CN114759182B - Graphene-coated tin oxalate negative electrode material, preparation method thereof and battery - Google Patents

Graphene-coated tin oxalate negative electrode material, preparation method thereof and battery Download PDF

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CN114759182B
CN114759182B CN202210583295.4A CN202210583295A CN114759182B CN 114759182 B CN114759182 B CN 114759182B CN 202210583295 A CN202210583295 A CN 202210583295A CN 114759182 B CN114759182 B CN 114759182B
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graphene
electrolyte
oxalate
anode
coated tin
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CN114759182A (en
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梁风
杨冬荣
张达
雷勇
杨斌
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Kunming University of Science and Technology
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • 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
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0464—Electro organic synthesis
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • H01M4/625—Carbon or graphite
    • 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 invention provides a graphene-coated tin oxalate negative electrode material, a preparation method thereof and a battery. The preparation method comprises the following steps: the method comprises the following steps of (1) dividing an electrolyte into an anode side electrolyte and a cathode side electrolyte by using a diaphragm, and adding graphene oxide and an antioxidant into the anode side electrolyte, wherein the electrolyte is a dilute sulfuric acid electrolyte system and contains oxalate ions with the concentration of 40-300 g/L; putting the anode and the cathode into the anode side electrolyte and the cathode side electrolyte respectively, and electrolyzing; filtering and drying the electrolyzed electrolyte to obtain the graphene-coated tin oxalate conductive material; and preparing the cathode material by using the conductive material. The battery comprises the anode material. The invention has short process flow, low preparation cost and simple and convenient operation; the material prepared by the invention has stable cycle performance and high electron transfer rate, and the formed battery has good initial charge-discharge capacity; the invention can improve the cycle life and electrochemical performance of the sodium ion battery.

Description

Graphene-coated tin oxalate negative electrode material, preparation method thereof and battery
Technical Field
The invention relates to the field of batteries, in particular to a graphene-coated tin oxalate negative electrode material, a preparation method thereof and a battery.
Background
The sodium ion battery has the characteristics of rich sodium resource, low cost and the like, attracts the wide attention of researchers at home and abroad, and is considered as the best candidate for possibly replacing the lithium ion battery in the field of large-scale energy storage in future. In recent years, the research on sodium ion batteries has been advanced continuously, and the research systems are continuously abundant. In the research process of the cathode material of the sodium-ion battery, the cathode material of the tin-based battery is proved to have good electrochemical performance, and the stannous oxalate is one of the most common precursors of the cathode material of the tin-based battery, so that the tin-based battery has good application prospect in the field of the sodium battery.
However SnC 2 O 4 The conductive performance is poor, so that the electrochemical performance such as capacity retention rate, rate capability, cycle performance and the like of the material is poor, and the problems of long production process flow, high raw material cost, environmental unfriendliness and the like are severe.
Disclosure of Invention
The present invention aims to address at least one of the above-mentioned deficiencies of the prior art. For example, one of the objects of the present invention is to improve the electrochemical performance of a battery negative electrode material; the second purpose is to provide a preparation method of the graphene-coated tin oxalate conductive material, which has the advantages of short process flow, low raw material cost and simple and convenient operation.
In order to achieve the above object, the present invention provides a method for preparing a graphene-coated tin oxalate conductive material.
The method may comprise the steps of: separating the electrolyte into an anode side electrolyte and a cathode side electrolyte by using a diaphragm, and adding graphene oxide and an antioxidant into the anode side electrolyte; wherein the electrolyte is a dilute sulfuric acid electrolyte system and contains oxalate ions with the concentration of 40 g/L to 300 g/L; respectively putting the anode and the cathode into the anode side electrolyte and the cathode side electrolyte for electrolysis; wherein the anode is metallic tin, and the cathode is an inert material; and filtering the electrolyzed electrolyte to obtain a filter cake, and drying the filter cake to obtain the graphene-coated tin oxalate conductive material.
Optionally, the method further comprises the step of preparing the electrolyte, which may comprise: mixing dilute sulfuric acid with an aqueous sodium oxalate solution, mixing an aqueous sodium oxalate solution with an aqueous sodium sulfate solution, or mixing an aqueous sodium sulfate solution with H 2 C 2 O 4 The aqueous solutions are mixed. Of course, the present invention is not limited thereto, and the electrolyte may be prepared by mixing the solution with a corresponding salt, for example, by dissolving a solid sodium sulfate in oxalic acid.
Alternatively, the pH of the sulfuric acid electrolyte can be 1-6, and the sulfuric acid electrolyte can contain 0.5-16 wt% of sulfate ions and 40-300 g/L of oxalate ions.
