CN114520302A - Aqueous metal battery and modified negative electrode thereof - Google Patents

Aqueous metal battery and modified negative electrode thereof Download PDF

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CN114520302A
CN114520302A CN202210117340.7A CN202210117340A CN114520302A CN 114520302 A CN114520302 A CN 114520302A CN 202210117340 A CN202210117340 A CN 202210117340A CN 114520302 A CN114520302 A CN 114520302A
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zinc
metal
ions
ion
negative electrode
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CN114520302B (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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    • 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

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Abstract

A modified negative electrode for an aqueous 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, then carrying out ion exchange on a crystallization product and a zinc ion solution for multiple times, forming a coating agent by the exchange product, a binder and a solvent, and coating the coating agent on a zinc foil to form the modified negative electrode. The invention finely regulates and controls the ion channel from the atomic size level, inhibits the large-diameter group from contacting with the metal cathode, thereby guiding the uniform deposition of metal ions while reducing the occurrence of side reactions on the surface of the electrode. The activity of water molecules directly contacted with the surface of the metal foil is reduced through coordination with polyvalent metal ions, and the corrosion resistance of the electrode is enhanced; reducing the polarization voltage by application of a negatively charged modifying substance layer; meanwhile, the deposition of metal is uniform through a tunnel guide mechanism, the growth of dendrite is inhibited, and the long-term stable circulation of the metal electrode is realized.

