CN114520302B - Aqueous metal battery and modified anode thereof - Google Patents

Aqueous metal battery and modified anode thereof Download PDF

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Publication number
CN114520302B
CN114520302B CN202210117340.7A CN202210117340A CN114520302B CN 114520302 B CN114520302 B CN 114520302B CN 202210117340 A CN202210117340 A CN 202210117340A CN 114520302 B CN114520302 B CN 114520302B
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zinc
ion
metal
ions
electrode
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CN114520302A (en
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吴川
赵然
白莹
吴锋
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Abstract

The modified cathode is used for the water-based metal battery. The preparation method of the negative electrode comprises the steps of carrying out hydrothermal crystallization on a mixed aqueous solution formed by silicon ions, aluminum ions and sodium hydroxide, carrying out ion exchange on a crystallized product and a zinc ion solution for a plurality of times, and then forming a coating agent together with a binder and a solvent to coat the exchange product on a zinc foil to form the modified negative electrode. According to the invention, the ion channel is finely regulated and controlled from the atomic size level, and the contact between a large-diameter group and a metal negative electrode is inhibited, so that the occurrence of side reaction on the surface of the electrode is reduced, and the uniform deposition of metal ions is guided. The activity of water molecules directly contacted with the surface of the metal foil is reduced through coordination with polyvalent metal ions, so that the corrosion resistance of the electrode is enhanced; reducing the polarization voltage by application of a negatively charged modified species layer; meanwhile, deposition of metal is uniform through a tunnel guiding mechanism, growth of dendrites is restrained, and long-term stable circulation of the metal electrode is realized.

Description

Aqueous metal battery and modified anode thereof
Technical Field
The present invention relates generally to aqueous metal batteries, and more particularly to modified cathodes for such batteries.
Background
In order to solve the important problems of dependence on fossil energy, ecological environment crisis, climate change and the like, which are currently and generally focused internationally, the requirements for clean renewable energy sources such as wind energy, solar energy, tidal energy, geothermal energy and the like are increasingly high, and an electrochemical energy storage system is an important link for storing and utilizing the new energy sources due to the instability of the energy sources. The lithium ion battery is used as the most advanced secondary battery system at present, plays a non-negligible role in daily life of people, such as portable electronic equipment and new energy power battery automobiles, and provides a short-term solution for large-scale renewable energy storage. However, because flammable organic electrolyte is used, the lithium ion battery has poor safety performance and has the danger of combustion explosion; the distribution of the required elements for producing lithium ion batteries, such as lithium, nickel, cobalt and the like, is relatively concentrated, and potential supply risks exist. In view of the above, it is not surprising to find battery systems that are safe, more stable in supply, high in energy density, environmentally compatible and low in cost.
Multivalent metal ion batteries are considered to be the most potential alternatives to lithium batteries, such as zinc ion batteries and aluminum ion batteries, which have divalent zinc ions or trivalent aluminum ions as charge carriers, with the potential to provide twice or three times the amount of charge as compared to lithium ions. Meanwhile, the flammable organic electrolyte is replaced by the aqueous electrolyte, so that the safety problem of the battery can be solved, and the production cost of the battery is greatly reduced. The zinc and aluminum metals also have stable ionic valence, low price, small radius, lower reduction voltage and higher theoretical mass specific capacity (Zn: 825mAh g) -1 ,Al:2 980mAh g -1 ) And the like, does not react with water like lithium metal, sodium and the like, and has potential to be directly applied to water-based batteries. However, the problems of zinc metal, aluminum metal and the like still exist in the use process, which are not neglected: when zinc is deposited on the surface of a zinc anode, flaky disordered accumulation is formed on the surface of an electrode, and continuous growth breaks through a diaphragm and causes short circuit between electrodes, so that the short circuit of a battery is invalid; the electrode surface is easy to generate hydrogen evolution reaction under the influence of working conditions, so that the coulomb efficiency of the battery is reduced and electrolyte leakage is caused; the local hydroxyl concentration rise caused by hydrogen evolution reaction is easy to react with metal and other ions existing in the electrolyte, and a passivation film is formed on the surface of the electrode to reduce the cycle performance of the battery. There is also a problem of surface hydrogen evolution and passivation of the electrode surface in aluminum metal anodes.