Alternatively, the sulfuric acid electrolyte solution includes any one of mixed solutions of:
mixed solution of dilute sulfuric acid and aqueous sodium oxalate solution, mixed solution of aqueous sodium oxalate solution and aqueous sodium sulfate solution, and H 2 C 2 O 4 A mixed solution of the aqueous solutions.
Optionally, the addition amount of the graphene oxide is 1-15% of the mass of oxalate in the anode side electrolytic solution. Further, the addition amount of the graphene oxide is 2-10% of the mass of oxalate in the anode side electrolytic solution.
Alternatively, the pH of the electrolyte can be 1-6, and the electrolyte also contains 0.5-16 wt% of sulfate ions.
Alternatively, the antioxidant may comprise: sodium sulfite, dibutylphenol, sodium hydrogen sulfite, sodium thiosulfate, t-butyl p-hydroxyanisole, 2, 6-di-t-butyl-p-cresol, octadecyl beta (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, 2 '-methylenebis (4-ethyl-6-t-butylphenol), N' -hexamethylenebis-3 (3, 5-di-t-butyl-4-hydroxyphenyl) propionamide, 1,3, 5-tris (3, 5-di-t-butyl-4-hydroxyphenyl) isocyanate, 4-hydroxydodecanoylanilide, 4-hydroxyoctadecanoylanilide and p-t-butylphthalide.
Alternatively, the anodic current density may be 80 to 150A/m 2 The cathode current density can be 300-700A/m 2 The temperature of the electrolysis can be 30-80 ℃, and the time can be 0.25-3 h.
Alternatively, stirring is carried out in the electrolysis process, and the stirring speed can be 100-300 r/min.
The invention provides a graphene-coated tin oxalate conductive material.
The conductive material is prepared by the preparation method of the graphene-coated tin oxalate conductive material.
The invention further provides a graphene-coated tin oxalate negative electrode material.
The negative electrode material can be prepared from the conductive material.
The invention further provides a preparation method of the graphene-coated tin oxalate negative electrode material.
The preparation method comprises the following steps: according to the mass ratio of 6-8: 1 to 1.5:1, mixing the conductive material, acetylene black and polyvinylidene fluoride to obtain a mixture; dispersing the intermediate product in a solvent, and then coating on a carrier; and cold-pressing the coated carrier to obtain the negative electrode material for the battery.
In yet another aspect, the present invention provides a battery.
The negative electrode of the battery may comprise a conductive material as described above.
Alternatively, the battery may include a graphene-coated tin oxalate negative electrode material as described above.
Compared with the prior art, the beneficial effects of the invention comprise at least one of the following:
(1) The invention has the advantages of short process flow, low preparation cost and simple and convenient operation.
(2) The material prepared by the invention has stable cycle performance and high electron transfer rate, and the formed battery has good initial charge-discharge capacity.
(3) The invention can improve the cycle life and electrochemical performance of the sodium ion battery.
Drawings
The above and other objects and/or features of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
fig. 1 shows a schematic flow chart of a preparation method of a graphene-coated tin oxalate conductive material of the present invention.
FIG. 2 shows a schematic of one configuration of a tin anode plate of the electrolytic reaction system of the present invention.
FIG. 3 shows a schematic of the construction of the inert cathode of the electrolytic reaction system of the present invention.
FIG. 4 shows the inventionG @ SnC prepared in example 1 2 O 4 A transmission electron micrograph of (a).
FIG. 5A shows G @ SnC prepared in example 2 of the present invention and comparative example 1 2 O 4 A constant current charging and discharging curve diagram of the button type sodium ion battery.
FIG. 5B shows G @ SnC prepared in example 3 of the present invention and comparative example 1 2 O 4 Constant current charging and discharging curve diagram of the base button sodium ion battery.
FIG. 5C shows G @ SnC prepared according to example 4 of the present invention and comparative example 1 2 O 4 Constant current charging and discharging curve diagram of the base button sodium ion battery.
FIG. 6 shows G @ SnC prepared in example 2 of the present invention 2 O 4 The multiplying power performance curve chart of the button sodium ion battery.
Detailed Description
Hereinafter, the graphene-coated tin oxalate anode material, the preparation method thereof, and the battery according to the present invention will be described in detail with reference to exemplary embodiments.
Exemplary embodiment 1
The exemplary embodiment provides a preparation method of a graphene-coated tin oxalate conductive material.
The method may comprise the steps of:
s1: an electrolyte (also referred to as an electrolyte system) is prepared.
In this embodiment, the electrolyte may have a pH of 1 to 6, and may contain 0.5wt% to 16wt% of sulfate ions and 40g to 300g/L of oxalate ions. For example, the electrolyte may have a pH of 2, 3,5, etc., a sulfate ion content of 1wt%, 5wt%, 10wt%, 15wt%, and an oxalate ion content of 50g/L, 100g/L, 200g/L, 290g/L, etc.