Description

Aqueous metal battery and modified negative electrode thereof
Technical Field
The present invention relates generally to an aqueous metal battery, and more particularly to a modified negative electrode for such a battery.
Background
In order to solve the significant problems of dependence on fossil energy, ecological environment crisis, climate change and the like which are generally concerned internationally at present, the demand of clean and renewable energy sources such as wind energy, solar energy, tidal energy, geothermal energy and the like is higher and higher at present, and due to the instability of the energy sources, an electrochemical energy storage system is an important link for storing and utilizing the new energy sources. Lithium ion batteries, as the most advanced secondary battery system at present, not only play a considerable role in people's daily life, such as portable electronic devices and new energy power battery automobiles, but also provide a short-term solution for large-scale renewable energy storage. However, because flammable organic electrolyte is used, the safety performance of the lithium ion battery is poor, and the danger of combustion and explosion is caused; the distribution of elements required for producing lithium ion batteries, such as lithium, nickel, cobalt, etc., is concentrated, and there is a potential risk of supply. In view of the foregoing, it is not easy to find a battery system that is safe, more stable in supply, high in energy density, environmentally friendly, and low in cost.
Multivalent metal ion batteries are considered to be the most promising alternatives to lithium batteries, such as zinc ion batteries and aluminum ion batteries, which have the potential to provide twice or three times the charge as compared to lithium ions, with divalent zinc ions or trivalent aluminum ions as charge carriers. Meanwhile, the combustible organic electrolyte is replaced by the water-based 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 metal also has stable ionic valence, low price, small radius, lower reduction voltage and higher theoretical specific mass capacity (Zn: 825mAh g)-1,Al:2 980mAh g-1) And the like, do not react with water violently like lithium metal, sodium and the like, and have potential to be directly applied to the water-based battery. However, zinc metal, aluminum metal and the like still have problems which cannot be ignored in the using process: when zinc is deposited on the surface of a zinc cathode, flaky disordered accumulation is formed on the surface of the electrode, and the continuous growth breaks through a diaphragm and causes short circuit between the electrodes, so that the short circuit failure of the battery is caused; under the influence of working conditions, hydrogen evolution reaction is easy to occur on the surface of the electrode, the coulomb efficiency of the battery is reduced, and electrolyte leakage is caused; the local hydroxyl concentration is increased due to the hydrogen evolution reaction, and the hydrogen is easy to react with metal and other ions existing in the electrolyte, so that a passivation film is formed on the surface of the electrode to reduce the cycle performance of the battery. The problems of surface hydrogen evolution and passivation of the electrode surface are also present in aluminum metal anodes.
In order to solve the problems of the metal negative electrode, the four aspects of an SEI film, an electrode body structure, an electrolyte and a diaphragm are mainly optimized at present: firstly, the construction of a multifunctional artificial protective layer inhibits side reactions and the growth of dendrites; secondly, optimizing the structural composition of the metal electrode body; thirdly, inhibiting the generation of hydrogen evolution reaction by using a salt-coated water electrolyte; and fourthly, constructing a functional diaphragm inducing the uniform deposition of ions. The method inhibits the occurrence of side reactions to a certain extent, but is limited in the application process, for example, the process for optimizing the structural composition of the metal electrode body is complex, the salt-coated water electrolyte is sensitive to temperature change, and the functional diaphragm cannot inhibit the occurrence of hydrogen evolution reaction.
Disclosure of Invention
It is an object of the present invention to provide a modified negative electrode for aqueous metal batteries, particularly zinc ion batteries, which overcomes at least some of the above-mentioned disadvantages.
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 a source of aluminum ions selected from at least one of the group consisting of hydrated aluminum sulfate and sodium metaaluminate;
forming a silicon ion source, an aluminum ion source and sodium hydroxide into a mixed aqueous solution, wherein the molar ratios of silicon ions, sodium ions and water molecules to aluminum ions are respectively 1.5-1, 5-3 and 90-80;
controlling the temperature of the mixed aqueous solution to carry out hydrothermal crystallization at 25-90 ℃ for at least 5 hours;
centrifugally separating out a crystallized product;
drying the crystallized product, adding the crystallized product into zinc ion aqueous solutions with different concentrations to perform ion exchange in sequence, wherein the mass ratio of the molar quantity of zinc ions to the dried product is between 0.01mol/g and 1mol/g, performing ion exchange in sequence from low to high according to the concentration of the zinc ion aqueous solution, and performing 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 a zinc foil to form a coating, wherein the thickness of the coating after the solvent is volatilized is 5-75 mu m.
The method of the invention adopts at least 3 kinds of zinc ion aqueous solutions with different concentrations in ion exchange, such as 0.01mol/g, 0.05mol/g, 0.1mol/g, 0.2mol/g, 0.5mol/g and 1mol/g zinc ion aqueous solutions 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.