In order to solve these problems of the metal negative electrode, optimization is currently mainly performed from four aspects of SEI film, electrode body structure, electrolyte and diaphragm: firstly, constructing a multifunctional artificial protection layer, and inhibiting side reaction and dendrite growth; secondly, optimizing the structural composition of the metal electrode body; thirdly, using a water-in-salt electrolyte to inhibit hydrogen evolution reaction; and fourthly, constructing a functional diaphragm for inducing uniform deposition of ions. The method inhibits side reactions to a certain extent, but is limited in the application process, such as complex process for optimizing the structural composition of the metal electrode body, the salt-covered water electrolyte is sensitive to temperature change, and the functional diaphragm cannot inhibit hydrogen evolution reaction.
Disclosure of Invention
It is an object of the present invention to provide a modified negative electrode for aqueous metal batteries, in particular zinc ion batteries, which overcomes at least some of the above-mentioned drawbacks.
According to a first aspect of the present invention, there is provided a method for preparing a negative electrode of a zinc ion battery, comprising:
providing a zinc foil;
providing a silicon ion source selected from at least one of the group consisting of silica gel, water glass, sodium silicate and ethyl orthosilicate;
providing an aluminum ion source selected from at least one of the group consisting of aluminum sulfate hydrate and sodium metaaluminate;
forming a mixed aqueous solution by a silicon ion source, an aluminum ion source and sodium hydroxide, wherein the molar ratio of silicon ions, sodium ions and water molecules to aluminum ions is 1.5-1, 5-3 and 90-80 respectively;
controlling the temperature of the mixed aqueous solution to be between 25 and 90 ℃ for hydrothermal crystallization for at least 5 hours;
centrifuging to separate out crystallized products;
drying the crystallized product, adding the dried product into zinc ion water solutions with different concentrations, sequentially carrying out ion exchange, wherein the mass ratio of the zinc ion molar quantity to the dried product is between 0.01mol/g and 1mol/g, sequentially carrying out ion exchange according to the concentration of the zinc ion water solution from low to high, and carrying out centrifugal drying treatment after each ion exchange;
mixing the dried product obtained after the last ion exchange with a binder and a solvent to obtain a coating agent;
the obtained coating agent is uniformly coated on zinc foil to form a coating, wherein the thickness of the coating is 5-75 mu m after the solvent volatilizes.
The method according to the invention, wherein at least 3 different concentrations of zinc ion aqueous solutions are used for the ion exchange, for example 0.01mol/g, 0.05mol/g, 0.1mol/g, 0.2mol/g, 0.5mol/g and 1mol/g of zinc ion aqueous solution, respectively.
The process according to the invention, wherein the mass ratio of the dry product obtained to the binder is preferably between 20:1 to 7: 1.
According to the method of the present invention, wherein the binder may be at least one selected from the group consisting of polyvinylidene fluoride (PVDF), polyethylene oxide (PEO) and carboxymethyl cellulose (CMC). When PVDF or PEO is used as the binder, NMP may be used as a solvent for forming the coating agent, and water may be used as a solvent when CMC is used as the binder.
According to the method of the present invention, sodium silicate is preferably used as the silicon ion source. In addition, sodium metaaluminate may be preferably used as the aluminum ion source.
According to the method of the invention, vacuum or non-vacuum drying can be adopted when each drying treatment is carried out, and the temperature can be set to be 50-200 ℃, preferably 60-80 ℃; the drying time may be 2 to 48 hours, preferably 12 to 24 hours.
According to the method of the invention, the binder can be coated on the surface of the cathode or zinc foil in a controlled thickness by a suitable manner such as knife coating, spin coating, spray coating and the like.
As an alternative embodiment of the present invention, an aluminum foil may be used instead of zinc foil to prepare a negative electrode for an aluminum battery.
According to another aspect of the present invention, there is provided a negative electrode of a zinc-ion battery, which is prepared by the above method.
According to still another aspect of the present invention, there is provided an aqueous zinc ion battery including the above-described negative electrode.
