector conventionally used in the battery field, for example, the second positive current collector is a graphite foil.
According to an embodiment of the present invention, referring to fig. 1, a composite resin layer 103 is provided on an active material layer 102. The inventors have found that by forming the composite resin layer 103 on the active material layer 102, the composite resin layer 103 can form a buffer layer, and absorb manganese ions and protons eluted from the active material layer 102 during charge and discharge, thereby improving electrical characteristics and reducing the occurrence of hydrogen evolution reaction in the negative electrode.
Further, the composite resin layer 103 includes a carbon fiber skeleton and a resin, wherein the resin is supported on the carbon fiber skeleton. Specifically, the formed composite resin layer can absorb manganese ions and protons dissolved out in the charging and discharging process through the resin serving as a buffer layer, can increase the deposition sites of the manganese ions through the carbon fiber framework, prevents the generation of a 'plate junction layer' on the surface of the electrode plate, which is not beneficial to the electrical performance, and simultaneously enhances the mechanical property of the electrode plate, and prevents the electrode plate from being damaged due to the volume swelling of the electrode plate caused by the charging and discharging process. It should be noted that the specific type of the above resin is not particularly limited, and the person skilled in the art can select the resin according to actual needs, for example, the resin includes at least one of a sodium type resin, a hydrogen type resin, a zinc type resin, and a manganese type resin.
Therefore, the three-dimensional structure anode has less anode active substance dissolved in the charging and discharging process, and can adsorb partial protons, so that the hydrogen evolution of the cathode is reduced, and the stability, the cycle life and the safety of the water system zinc-manganese battery can be improved by applying the three-dimensional structure anode to the water system zinc-manganese battery.
In a second aspect of the invention, an aqueous zinc-manganese battery is provided. According to an embodiment of the present invention, referring to fig. 3, the water-based zinc-manganese battery includes a positive electrode 100, a negative electrode 300, an electrolyte 400, and a separator 200, wherein the positive electrode adopts the above-described three-dimensional structure. This improves the stability, cycle life, and safety of the aqueous zinc-manganese battery.
The specific types of the negative electrode 300 and the separator 200 of the water-based zinc-manganese battery may be selected by those skilled in the art according to actual needs, for example, the separator 200 includes at least one of a glass fiber separator, a PP separator, a dust-free paper separator, and a cellulose separator; the negative electrode 300 includes at least one of zinc and an alloy of zinc.
Further, the electrolyte 400 is a mixed aqueous solution of zinc sulfate and manganese sulfate, and the ion concentration of the mixed aqueous solution is 0.1 to 5mol/L. The inventors have found that when the ion concentration of the mixed aqueous solution is too low, the ion conductivity is lowered, and the performance of the electrical properties of the positive electrode material is impaired, and when the ion concentration of the mixed aqueous solution is too high, the electrolyte is likely to be deposited during the cycle, and the performance of the battery is impaired, and the total mass of the battery is increased, and the energy density of the battery is lowered.
It should be noted that the features and advantages described above for the three-dimensional positive electrode are also applicable to the aqueous zinc-manganese battery, and will not be described herein again.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way. The examples do not specify particular techniques or conditions, and are performed according to techniques or conditions described in literature in the art or according to the product specification. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Electrolytic manganese dioxide is loaded on a carbon fiber framework in an electrodeposition mode to serve as an active substance layer, hydrogen type cation exchange resin is dispersed in the middle of the carbon fiber framework to serve as a composite resin layer, the active substance layer is formed on a positive electrode current collector (graphite foil), the composite resin layer is formed on the active substance layer to form a three-dimensional structure positive electrode, a pole piece made of zinc alloy powder through slurry drawing on a copper mesh serves as a negative electrode, the membrane is a glass fiber membrane, and electrolyte is 0.5 mol.L -1 Zinc sulfate and 0.5 mol. L -1 A mixed aqueous solution of manganese sulfate.
And assembling the battery, and carrying out electrochemical performance test. The test conditions were: constant current charging and discharging, voltage range of 1.0-1.9V, and current density of 50mA/g. Test data results: the gram capacity is maximally exerted to 250mAh/g, the capacity tends to be in a stable stage after the first 5 circles are reduced, the capacity can be stabilized to about 160mAh/g in the later period, the attenuation basically does not occur after 100 circles of circulation, and the average coulombic efficiency is 98.21%. The electrical performance data of the cells are shown in figure 4.
Example 2
Mixing manganese dioxide, a conductive agent and an adhesive according to a mass ratio of 8. Coating the slurry on a positive current collector (graphite foil), drying to obtain a manganese dioxide electrode plate serving as an active substance layer, forming the active substance layer on a first positive current collector (graphite foil), wherein the copper foil in the active substance layer is in contact with the first positive current collector, and then forming a composite resin layer on the active substance layer, wherein the composite resin layer is formed by uniformly dispersing hydrogen type cation exchange resin in the middle of a carbon fiber framework, so that the positive electrode with a three-dimensional structure is prepared. A pole piece made of zinc alloy powder on a copper mesh by slurry drawing is used as a negative electrode, the diaphragm is a glass fiber diaphragm, and the electrolyte is 1.8 mol.L -1 Zinc sulfate and 0.2 mol. L -1 A mixed aqueous solution of manganese sulfate.
