CN114530572A - Composite modified negative electrode for aqueous metal battery - Google Patents

Composite modified negative electrode for aqueous metal battery Download PDF

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CN114530572A
CN114530572A CN202210117307.4A CN202210117307A CN114530572A CN 114530572 A CN114530572 A CN 114530572A CN 202210117307 A CN202210117307 A CN 202210117307A CN 114530572 A CN114530572 A CN 114530572A
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zinc
negative electrode
temperature
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coating
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CN114530572B (en
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吴川
赵然
杨菁菁
白莹
吴锋
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Beijing Institute of Technology BIT
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    • H01—ELECTRIC ELEMENTS
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    • H01M4/02—Electrodes composed of, or comprising, active material
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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
    • H01M10/36—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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M4/624—Electric conductive fillers
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    • H—ELECTRICITY
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    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
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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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • 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
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Abstract

A composite modified negative electrode for an aqueous metal battery. The preparation method of the negative electrode comprises the steps of preparing a carbon-coated composite material precursor through a sol-gel method, calcining the precursor in a protective atmosphere to form black powder, and finally forming a coating agent together with a binder and a solvent to coat the black powder on a zinc foil to form the modified negative electrode. The invention realizes double-layer metal deposition by the synergistic action of the prepared composite modified negative electrode and inhibits dendritic crystal growth; the polarization voltage of the battery is further reduced while the conductive carbon is introduced, and the long-term stable circulation of the battery is realized.