The method according to 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 when CMC is used as the binder, water may be used as a solvent.
According to the process of the present invention, sodium silicate is preferably used as the source of silicon ions. In addition, sodium metaaluminate can 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 can 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 negative electrode or the zinc foil with a controllable thickness by adopting a suitable mode of knife coating, spin coating, spray coating and the like.
As an alternative embodiment of the present invention, aluminum foil may also 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 for 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 present invention, wherein the electrolyte salt is preferably zinc sulfate and manganese sulfate or zinc trifluoromethanesulfonate. In addition, the membrane material can adopt glass fiber, filter paper or non-woven fabric.
In addition, as an alternative embodiment of the present invention, the present invention may also be applied to an aluminum ion battery or a multi-ion type battery containing zinc ions, such as a zinc-aluminum ion mixed ion battery. The electrolyte salt applied to the aluminum ion battery can be aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum perchlorate, aluminum trifluoromethanesulfonate and the like; mixtures of zinc and aluminum salts may be used for multi-ion batteries.
The invention can finely regulate and control ion channels from an atomic size level, and inhibit the contact of groups with the diameter of more than 0.52nm and a metal cathode, thereby reducing the occurrence of side reactions on the surface of an electrode, and simultaneously reducing the activity of water molecules in multivalent ion hydration groups through a space effect. The number of water molecules directly contacting with the surface of the metal foil is reduced through coordination with polyvalent metal ions, the corrosion resistance of the electrode is enhanced, and the polarization voltage is reduced; meanwhile, the deposition of metal is uniform through a tunnel guide mechanism, the growth of dendrite is inhibited, and the long-term stable circulation of the metal electrode is realized.
The modified electrode prepared according to 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 efficiency of the battery.
In a word, the method is simple to operate and low in cost, and the modified metal cathode is corrosion-resistant and effectively inhibits side reactions.
Drawings
FIG. 1 is a BET nitrogen adsorption diagram of a modified layer obtained in example 8 of the present invention.
Fig. 2 is a graph of the polarization voltage of a metal electrode protected by a 20 μm modified layer in example 8 of the present invention, an unmodified electrode of comparative example 1, and a modified metal electrode used in comparative example 2.
Fig. 3 is a graph comparing long cycle capacity versus number of cycles for the aqueous zinc-ion cells of example 8 and comparative example 3.
Detailed Description
The present invention will be described in detail below with reference to examples, comparative examples and the accompanying drawings. It is to be understood that these are for purposes of illustration and explanation only and are not limiting of the invention.
In the following examples and comparative examples, the LAND CT2001A tester was obtained from Blueelectronics, Inc., Wuhan, Inc.
Example 1
(1) Preparing a solution A: 2.24g of sodium silicate dissolved in 15ml of deionized water; preparing a solution B: 2.04g of sodium metaaluminate are dissolved in 15ml of deionized water. Slowly pouring the solution A into the solution B, stirring vigorously, and adjusting the molar ratio Na by using sodium hydroxide2O：Al2O3：SiO2：H2O ═ 3.58: 1: 1.24: 171.18. crystallizing at 40 deg.C for 5 days.
(2) And centrifuging and drying the crystallized product, dispersing the crystallized product 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 for 6 hours at room temperature, and centrifuging and drying. Then, the ion exchange steps are respectively repeated in sequence: 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, 1mol/g, respectively.
(3) Mixing the finally obtained dry product with PVDF, wherein the mass fraction of the PVDF is 5%, adding a proper amount of NMP, uniformly mixing to prepare a coating agent, coating the coating agent on a zinc foil through blade coating, and uniformly covering the surface of the zinc foil with a coating to form a modified electrode;
(4) placing the modified electrode in a 60 ℃ drying oven for vacuum drying to obtain a protective layer with the thickness of 5 mu m, cutting the modified cathode into a wafer with the thickness of 11mm, and waiting for assembling the battery;
(5) the modified electrode is used for assembling a symmetrical battery, the glass fiber is used as a diaphragm, and the electrolyte is mixed solution of 2mol of zinc sulfate per liter and 0.2mol of manganese sulfate per liter. The CR2025 button cell was assembled in air, left for 10h and tested on the 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 procedure as in example 1 was repeated.
Example 3
Crystallizing in a reaction kettle in the step (1) at 70 ℃ for 6 hours. Otherwise, the same procedure as in example 1 was repeated.
Example 4
Crystallizing in a reaction kettle in the step (1) at 45 ℃ for 6 hours. Otherwise, the same procedure as in example 1 was repeated.
Example 5
In the step (3), the binder is CMC, and the solvent is water. Otherwise, the same procedure as in example 1 was repeated.
Example 6
In the step (3), the binder is PEO, and the solvent is NMP. Otherwise, the same procedure as in example 1 was repeated.
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 μm.
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 μm. Otherwise, the same procedure as in example 1 was repeated.