In this embodiment, as an embodiment of the present invention, the preparation process of the electrolyte may include: at least one of oxalic acid and oxalate is mixed with sulfuric acid or sulfuric acid containing salt according to a certain proportion, and water is added or not added according to actual requirements to obtain electrolyte with the concentration of oxalate ions of 40 g-300 g/L. Wherein, the salt contained in the sulfuric acid can be at least one of sodium oxalate and sodium sulfate.
In this embodiment, as another embodiment of the present invention, the preparation process of the electrolyte may include: adding oxalic acid and/or oxalate to the initial electrolyte solution to obtain an electrolyte. Wherein the oxalate may include at least one of sodium oxalate, potassium oxalate and ammonium oxalate.
The initial electrolyte solution may be: 0.1-1 wt% of dilute sulphuric acid and 5-28 wt% of sodium oxalate aqueous solution, namely the initial electrolyte solution is the mixed solution of dilute sulphuric acid and sodium oxalate aqueous solution. Wherein, H in dilute sulfuric acid 2 SO 4 0.1wt% to 1wt%, for example, 0.2wt%, 0.5wt%, 0.9wt%, etc.; na in sodium oxalate aqueous solution 2 C 2 O 4 5 to 28wt%, for example, 6, 15, 20, 25, 27wt%, etc.; the volume ratio of the dilute sulfuric acid to the sodium oxalate aqueous solution is 1:0.8 to 1.2, for example 1:1.
alternatively, the initial electrolyte solution may be: 0.1-2 wt% of sodium sulfate aqueous solution and 10-30 wt% of sodium oxalate aqueous solution. Wherein the volumes of the sodium sulfate aqueous solution and the sodium oxalate aqueous solution can be 1:0.8 to 1.2, for example 1:1. the concentration of the aqueous sodium sulfate solution may be 0.2wt%, 0.5wt%, 1wt%, 1.5wt%, 1.9wt%, etc., and the concentration of the aqueous sodium oxalate solution may be 11wt%, 15wt%, 20wt%, 25wt%, 29wt%, etc.
Alternatively, the initial electrolyte solution may be: 1wt% -5 wt% of sodium sulfate aqueous solution and 5wt% -20 wt% of oxalic acid aqueous solution. Wherein, the volume of the sodium sulfate aqueous solution and the oxalic acid aqueous solution can be 1:0.8 to 1.2, for example 1:1. the concentration of the aqueous sodium sulfate solution may be 2wt%, 3wt%, 4wt%, 4.5wt%, etc., and the concentration of the aqueous oxalic acid solution may be 6wt%, 10wt%, 15wt%, 19wt%, etc.
Alternatively, the initial electrolyte solution may be: 10 to 30wt% of a mixed solution of an aqueous sodium sulfate solution, for example, 15wt%, 20wt%, 25wt%, 29wt%.
For example, initial powerThe decomposing solution can contain 0.1wt% -1 wt% of H 2 SO 4 、5wt％～28wt％Na 2 C 2 O 4 、1wt％～5wt％Na 2 SO 4 And 5wt% to 20wt%/L H 2 C 2 O 4 。
S2: the electrolyte is divided into an anode side electrolyte and a cathode side electrolyte by a diaphragm, and graphene oxide and an antioxidant are added into the anode side electrolyte.
In this embodiment, the addition amount of the graphene oxide is 1wt% to 15wt% of the oxalate content in the anode side electrolyte. Such as 7wt%, 8wt%, etc.
In this embodiment, the antioxidant may include: sodium sulfite, dibutylphenol, sodium hydrogen sulfite, sodium thiosulfate, t-butyl p-hydroxyanisole, 2, 6-di-t-butyl-p-cresol, octadecyl beta (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, 2 '-methylenebis (4-ethyl-6-t-butylphenol), N' -hexamethylenebis-3 (3, 5-di-t-butyl-4-hydroxyphenyl) propionamide, 1,3, 5-tris (3, 5-di-t-butyl-4-hydroxyphenyl) isocyanate, 4-hydroxydodecanoylanilide, 4-hydroxyoctadecanoylanilide and p-t-butylphthalide.
S3: putting the anode and the cathode into the anode side electrolyte and the cathode side electrolyte respectively for electrolysis; wherein the anode is metallic tin and the cathode is an inert material.
In this embodiment, the anode current density may be 50 to 150A/m 2 E.g. 60, 70, 80, 85, 100, 120, 145A/m 2 And the like. The cathode current density may be 300 to 700A/m 2 E.g. 340, 400, 500, 600, 655A/m 2 And the like.