Description

Composite modified negative electrode for aqueous metal battery
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 environmental pollution aggravation and climate change caused by the excessive dependence on fossil fuel, the demand for clean and sustainable energy has been rapidly increased in recent years. Solar, wind, tidal, etc. as renewable energy sources limit their further use due to their inherent intermittency, unpredictability and dispersability, while electrochemical energy storage is extremely competitive due to reliable and manageable energy delivery. Currently, lithium ion batteries are dominant in secondary battery applications ranging from portable electronic devices (mobile phones and notebook computers, etc.) to electric vehicles due to their high energy density and mature manufacturing technology. However, due to the problems of insufficient metal lithium resources, high cost, harsh preparation conditions, toxic organic electrolyte, flammability, potential safety hazard and the like, a safe and low-cost alternative battery system is urgently sought.
The water-based secondary battery has the advantages of no toxicity, low cost, high safety, high ionic conductivity and the like, and is a promising substitute for the lithium battery. Zinc and aluminium ions act as multivalent ions, theoretically capable of transferring multiple charges per ion unit, meaning that for the same number of reactive ions the capacity will be twice or three times that of lithium ions, respectively. Wherein the ionic radius of zinc is small
Figure BDA0003496939650000011
Has relatively high capacity density (5855mAh cm)-3，820mAh g-1) Compared with a Standard Hydrogen Electrode (SHE), zinc has an oxidation-reduction potential of-0.763V and is more suitable for aqueous electrolytes. However, the following problems are generally encountered in the metal plating and stripping processes: (1) the uneven deposition of zinc ions can lead to the formation of zinc dendrites, the accumulation of dendrites can pierce a membrane to cause short circuit, and the increased specific surface area can also accelerate the consumption of electrolyte; (2) hydrogen evolution reaction is carried out, so that the local hydroxyl concentration is increased, and insoluble substances are formed in the charging process; (3) the by-products adhere to the surface of the metal foil, and the surface of the electrode is passivated. On the metal aluminum watchFacets, too, are accompanied by hydrogen evolution and passivation problems.
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 of preparing a negative electrode for a zinc ion battery, comprising:
providing a zinc foil;
dissolving a carbon source, a titanium source, a sodium source and a phosphorus source in absolute ethyl alcohol to form a mixed solution, wherein the molar ratios of the carbon source, the titanium source and the sodium source to the phosphorus source are respectively 0.5-1, 0.5-1 and 0.2-0.5;
carrying out sol-gel reaction on the mixed solution under the oil bath condition of 60-80 ℃ until white gel is formed;
drying the gel to obtain a precursor;
calcining the precursor in a protective atmosphere, wherein the calcining condition is that the temperature is increased to 320-380 ℃ from room temperature at the heating rate of 2-5 ℃/min, the temperature is kept for 3-5 h, then the temperature is continuously increased to 680-720 ℃ at the same heating rate, and the temperature is kept for 7-9 h to obtain black powder;
mixing the obtained black powder 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 10-50 mu m.
The process according to the invention, wherein the mass ratio of the dry product obtained to the binder is preferably between 9.5: 0.5 to 7: 3, or less.
The method according to the present invention, wherein the binder may be selected from at least one of the group consisting of polyvinylidene fluoride (PVDF), polyethylene oxide (PEO) and carboxymethylcellulose (CMC).
The method according to the invention, wherein the solvent used for forming the coating agent may be N-methylpyrrolidone (NMP) or water, preferably NMP is used.
According to the method of the invention, vacuum or non-vacuum drying can be adopted when the 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 coating agent can be coated on the surface of the negative electrode or the zinc foil with controllable thickness by adopting a suitable mode of knife coating, spin coating, spray coating and the like.
As an alternative embodiment of the invention, glucose, ascorbic acid, dopamine hydrochloride or tartaric acid may be used instead of citric acid. Sodium acetate may also be replaced by sodium carbonate, sodium citrate, sodium carboxymethylcellulose or sodium dihydrogen phosphate. Phosphoric acid may also be replaced with ammonium dihydrogen phosphate.
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 may further include an electrolytic aqueous solution formed of at least one selected from the group consisting of zinc sulfate, zinc chloride, zinc acetate, and zinc trifluoromethanesulfonate. The electrolyte is preferably formed from zinc sulphate.
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 black powder material prepared according to the invention is a carbon-coated composite material (NaTi)2(PO4)3@ C), the ion channel of such fast ion conductors redistributes the zinc ion flux near the electrode/electrolyte interface, enabling uniform deposition of metal between the metal foil and the interface layer or coating; at the same timeThe introduced carbon is utilized to increase active sites, reduce local current density, homogenize electric field distribution and guide metal to be uniformly deposited at carbon vacancies. Through the synergistic effect, a double-layer metal deposition layer can be obtained, and the growth of dendritic crystals is inhibited; the introduction of the conductive carbon further reduces the polarization voltage of the battery, and the long-term stable circulation of the battery is realized.
The cathode of the water-based metal battery prepared by the invention can reduce the polarization voltage of the metal symmetrical battery and improve the cycling stability; the charge transfer resistance of the full cell is reduced, and the cycle performance and the rate performance are improved.
In a word, the method is simple to operate and low in cost, and the metal cathode modified by double protection and modification is corrosion-resistant and effectively inhibits side reactions.
Drawings
FIG. 1 is a TEM image of a black powder obtained in example 1 of the present invention.
Fig. 2 is a graph showing polarization voltages of a metal electrode protected by a 20 μm composite modified layer in example 8 of the present invention, an unmodified electrode of comparative example 1, and an uncoated carbon modified metal electrode used in comparative example 2.
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 purchased from blue-ray electronics, Inc., Wuhan, Inc. The metal negative electrode matrix is zinc foil.
Example 1
(1) 4mmol of citric acid, 4mmol of tetrabutyl titanate, 2mmol of sodium acetate and 6mmol of phosphoric acid are respectively dissolved in 40,40,20 and 20mL of absolute ethyl alcohol, and are mixed in sequence after being fully stirred and dissolved. The combined solution was heated at 70 ℃ with oil bath stirring until a white gel was formed. The gel was dried at 70 ℃ overnight to obtain a complex precursor.
(2) And calcining the precursor in a tube furnace (Ar protective gas) to obtain the carbon-coated composite material NTP @ C. The calcining condition is that the temperature is raised to 350 ℃ from the room temperature at the temperature raising speed of 2 ℃/min, and the temperature is kept for 4 h; then, the temperature is continuously raised to 700 ℃ at the same temperature raising speed, and the temperature is kept for 8h to obtain black powder (NTP @ C).
(3) Mixing NTP @ C and PVDF in a mass ratio of 9:1, adding a proper amount of NMP, stirring to prepare coating agent slurry, and uniformly coating the coating agent slurry on a zinc foil by adopting a blade coating method to prepare the modified negative electrode.