The battery according to the invention, wherein the electrolyte salt is preferably zinc sulfate and manganese sulfate or zinc triflate. In addition, glass fiber, filter paper or non-woven fabric can be used as the membrane material.
In addition, as an alternative embodiment of the present invention, the present invention can also be applied to an aluminum ion battery or a multi-ion battery containing zinc ions, such as a mixed ion battery of zinc and aluminum ions. The electrolyte salt used in the aluminum ion battery can be aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum perchlorate, aluminum triflate, etc.; when applied to a multi-ion battery, a mixture of zinc salts and aluminum salts can be used.
The invention can finely regulate and control the ion channel from the atomic size level, inhibit the group with the diameter larger than 0.52nm from contacting with the metal negative electrode, thereby reducing the occurrence of side reaction on the surface of the electrode, and simultaneously reducing the activity of water molecules in the multivalent ion hydration group through the space effect. The number of water molecules directly contacted with the surface of the metal foil is reduced through coordination with polyvalent metal ions, so that the corrosion resistance of the electrode is enhanced and the polarization voltage is reduced; meanwhile, deposition of metal is uniform through a tunnel guiding mechanism, growth of dendrites is restrained, and long-term stable circulation of the metal electrode is realized.
The modified electrode prepared by the invention can reduce the polarization voltage of the metal symmetrical battery in the water-based battery, improve the stability of the whole battery and improve the battery efficiency.
In a word, the method is simple to operate and low in cost, and the modified metal negative electrode is corrosion-resistant and effectively inhibits side reactions.
Drawings
FIG. 1 is a BET nitrogen adsorption drawing of a modified layer obtained in example 8 of the present invention.
FIG. 2 is a polarization voltage plot of a 20 μm modified layer protected metal electrode of example 8 of the present invention versus an unmodified electrode of comparative example 1 and a modified metal electrode used in comparative example 2.
Fig. 3 is a graph showing the long cycle capacity-number of turns comparison of the aqueous zinc-ion batteries of example 8 and comparative example 3.
Detailed Description
The present invention will be described in detail with reference to examples, comparative examples and drawings. It is to be understood that this is by way of illustration and explanation only and is not intended to be limiting of the invention.
In the following examples and comparative examples, the LAND CT2001A tester was purchased from blue electric Co., ltd.
Example 1
(1) Preparing a solution A:2.24g sodium silicate was dissolved in 15ml deionized water; preparing a solution B:2.04g of sodium metaaluminate was dissolved in 15ml of deionized water. Slowly pouring the solution A into the solution B, vigorously stirring, and adjusting the molar ratio Na by using sodium hydroxide 2 O：Al 2 O 3 ：SiO 2 ：H 2 O=3.58: 1:1.24: 171.18. crystallizing at 40deg.C for 5 days.
(2) And (3) centrifuging and drying the crystallized product, dispersing in deionized water, adding zinc sulfate solutions with different concentrations, wherein the ratio of zinc ions to the dried crystallized product is 0.01mol/g, stirring at room temperature for 6 hours, and centrifuging and drying. Then the ion exchange steps are respectively repeated in turn: the ratio of zinc ions in the zinc sulfate solution to the last dried product is 0.05mol/g, 0.1mol/g, 0.2mol/g, 0.5mol/g and 1mol/g respectively.
(3) Mixing the finally obtained dried product with PVDF, wherein the PVDF has the mass fraction of 5%, adding a proper amount of NMP, uniformly mixing to prepare a coating agent, and coating the coating agent on zinc foil by blade coating to uniformly cover the surface of the zinc foil to form a modified electrode;
(4) Vacuum drying the modified electrode in a 60 ℃ oven to obtain a protective layer with a coating thickness of 5 mu m, cutting the modified cathode into a wafer with a thickness of 11mm, and assembling the battery;
(5) The symmetrical cell was assembled using modified electrodes, glass fiber as separator, electrolyte with a mixture of 2 moles per liter of zinc sulfate and 0.2 moles per liter of manganese sulfate. CR2025 button cell was assembled in air, and after 10h of standing, tested on LAND CT2001A tester.