In addition to the symmetric cell test, the present example also performed the full cell test simultaneously: manganese dioxide is used as a positive electrode, a zinc metal negative electrode after protection is matched to assemble a CR2025 button cell, and the cell is placed still for 10 hours and then tested on a LAND CT2001A tester.
The manganese dioxide anode is prepared by mixing an alpha manganese dioxide conductive agent and an adhesive, adding an organic solvent to prepare slurry, coating the slurry on carbon cloth, and drying the carbon cloth in vacuum.
Example 9
The coating amount of the coating agent in the step (3) was adjusted so that the coating thickness obtained in the step (4) was 30 μm.
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 μm.
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 μm.
Comparative example 1
Zinc foils are respectively used as a positive electrode and a negative electrode, glass fibers are used as a diaphragm, and the electrolyte is mixed solution of 2mol per liter of zinc sulfate and 0.2mol per liter of manganese sulfate. The CR2025 button cells were assembled in air and left for 10h before testing on the LAND CT2001A tester.
Comparative example 2
In the step (2), only one-time low-concentration ion exchange is carried out, namely, the ratio of zinc ions to the dry crystallized product is 0.01 mol/g. The other steps were the same as those described in example 8.
Comparative example 3
Zinc foil is used as a negative electrode, manganese dioxide is used as a positive electrode, glass fiber is used as a diaphragm, and the electrolyte is mixed solution of 2mol per liter of zinc sulfate and 0.2mol per liter of manganese sulfate. The CR2025 button cells were assembled in air and left for 10h before testing on the LAND CT2001A tester.
Table 1: polarization voltage and cycle length table after metal symmetrical battery stabilization in each embodiment and each proportion
Figure BDA0003496968850000081
FIG. 1 is a BET nitrogen adsorption diagram of a modified layer obtained in example 8 of the present invention. Fig. 2 is a graph of the polarization voltage of a metal electrode protected by a 20 μm modified layer in example 8 of the present invention, an unmodified electrode of comparative example 1, and a modified metal electrode used in comparative example 2. Fig. 3 is a graph comparing long cycle capacity versus number of turns of the aqueous zinc-ion battery in example 8 and comparative example 3.
As can be seen from table 1 and fig. 1-3:
the increase of the crystallization temperature has a negative influence on the polarization voltage and cycle performance of the battery, and a crystallization method at a low temperature for a long time is preferred.
The binder used has substantially no significant effect on the polarization voltage of the cell and the cycle length.
The optimum choice of coating thickness is 20 μm.
In the coating obtained in example 8, ion exchange enlarged the pores of the molecular sieve to an average pore size of 0.523nm, while removing most of the sodium ions that could not participate in the deposition process. This may 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 system electrolyte is in the range of 15mV-40mV, which is obviously smaller than that of the zinc metal symmetrical battery without modification of the comparative example 1. XRD and Tafel curve tests are carried out on the electrode slice after circulation, and the modified electrode surface of each embodiment of the invention is found to have no obvious side reaction product and enhanced corrosion resistance, while the electrode slice surface of the comparative example 1 generates basic zinc sulfate as a by-product. This demonstrates that the modified electrode of the present invention suppresses hydrogen evolution and passivation reactions of the electrode surface. The metal symmetrical battery provided by the embodiment of the invention can stably circulate for more than 2000h, and the stable circulation time is more than twenty times of that of an unmodified zinc cathode, so 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 the comparative example 3, which shows that the full battery provided by the invention successfully improves the actual application prospect through the application of the modified negative electrode.

Claims (6)

1. A preparation method of a negative electrode of a zinc ion battery comprises the following steps:
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 a source of aluminum ions selected from at least one of the group consisting of hydrated aluminum sulfate and sodium metaaluminate;
forming a silicon ion source, an aluminum ion source and sodium hydroxide into a mixed aqueous solution, wherein the molar ratios of silicon ions, sodium ions and water molecules to aluminum ions are respectively 1.5-1, 5-3 and 90-80;
controlling the temperature of the mixed aqueous solution to carry out hydrothermal crystallization at 25-90 ℃ for at least 5 hours;
centrifugally separating out a crystallized product;
drying the crystallized product, adding the crystallized product into zinc ion aqueous solutions with different concentrations to perform ion exchange in sequence, wherein the mass ratio of the molar quantity of zinc ions to the dried product is between 0.01mol/g and 1mol/g, performing ion exchange in sequence from low to high according to the concentration of the zinc ion aqueous solution, and performing 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 a zinc foil to form a coating, wherein the thickness of the coating after the solvent is volatilized is 5-75 mu m.
2. The method of claim 1, wherein the mass ratio of the resulting dried product to binder is in the range of 20: 1 to 7: 1.
3. The method of claim 1, wherein the binder is at least one selected from 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 anode 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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