In this embodiment, the temperature of the electrolytic reaction may be 30 to 80 ℃, for example, 35, 40, 50, 60, 79 ℃ or the like; the electrolysis time may be 0.25 to 3 hours, e.g., 0.3, 1, 2, 2.5, 2.8 hours, etc.
In the embodiment, stirring can be carried out during the electrolysis, and the stirring speed can be 100-300 r/min,105, 120, 150, 200, 250 and 290r/min.
In this embodiment, the inert material may be one of a titanium rod and a graphite rod.
S4: and filtering the electrolyzed electrolyte to obtain a filter cake, and drying the filter cake to obtain the graphene-coated tin oxalate conductive material.
In this embodiment, step S4 may further include the steps of washing the filter cake, and drying the filter cake after washing.
In this embodiment, the drying may include drying under reduced pressure. Further, the temperature for the reduced pressure drying may be 30 to 80 ℃ such as 40 ℃, 50 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ and the like.
In this embodiment, the method may further include the steps of: and washing the obtained graphene coated tin oxalate conducting material. Wherein, the pulp can be washed for at least 1 to 3 times by using mixed solution of purified water and ethanol. The dosage relationship of the pure water and the ethanol in the mixture is 1-1.5: 0.1.
exemplary embodiment 2
The exemplary embodiment provides a preparation method of a graphene coated tin oxalate conductive material, and one basis of the technical concept of the method is that a stannous oxalate solid product is insoluble in dilute sulfuric acid and is easy to separate and purify; the principle of the preparation method is as follows:
and (3) anode reaction: sn (tin) 2+ +2e→Sn
And (3) cathode reaction: 2H 2 O+2e→2OH - +H 2 ↑
The main reaction: sn (tin) 2+ +(C 2 O 4 ) 2- →SnC 2 O 4 ↓
Fig. 1 shows a schematic flow chart of a preparation method of a graphene-coated tin oxalate conductive material of the present invention. As shown in fig. 1, the raw materials of the present invention include an electrolyte, metallic tin, an antioxidant, and graphene oxide; performing electrolysis under controlled conditions, performing solid-liquid separation after electrolysis, washing and drying the obtained solid to obtain G @ SnC product 2 O 4 . Further, electricity after solid-liquid separationThe electrolyte can be returned for further use.
Specifically, the preparation method may include the steps of:
a1: mixing sulfuric acid or sulfuric acid added with salt with oxalic acid or oxalate according to a certain proportion, adding water to dissolve until the concentration of oxalate ions is in the range of 40 g-300 g/L, and obtaining an electrolyte system.
A2: a proton membrane is assembled into a diaphragm electrolytic system, the electrolyte systems on both sides of a cathode and an anode are kept consistent, graphene oxide is added to the anode side in an amount which is 1 to 15 percent of the mass of oxalate in the electrolytic solution, an antioxidant is added, metal tin is used as the anode, an inert conductor material is used as the cathode, and the current density of the anode is 50 to 150A/m 2 The cathode current density is 300-700A/m 2 The stirring speed is 100-300 r/min, and the reaction is carried out for 0.25-5 h at the temperature of 25-80 ℃. After the reaction is finished, the slurry is subjected to solid-liquid separation, a filter cake is washed for 1 to 3 times, and the filter cake is dried under reduced pressure at the temperature of between 30 and 80 ℃ to obtain the G @ SnC 2 O 4 And (c) a complex.
In this example, in step A1 above, the sulfuric acid to which the salt is added may be: the volume ratio is 1:1, 0.1-1 wt% of dilute sulfuric acid and 5-28 wt% of sodium oxalate aqueous solution; or, the volume ratio is 1:1, a mixed solution of 0.1-2 wt% of sodium sulfate aqueous solution and 10-30 wt% of sodium oxalate aqueous solution; or, the volume ratio is 1:1 of a mixed solution of 1wt% -5 wt% of sodium sulfate aqueous solution and 5wt% -20 wt% of oxalic acid aqueous solution. Of course, the invention is not limited to this, but can also be the sulfuric acid with added salt after adding corresponding salt to the sulfuric acid solution, according to the actual situation to choose to add water or not to add water to adjust and get.
In this embodiment, in the step A1, the oxalate is at least one of sodium oxalate, potassium oxalate and ammonium oxalate.
In this embodiment, in the step A1, the concentration of oxalate ions is 40g to 300g/L, such as 50g/L, 60g/L, 80g/L, 120g/L, 200g/L, 250g/L, etc.; preferably, the concentration of the oxalate ions is 40 g-100 g/L.
In this embodiment, in the step A2, the amount of the graphene oxide added is 1% to 15% of the mass of oxalate in the anode-side electrolytic solution, and preferably, the amount of the graphene oxide added is 2% to 10%, for example, 3%, 5%, 6%, 9%, and the like.