(4) Vacuum drying at 80 ℃ overnight gave a modified or protective layer with a coating thickness of 10 μm on the zinc foil. After that, the modified negative electrode (zinc foil covered with the modified coating) was blanked into a pole piece with a diameter of 11mm for assembling the battery.
(5) Assembling a CR2025 type button battery in the air, wherein a pole piece covered with a modified coating is used as a positive electrode and a negative electrode, glass fiber is used as a diaphragm, and 2 mol of zinc sulfate per liter is used as electrolyte. After standing for 12h, the test was carried out on a LAND CT2001A tester.
Example 2
The calcination condition in the step (2) is that the temperature is raised to 350 ℃ from room temperature at the temperature raising speed of 2 ℃/min, and the temperature is kept for 4 h; then, the temperature is raised to 600 ℃ continuously at the same heating rate, and the temperature is kept for 8h to obtain black powder. Otherwise, the same procedure as in example 1 was repeated.
Example 3
The calcining condition in the step (2) is that the temperature is raised to 350 ℃ from room temperature at the temperature raising speed of 2 ℃/min, and the temperature is kept for 4 h; then, the temperature is continuously raised to 800 ℃ at the same temperature raising speed, and the temperature is kept for 8h to obtain black powder. Otherwise, the same procedure as in example 1 was repeated.
Example 4
The calcining condition in the step (2) is that the temperature is raised to 350 ℃ from room temperature at the temperature raising speed of 5 ℃/min, and the temperature is kept for 4 h; then, the temperature is continuously raised to 700 ℃ at the same temperature raising speed, and the temperature is kept for 8h to obtain black powder. Otherwise, the same procedure as in example 1 was repeated.
Example 5
The calcining condition in the step (2) is that the temperature is raised to 350 ℃ from room temperature at the heating rate of 10 ℃/min, and the temperature is kept for 4 h; then, the temperature is continuously raised to 700 ℃ at the same temperature raising speed, and the temperature is kept for 8h to obtain black powder. 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
In the step (3), the binder is CMC, and the solvent is water. Otherwise, the same procedure as in example 1 was repeated.
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 full cell test was also performed with the CR2025 button cell simultaneously assembled. Wherein, alpha manganese dioxide is used as a positive electrode, NTP @ C modified zinc metal is used as a negative electrode, 2 mol per liter of zinc sulfate and 0.2 mol per liter of manganese sulfate are used as electrolyte, and glass fiber is used as a diaphragm. After standing for 12h, the test was carried out on a LAND CT2001A tester.
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 40 μm.
Example 11
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 50 μm.
Comparative example 1
The CR2025 button cell was assembled in air, with unmodified zinc plates as the positive and negative electrodes, glass fiber as the separator, and 2 moles per liter of zinc sulfate as the electrolyte. After standing for 12h, the test was carried out on a LAND CT2001A tester.
In addition to the symmetric cell test, the present comparative example also simultaneously assembled CR2025 coin cells for full cell testing. Wherein, alpha manganese dioxide is used as a positive electrode, unmodified zinc metal is used as a negative electrode, 2 mol per liter of zinc sulfate and 0.2 mol per liter of manganese sulfate are used as electrolyte, and glass fiber is used as a diaphragm. After standing for 12h, the test was carried out on a LAND CT2001A tester.
Comparative example 2
And (3) calcining the precursor in the step (2) in a muffle furnace (in an air atmosphere) to obtain the uncoated material NTP. Wherein the calcining condition is that the temperature is raised to 350 ℃ from the room temperature at the temperature raising speed of 2 ℃/min, and the temperature is kept for 4 h; then, the temperature is raised to 700 ℃ continuously at the same temperature raising speed, and the temperature is kept for 8h to obtain white powder. 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 procedure is as described in example 1.
In addition to the symmetric cell test, the present comparative example also simultaneously assembled CR2025 coin cells for full cell testing. Wherein, alpha manganese dioxide is used as a positive electrode, zinc metal modified by NTP is used as a negative electrode, 2 mol per liter of zinc sulfate and 0.2 mol per liter of manganese sulfate are used as electrolyte, and glass fiber is used as a diaphragm. After standing for 12h, the test was carried out on a LAND CT2001A tester.
Table 1: polarization voltage and cycle length table after metal symmetrical battery stabilization in each embodiment and each proportion
Figure BDA0003496939650000071
Table 2: full battery cycle performance contrast table
Figure BDA0003496939650000081
FIG. 1 is a TEM image of a black powder obtained in example 1 of the present invention. Fig. 2 is a graph showing polarization voltages of a metal electrode protected by a 20 μm composite modified layer in example 8 of the present invention, an unmodified electrode of comparative example 1, and an uncoated carbon modified metal electrode used in comparative example 2.
As can be seen from tables 1 and 2 and fig. 1 and 2:
the calcination temperature is either too high or too low, preferably 700 ℃, which adversely affects the polarization voltage and cycle performance of the battery.
Too fast a temperature rise rate can cause sample particle agglomeration, effective uniform zinc ion flux cannot be guaranteed, and negative effects can be generated on polarization voltage and cycle performance of the battery, and a low temperature rise rate (2 ℃/min) method is preferred.
The type of binder had no significant effect on the polarization voltage of the cell and the cycle length, illustrating the flexibility in binder selection according to the present invention.
The thickness of the coating is preferably 20 μm.
The incorporation of a dual protective coating can improve the cycling performance of the cell, and the incorporation of carbon can provide a synergistic effect that, together with NTP, induces uniform zinc deposition. The TEM image of FIG. 1 shows that the particle size of the nanoparticles is about 20-30 nm, and the citric acid simultaneously acts as a chelating agent and a carbon source, so that the grain size can be controlled, and a carbon matrix and a coating layer are formed.
The polarization voltage range of the zinc metal symmetrical battery modified by NTP @ C in an aqueous electrolyte is 15-40 mV, which is obviously reduced compared with the unmodified zinc electrode in the comparative example 1. XRD results after electrode slice circulation show that basic zinc sulfate as a byproduct on the surface of the electrode after NTP and NTP @ C modification is obviously reduced, and side reactions are inhibited. The aqueous zinc metal symmetrical battery protected by NTP @ C can stably circulate for more than 600 hours, and the circulation stability is respectively improved by 6 times and 3 times compared with that of unmodified zinc and zinc modified by NTP. The test result of the full battery shows that the introduction of the protective layer obviously improves the cycling stability of the battery, and after the cycling of 100000 times, the capacity retention rate of the full battery modified based on NTP @ C is still 70%. The capacity of a full cell based on an unmodified zinc anode decays rapidly to less than 30% of the initial specific capacity only in less than 500 cycles. The above examples illustrate that, by protecting the metal negative electrode with the carbon-coated composite material, the problems in the metal negative electrode can be improved by the synergistic effect of NTP and carbon, the generation of dendrites is inhibited, side reactions are reduced, the polarization voltage is significantly reduced, and the cycle stability of the metal battery is significantly improved.