Example 2
In the step (1), hydrothermal crystallization is carried out in a reaction kettle at the temperature of 95 ℃ for 6 hours. Otherwise, the same as in example 1 was conducted.
Example 3
Crystallizing in the step (1) in a reaction kettle at 70 ℃ for 6 hours. Otherwise, the same as in example 1 was conducted.
Example 4
Crystallizing in the step (1) in a reaction kettle at 45 ℃ for 6 hours. Otherwise, the same as in example 1 was conducted.
Example 5
In the step (3), the binder is CMC, and the solvent is water. Otherwise, the same as in example 1 was conducted.
Example 6
In the step (3), the binder is PEO and the solvent is NMP. Otherwise, the same as in example 1 was conducted.
Example 7
The coating amount of the coating agent in the step (3) was adjusted so that the coating thickness obtained in the step (4) was 10. Mu.m.
Example 8
The coating amount of the coating agent in the step (3) was adjusted so that the coating thickness obtained in the step (4) was 20. Mu.m. Otherwise, the same as in example 1 was conducted.
In addition to the symmetrical battery test, this example also performed a full battery test at the same time: manganese dioxide is used as a positive electrode, a CR2025 button cell is assembled by matching the protected zinc metal negative electrode, and the battery is subjected to a test on a LAND CT2001A tester after standing for 10 hours.
The manganese dioxide anode is prepared by mixing an alpha manganese dioxide mixed conductive agent with an adhesive, adding an organic solvent to prepare slurry, coating the slurry on carbon cloth, and vacuum drying.
Example 9
The coating amount of the coating agent in the step (3) was adjusted so that the thickness of the coating layer obtained in the step (4) was 30. Mu.m.
Example 10
The coating amount of the coating agent in the step (3) was adjusted so that the coating thickness obtained in the step (4) was 60. Mu.m.
Example 11
The coating amount of the coating agent in the step (3) was adjusted so that the coating thickness obtained in the step (4) was 75. Mu.m.
Comparative example 1
Zinc foil is used as a positive electrode and a negative electrode respectively, glass fiber is used as a diaphragm, and the electrolyte is a mixed solution of 2mol of zinc sulfate per liter and 0.2mol of manganese sulfate per liter. CR2025 button cell was assembled in air, and after 10h of standing, tested on LAND CT2001A tester.
Comparative example 2
In the step (2), only one low-concentration ion exchange is carried out, namely the ratio of zinc ions to dry crystallization products is 0.01mol/g. Otherwise, the method was as described in example 8.
Comparative example 3
The zinc foil is used as a negative electrode, the manganese dioxide is used as a positive electrode, the glass fiber is used as a diaphragm, and the electrolyte is a mixed solution of 2mol of zinc sulfate per liter and 0.2mol of manganese sulfate per liter. CR2025 button cell was assembled in air, and after 10h of standing, tested on LAND CT2001A tester.
Table 1: polarization voltage and cycle duration table after stabilization of metal symmetrical battery in each example and each comparative example
FIG. 1 is a BET nitrogen adsorption drawing of a modified layer obtained in example 8 of the present invention. FIG. 2 is a polarization voltage plot of a 20 μm modified layer protected metal electrode of example 8 of the present invention versus an unmodified electrode of comparative example 1 and a modified metal electrode used in comparative example 2. Fig. 3 is a graph showing the long cycle capacity-number of turns comparison of the aqueous zinc-ion batteries of example 8 and comparative example 3.
As can be seen from table 1 and fig. 1-3:
the rise of crystallization temperature has a negative effect on the polarization voltage and cycle performance of the battery, and a crystallization method at low temperature for a long time is preferable.
The binder used has substantially no significant effect on the polarization voltage of the cell and the cycle length.
The optimal choice of coating thickness is 20 μm.
In the coating obtained in example 8, the ion exchange enlarged the molecular sieve pores, with an average pore size of 0.523nm, while removing most of the sodium ions that could not participate in the deposition process. This can significantly enhance the molecular dynamics of the reaction.