In this embodiment, in the above step A2, the antioxidant may include at least one of sodium sulfite, dibutylphenol, sodium hydrogen sulfite, sodium thiosulfate, t-butyl p-hydroxyanisole, 2,6 di-t-butyl p-cresol, octadecyl beta (3, 5 di-t-butyl-4-hydroxyphenyl) propionate, 1,3 tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5 di-t-butyl-4-hydroxybenzyl) benzene, 2 '-methylenebis (4-ethyl-6-t-butylphenol), N' -hexamethylenebis-3 (3, 5 di-t-butyl-4-hydroxyphenyl) propionamide, 1,3, 5-tris (3, 5 di-t-butyl-4-hydroxyphenyl) isocyanate, 4-hydroxydodecanoic acid anilide, 4-hydroxyoctadecanoic acid anilide, and p-t-butyl catechol.
In this embodiment, in the step A2, the mass ratio of the antioxidant to the oxalate in the anolyte is 0.01% to 0.5%. Preferably, the mass ratio of the antioxidant to the oxalate is 0.01-0.1%.
In this embodiment, the anode used in the electrolysis process of the present invention may be a tin anode plate as shown in fig. 2, wherein (a) is a front view and (b) is a side view in fig. 2.
In this embodiment, in the step A2, the anode current density is 80 to 150A/m 2 The cathode current density is 300-700A/m 2 。
In this embodiment, in the step A2, the reaction stirring speed is 100 to 300r/min, the reaction temperature is 30 to 80 ℃, and the reaction time is 0.5 to 2 hours.
In this embodiment, in the step A2, the solution for cake washing may be a solution having a mass ratio of 1 to 1.5:0.1 of a mixture of purified water and ethanol, for example 1.1:0.1, 1.3:0.1, 1.4:0.1, etc.
In this embodiment, in the step A2, G @ SnC may be further processed 2 O 4 And (3) washing the compound, wherein the solution used for washing can be pure solution with the mass ratio of 1-1.5The mixed liquid of water and ethanol is beaten and washed for at least 1 to 3 times to remove electrolyte ions at G @ SnC 2 O 4 The residue of (2).
In the present embodiment, in the above step A2, G @ SnC 2 O 4 The temperature for decompression drying is 30-80 ℃, and the drying time is 12-48 h.
In this embodiment, in the step A2, the cathode inert conductor material is one of a titanium rod and a graphite rod. The cathode used in the electrolysis process of the present invention may be constructed as shown in FIG. 3.
In order that the above-recited two exemplary embodiments of the invention may be better understood, further description thereof with reference to specific examples is provided below.
Example 1
To a 500mL beaker was added 480mL of a mixture of 0.1wt% dilute sulfuric acid and 25wt% sodium sulfate in water at a volume ratio of 1 2 C 2 O 4 Fully dissolving, assembling a diaphragm electrolysis reaction system by using a proton membrane, keeping the electrolyte systems on both sides of a cathode and an anode consistent, adding 3g of graphene oxide and 0.01g of antioxidant to the anode side, wherein the antioxidant is prepared by compounding m (2, 6-di-tert-butyl-p-cresol) and m (p-tert-butyl catechol) = 0.5.
The tin metal block is used as an anode, two conjoined graphite rods with the diameter of phi 5.0mm are used as a cathode, the distance between the two electrodes is 80mm, and direct current is introduced to stir and carry out electrolytic reaction. Wherein the anode current density is 100A/m 2 Cathode current density 410A/m 2 The temperature of the electrolyte is 65 ℃, and the stirring-electrolysis reaction is carried out for 30min at the speed of 200 r/min.
Stopping liquid-solid separation after the reaction, pulping and washing for 3 times by using a mixed solution of purified water and ethanol (the mass ratio of the purified water to the ethanol is 1: 0.1), and then putting the product into a vacuum drying oven for drying for 12h at 60 ℃ to obtain graphene coated G @ SnC 2 O 4 And (c) a complex. Dissolving quantitative SnC with dilute hydrochloric acid in nitrogen atmosphere glove box 2 O 4 Then using starch-potassium iodide solution as indicator and using potassium iodate to make chemical titration analysis, and converting to obtain SnC 2 O 4 Content, G @ SnC 2 O 4 Contains 16.3 percent of tin.
Graphene coated G @ SnC prepared in this embodiment 2 O 4 The transmission electron micrograph of the composite is shown in FIG. 4.