Claims (7)

1. A preparation method of a negative electrode of a zinc ion battery comprises the following steps:
providing a zinc foil;
dissolving a carbon source, a titanium source, a sodium source and a phosphorus source in absolute ethyl alcohol to form a mixed solution, wherein the molar ratios of the carbon source, the titanium source and the sodium source to the phosphorus source are respectively 0.5-1, 0.5-1 and 0.2-0.5;
carrying out sol-gel reaction on the mixed solution under the oil bath condition of 60-80 ℃ until white gel is formed;
drying the gel to obtain a precursor;
calcining the precursor in a protective atmosphere, wherein the calcining condition is that the temperature is increased to 320-380 ℃ from room temperature at the temperature increasing speed of 2-5 ℃/min, the temperature is kept for 3-5 h, then the temperature is continuously increased to 680-720 ℃ at the same temperature increasing speed, and the temperature is kept for 7-9 h to obtain black powder;
mixing the obtained black powder 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 10-50 mu m.
2. The method of claim 1, wherein the mass ratio of black powder to binder obtained is in the range of 9.5: 0.5 to 7: 3, or less.
3. The method of claim 1, wherein the binder is selected from at least one of the group consisting of polyvinylidene fluoride and polyethylene oxide and carboxymethyl cellulose.
4. The method according to claim 1, wherein the solvent for forming the coating agent is N-methylpyrrolidone and/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.
7. The battery of claim 6, further comprising an electrolytic aqueous solution formed from at least one selected from the group consisting of zinc sulfate, zinc chloride, zinc acetate, and zinc triflate.
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CN111900388A (en) * 2020-05-26 2020-11-06 北京理工大学 Zinc ion battery negative electrode material, preparation and application thereof
CN111900406A (en) * 2020-08-03 2020-11-06 常州工学院 Preparation method and application of carbon-coated manganese silicate material

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CN116495714A (en) * 2023-04-04 2023-07-28 陕西则明未来科技有限公司 Preparation and application of amorphous sodium titanium phosphate
CN117458009A (en) * 2023-11-02 2024-01-26 中国科学院苏州纳米技术与纳米仿生研究所 Composite zinc electrode and preparation method and application thereof
CN118040092A (en) * 2024-03-19 2024-05-14 江苏贾儒科技有限公司 High-performance water-based zinc ion battery

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