The polarization voltage of the zinc metal symmetrical battery of each embodiment of the invention in the water-based electrolyte is in the range of 15mV-40mV, which is obviously smaller than that of the zinc metal symmetrical battery without modification of comparative example 1. XRD and Tafil curve tests are carried out on the electrode plate after circulation, and it is found that no obvious side reaction products are generated on the surface of the modified electrode in each embodiment of the invention, the corrosion resistance is enhanced, and a byproduct basic zinc sulfate is generated on the surface of the electrode plate in comparative example 1. This demonstrates that the modified electrode of the present invention suppresses hydrogen evolution and passivation of the electrode surface. The metal symmetrical battery provided by the embodiment of the invention can stably circulate for more than 2000 hours, and the stable circulation time is twenty times longer than that of an unmodified zinc cathode, which indicates that the modified electrode provided by the invention inhibits the growth of zinc dendrites. The water-based zinc ion battery provided by the embodiment of the invention still shows higher specific capacity after 8000 cycles, and shows stronger capacity retention rate compared with comparative example 3, so that the application success of the full battery provided by the invention through the modified cathode is improved.

Claims (6)

1. A method for preparing a negative electrode of a zinc ion battery, comprising:
providing a zinc foil;
providing a silicon ion source selected from at least one of the group consisting of silica gel, water glass, sodium silicate and ethyl orthosilicate;
providing an aluminum ion source selected from at least one of the group consisting of aluminum sulfate hydrate and sodium metaaluminate;
forming a mixed aqueous solution by a silicon ion source, an aluminum ion source and sodium hydroxide, wherein the molar ratio of silicon ions, sodium ions and water molecules to aluminum ions is 1.5-1, 5-3 and 90-80 respectively;
controlling the temperature of the mixed aqueous solution to be between 25 and 90 ℃ for hydrothermal crystallization for at least 5 hours;
centrifuging to separate out crystallized products;
drying the crystallized product, adding the dried product into zinc ion water solutions with different concentrations, sequentially carrying out ion exchange, wherein the mass ratio of the zinc ion molar quantity to the dried product is between 0.01mol/g and 1mol/g, sequentially carrying out ion exchange according to the concentration of the zinc ion water solution from low to high, and carrying out centrifugal drying treatment after each ion exchange;
mixing the dried product obtained after the last ion exchange with a binder and a solvent to obtain a coating agent;
the obtained coating agent is uniformly coated on zinc foil to form a coating, wherein the thickness of the coating is 5-75 mu m after the solvent volatilizes.
2. The method of claim 1, wherein the mass ratio of the resulting dried product to binder is between 20:1 to 7: 1.
3. The method of claim 1, wherein the binder is selected from at least one of the group consisting of polyvinylidene fluoride, polyethylene oxide, and carboxymethyl cellulose.
4. The method of claim 1, wherein the solvent used to form the coating agent is N-methylpyrrolidone or water.
5. A negative electrode for a zinc-ion battery, prepared by the method according to any one of claims 1 to 4.
6. A zinc ion battery comprising the negative electrode of claim 5.
CN202210117340.7A 2022-02-08 2022-02-08 Aqueous metal battery and modified anode thereof Active CN114520302B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109167095A (en) * 2018-08-21 2019-01-08 成都新柯力化工科技有限公司 A kind of the modified aluminosilicate additive and preparation method of lithium-sulfur cell electrolyte
CN109967118A (en) * 2019-05-05 2019-07-05 北京化工大学 A kind of Method in situ modification of the HZSM-5 molecular sieve catalyst for methanol conversion for preparing arene
JP6604451B1 (en) * 2019-03-28 2019-11-13 住友大阪セメント株式会社 Positive electrode material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, lithium ion secondary battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109167095A (en) * 2018-08-21 2019-01-08 成都新柯力化工科技有限公司 A kind of the modified aluminosilicate additive and preparation method of lithium-sulfur cell electrolyte
JP6604451B1 (en) * 2019-03-28 2019-11-13 住友大阪セメント株式会社 Positive electrode material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, lithium ion secondary battery
CN109967118A (en) * 2019-05-05 2019-07-05 北京化工大学 A kind of Method in situ modification of the HZSM-5 molecular sieve catalyst for methanol conversion for preparing arene

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