The cathode material is prepared by coating according to the method in the following exemplary embodiment 4, a CR2032 type button cell is assembled by taking sodium foil as a counter electrode, the electrochemical performance of the button cell is tested under the condition of 0.5C and the voltage range of 0.1-3.8V, and the initial specific discharge capacity of the button cell can reach 356.5mAhg -1 。
Example 2
480mL of a mixed solution prepared by mixing 0.1wt% of dilute sulfuric acid and 25wt% of an aqueous sodium sulfate solution at a volume ratio of 1 2 C 2 O 4 And 30g of H 2 C 2 O 4 Fully dissolving, assembling a diaphragm electrolysis reaction system by using a proton membrane, keeping the electrolyte systems on both sides of a cathode and an anode consistent, adding 2.2g of graphene oxide to the anode side, and adding 0.015g of antioxidant, wherein the antioxidant is prepared by compounding m (dibutyl phenol) m (4-hydroxy octadecanoic acid acyl aniline catechol) = 0.5.
The tin metal block is used as an anode, two conjoined titanium rods with the diameter of phi 5.0mm are used as cathodes, the distance between the electrodes is 80mm, and direct current is introduced to stir and carry out electrolytic reaction. Anode current density 105A/m 2 Cathode current density 400A/m 2 The temperature of the electrolyte is 45 ℃, and the stirring-electrolysis reaction is carried out for 40min at the speed of 250 r/min.
Stopping reaction, carrying out liquid-solid separation, pulping and washing for 2 times by using a mixed solution of purified water and ethanol (the mass ratio of the purified water to the ethanol is 1.1), and then putting the product into a vacuum drying oven to dry for 18 hours at 70 ℃ to obtain graphene coated G @ SnC 2 O 4 And (c) a complex. Dissolving quantitative SnC with dilute hydrochloric acid in nitrogen atmosphere glove box 2 O 4 Then using starch-potassium iodide solution as indicator and using potassium iodate to make chemical titration analysis, and converting to obtain SnC 2 O 4 Content, G @ SnC 2 O 4 Contains 15.9 percent of tin.
The cathode material was coated according to the method of the following exemplary embodiment 4, and assembled into a CR2032 button cell using sodium foil as a counter electrode, and the electrochemical performance was tested under 0.5C condition and in a voltage range of 0.1 to 3.8V, and the initial specific discharge capacity of the cell was up to 366.1mAh/g, and the rate performance is shown in fig. 6.
Example 3
480mL of 27wt% aqueous sodium sulfate solution was added to a 500mL beaker, followed by 40gH 2 C 2 O 4 Fully dissolving to form an electrolyte system, assembling a diaphragm electrolysis reaction system by using a proton membrane, keeping the electrolyte system on both sides of a cathode and an anode consistent, adding 3.5g of graphene oxide to the anode side, and adding 0.015g of antioxidant, wherein the antioxidant is prepared by compounding m (2, 6 di-tert-butyl-p-cresol): m (2, 2' -methylene bis (4-ethyl-6 tert-butylphenol)) = 0.5.
The tin metal block is used as an anode, two conjoined titanium rods with the diameter of phi 5.0mm are used as cathodes, the distance between the electrodes is 80mm, and direct current is introduced to stir and carry out electrolytic reaction. Anode current density 110A/m 2 Cathode current density 400A/m 2 And the temperature of the electrolyte is 50 ℃, and the stirring at 210r/min is carried out for 50min.
And (2) stopping reaction, performing liquid-solid separation, pulping and washing for 3 times by using a mixed solution of purified water and ethanol (the mass ratio of the purified water to the ethanol is 1: 0.1), and then putting the product into a vacuum drying oven to be dried for 24 hours at 65 ℃ to obtain the graphene coated G @ SnC 2 O 4 And (c) a complex. Dissolving quantitative SnC with dilute hydrochloric acid in nitrogen atmosphere glove box 2 O 4 Then using starch-potassium iodide solution as indicator and using potassium iodate to make chemical titration analysis, and converting to obtain SnC 2 O 4 Content, G @ SnC 2 O 4 16.1 percent of tin.
The cathode material is prepared by coating according to the method in the following exemplary embodiment 4, a CR2032 type button cell is assembled by using sodium foil as a counter electrode, the electrochemical performance of the button cell is tested under the condition of 0.5C and in the voltage range of 0.1 to 3.8V, and the initial specific discharge capacity of the button cell can reach 362.9mAh/g.
Example 4
Adding a mixture of the following materials in a volume ratio of 1: 0.1% by weight of 1, a 25% by weight aqueous solution of sodium sulfate in a volume of 480mL, and then 40g of H 2 C 2 O 4 Fully dissolved to form an electrolyte system. Assembled into a diaphragm by a proton membraneIn the membrane electrolysis reaction system, electrolyte systems on the cathode side and the anode side are kept consistent, 2.8g of graphene oxide is added to the anode side, and 0.012g of antioxidant is added, wherein the antioxidant is formed by compounding m (2, 6 di-tert-butyl-p-cresol) and m (dibutyl phenol) = 0.5.