And assembling the battery, and carrying out electrochemical performance test. The test conditions were: constant current charging and discharging, voltage range of 1.0-1.9V, and current density of 50mA/g. Analyzing the test data result: the gram capacity can be maximally exerted to 200mAh/g, the gram capacity does not have large fluctuation in the circulation process, the circulation stability is good, the circulation can be stably carried out to 160 circles, the capacity retention rate is 84%, and the average coulombic efficiency is 99.59%. The electrical performance data of the cells are shown in figure 5.
Comparative example 1
The procedure of example 2 was repeated except that the hydrogen type cation exchange resin was replaced with an epoxy resin.
And assembling the battery, and carrying out electrochemical performance test. The test conditions were: constant current charging and discharging, voltage range of 1.0-1.9V, and current density of 50mA/g. Analyzing the test data result: the gram capacity is maximally exerted to 205mAh/g, the gram capacity does not have large fluctuation in the circulation process, the circulation stability is good, the gram capacity can be stably circulated to 65 circles, the capacity retention rate is 80%, and the average coulombic efficiency is 98.6%.
Comparative example 2
The process was the same as in example 2 except that no carbon fiber skeleton was used.
And assembling the battery, and carrying out electrochemical performance test. The test conditions were: constant current charging and discharging, voltage range of 1.0-1.9V, and current density of 50mA/g. Analyzing the test data result: the gram capacity is maximally exerted to 185mAh/g, the gram capacity does not have large fluctuation in the circulation process, the circulation stability is good, the circulation can be stably carried out to 60 circles, the capacity retention rate is 81.5%, and the average coulombic efficiency is 98.4%.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A three-dimensional structure positive electrode, characterized by comprising:
a first positive current collector;
an active material layer formed on the first positive electrode current collector;
a composite resin layer provided on the active material layer,
the active substance layer is a carbon fiber deposition layer loaded with manganese dioxide or an electrode pole piece containing manganese oxide.
2. The three-dimensional structure positive electrode according to claim 1, wherein the carbon fiber deposition layer supporting manganese dioxide is obtained by electrodeposition, and the manganese dioxide is electrolytic manganese dioxide.
3. The three-dimensional structure positive electrode according to claim 1, wherein the method for preparing the manganese oxide electrode sheet comprises:
(1) Mixing manganese oxide, a conductive agent, a binder and a solvent to obtain slurry;
(2) And attaching the slurry to a second positive current collector to obtain the manganese oxide electrode pole piece.
4. The three-dimensional structure positive electrode according to claim 3, wherein in the step (1), the mass ratio of the manganese oxide, the conductive agent and the binder is (60-80): (20-5): (20-15);
optionally, the slurry has a solids content of 40 to 60wt%.
5. The three-dimensional structure positive electrode according to claim 3, wherein, in the step (1), the manganese oxide comprises at least one of manganous oxide, manganese dioxide, manganous manganic oxide, and lithium manganate;
optionally, the conductive agent includes at least one of a graphite-based conductive agent and a carbon black-based conductive agent;
optionally, the adhesive comprises at least one of styrene butadiene rubber, sodium carboxymethyl cellulose, and an acrylate polymer.
6. The three-dimensional structure positive electrode according to claim 1, wherein the composite resin layer comprises a carbon fiber skeleton and a resin, the resin being supported on the carbon fiber skeleton;
optionally, the resin includes at least one of a sodium-type resin, a hydrogen-type resin, a zinc-type resin, and a manganese-type resin.
7. An aqueous zinc-manganese dioxide battery comprising a positive electrode, a negative electrode, an electrolyte and a separator, wherein the positive electrode has the three-dimensional structure according to any one of claims 1 to 6.
8. The aqueous zinc-manganese dioxide cell of claim 7, wherein the separator comprises at least one of a glass fiber separator, a PP separator, a dust-free paper separator, and a cellulose separator.
9. The aqueous zinc-manganese battery of claim 7, wherein the negative electrode includes at least one of zinc and an alloy of zinc.
10. The aqueous zinc-manganese battery of claim 7, wherein the electrolyte is a mixed aqueous solution of zinc sulfate and manganese sulfate;
optionally, the ion concentration of the mixed aqueous solution is 0.1-5 mol/L.
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| CN118486803A (en) * | 2024-05-08 | 2024-08-13 | 苏州市易予新能源科技有限公司 | Water-based zinc ion battery positive electrode material and preparation method thereof |
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