Using a tin metal block as an anode, two connected graphite rods with the diameter of 5.0mm as cathodes, leading direct current to stir and carry out electrolytic reaction with the electrode spacing of 80mm, and leading the current density of the anode to be 105A/m 2 Cathode current density 405A/m 2 The temperature of the electrolyte is 55 ℃, and stirring-electrolysis reaction is carried out for 60min at the speed of 180 r/min.
Stopping reaction, carrying out liquid-solid separation, pulping and washing for 2 times by using a mixed solution of purified water and ethanol (the mass ratio of the purified water to the ethanol is 1.1), and then drying the product in a vacuum drying oven at 75 ℃ for 20 hours to obtain graphene coated G @ SnC 2 O 4 And (3) a compound. Dissolving quantitative SnC with dilute hydrochloric acid in nitrogen atmosphere glove box 2 O 4 Then using starch-potassium iodide solution as indicator and using potassium iodate to make chemical titration analysis, and converting to obtain SnC 2 O 4 Content, G @ SnC 2 O 4 16.5 percent of tin.
According to the method in the following exemplary embodiment 4, a negative electrode material is prepared by coating, a CR2032 type button cell is assembled by taking sodium foil as a counter electrode, the electrochemical performance of the button cell is tested under the condition of 0.5C and in the voltage range of 0.1-3.8V, and the initial specific discharge capacity of the button cell can reach 353.9mAh/g.
Example 5
Adding 5wt% aqueous sodium sulfate solution and 15wt% to a 500mL vessel 2 C 2 O 4 Aqueous solution, the volume ratio of the two is 1 2 C 2 O 4 Fully dissolved to form an electrolyte system. A proton membrane is assembled into a diaphragm electrolysis reaction system, electrolyte systems on both sides of a cathode and an anode are kept consistent, 3.3g of graphene oxide is added to the anode side, an antioxidant is added, and 0.018g of the antioxidant is added, wherein the antioxidant is prepared by compounding m (dibutyl phenol) m (2, 2' -methylene bis (4-ethyl-6-tert-butyl phenol)) = 0.5. Wherein the mixture is composed of 5wt% sodium sulfate aqueous solution and 15% 2 C 2 O 4 The aqueous solution is mixed according to the volume ratio of 1.
The tin metal block is used as an anode, two graphite rods with a diameter of 5.0mm are connected to be used as a cathode, the distance between the electrodes is 80mm, and direct current is introduced to stir and carry out electrolytic reaction. Anode current density 110A/m 2 Cathode current density 405A/m 2 The temperature of the electrolyte is 60 ℃, and the stirring-electrolysis reaction is carried out for 35min at the speed of 280 r/min.
Stopping liquid-solid separation after the reaction, beating and washing for 3 times by using a mixed solution of purified water and ethanol in a mass ratio of 1.1, and then drying the product in a vacuum drying oven at 50 ℃ for 15 hours to obtain graphene coated G @ SnC 2 O 4 And (c) a complex. Dissolving quantitative SnC with dilute hydrochloric acid in nitrogen atmosphere glove box 2 O 4 Then using starch-potassium iodide solution as indicator and using potassium iodate to make chemical titration analysis, and converting to obtain SnC 2 O 4 Content, G @ SnC 2 O 4 16.0 percent of tin.
The cathode material is prepared by coating according to the method in the following exemplary embodiment 4, a CR2032 type button cell is assembled by taking sodium foil as a counter electrode, the electrochemical performance of the button cell is tested under the condition of 0.5C and the voltage range of 0.1-3.8V, and the initial specific discharge capacity of the button cell can reach 352.5mAh/g.
Comparative example 1
A200 mL round-bottomed flask was charged with 0.4g of oxalic acid, 3g of graphene oxide and 100mL of distilled water, and the mixture was dissolved with stirring. Preparing 50mL of solution from 0.45g of stannous sulfate, slowly dropwise adding the solution into the oxalic acid solution system, reacting for 3h at 80 ℃, cooling to room temperature, performing solid-liquid separation by a centrifugal method, pulping and washing a filter cake for 3 times by pure water until the pH of a washing solution is = 6-7, and drying the solid for 12h at 80 ℃ in a vacuum drying oven to obtain graphene coated G @ SnC 2 O 4 And (5) producing the product. The results show that the coating G @ SnC 2 O 4 Contains 16.9 percent of tin.
The composite cathode is assembled into a CR2032 type button cell, the electrochemical performance of the button cell is tested under the condition of 0.5C and the voltage range of 0.1-3.8V, and the initial discharge specific capacity of the button cell can reach 356.3mAh/g.
Comparative example 2
0.4g of oxalic acid and 0.28g of oxidizing agent were added to a 200mL three-necked flaskAdding 3g of graphene oxide and 100mL of distilled water into stannous powder, stirring for dissolving, adding 0.01g of antioxidant, compounding the antioxidant by m (2, 6-di-tert-butyl-p-cresol) and m (p-tert-butyl catechol) =0.5, adding 0.5% of stannous sulfate (calculated by stannous oxide), slowly heating to 100 ℃, and reacting for 7 hours. And (3) stopping liquid-solid separation after the reaction, pulping and washing for 3 times by using a mixed solution of purified water and ethanol 1.1 (mass ratio) until the pH of the filtrate is approximately equal to 6-7, and then putting the product into a vacuum drying oven to dry for 12 hours at 60 ℃ to obtain graphene coated G @ SnC 2 O 4 And (c) a complex. The result shows that the graphene is coated with G @ SnC 2 O 4 Contains 17.1% of tin.
The composite cathode is assembled into a CR2032 type button cell, the electrochemical performance of the button cell is tested under the condition of 0.5C and the voltage range of 0.1-3.8V, and the initial discharge specific capacity of the button cell can reach 349.8mAh/g.
Comparison of results of examples 1-5 and comparative examples 1-2 is shown in the following table, and it can be seen from the following table 1 that the graphene coated with G @ SnC prepared according to the present invention 2 Specific capacity of O negative electrode material in sodium ion battery is integrated with graphene coated G @ SnC prepared by traditional process 2 The specific capacity of the O negative electrode material is basically kept flat, and the specific capacity of the negative electrode material prepared in some embodiments is higher than that of the traditional process, which shows that the graphene prepared in the patent is coated with G @ SnC 2 The O negative electrode material has better sodium ion storage performance, and in addition, the graphene-coated G @ SnC is prepared by using a metallic tin one-step method 2 And the O product greatly reduces the production cost, is environment-friendly and energy-saving and is suitable for large-scale industrial production.
TABLE 1
Figure BDA0003662480120000111
Figure BDA0003662480120000121
FIG. 5A shows charge and discharge curves of example 2 and comparative example 1, FIG. 5B shows charge and discharge curves of example 3 and comparative example 1, and FIG. 5C shows an exampleFig. 5 shows the charge-discharge curves of examples 2 to 4 and comparative example 1, where o represents a point on the curve of example 2, a point on the curve of example 3, a point on the curve of example 4, and a point on the curve of comparative example 1. From the abscissa of FIGS. 5A to 5C, it can be seen that G @ SnC 2 The specific capacity of the O-based button sodium ion battery reaches more than 350mAh/g, and G @ SnC is displayed by the ordinate 2 The polarization of the O-button sodium ion cell is about 0.45V.
FIG. 6 shows the rate performance curve of example 2, and G @ SnC is known from FIG. 6 2 O 4 The CR2032 type sodium-ion button cell battery as the cathode active material has good rate capability.
Exemplary embodiment 3
The present exemplary embodiment provides a graphene-coated tin oxalate conductive material.
The conductive material is prepared by the preparation method of the graphene-coated tin oxalate conductive material of the above exemplary embodiment 1 or exemplary embodiment 2.
As can be seen from the following table 1 of the conductive material, the graphene coated G @ SnC prepared by the method 2 Specific capacity of O negative electrode material in sodium ion battery is integrally higher than that of graphene coated G @ SnC prepared by traditional process 2 The specific capacity of the O negative electrode material is high, and the graphene coated G @ SnC prepared by the patent is explained 2 The O negative electrode material has better sodium ion storage performance. In addition, with preparation of G @ SnC from stannous salt 2 Compared with the O process, the graphene-coated G @ SnC is prepared by using the metallic tin one-step method 2 The O process is simple, environment-friendly and suitable for large-scale industrial production.
Exemplary embodiment 4
The present exemplary embodiment provides a graphene-coated tin oxalate negative electrode material.
The negative electrode material can be prepared from the conductive material.
As one example, the method for preparing the anode material may include the steps of: ball-milling and mixing the conductive materials comprising acetylene black and polyvinylidene fluoride (PVDF) = 6-8 (mass ratio) = 1-1.5), coating N-methylpyrrolidone (NMP) serving as a dispersing agent and a solvent on a copper foil, and then cold-pressing at 10-40 MPa for 15-60 minutes to obtain the negative electrode material.
Of course, the method for preparing the conductive material into the negative electrode material is not limited to the above process, and may be other methods capable of realizing preparation of the negative electrode material by the technology in the art.
Exemplary embodiment 5
The present exemplary embodiment provides a battery.
The battery may include a graphene-coated tin oxalate negative electrode material as described above.
Alternatively, the negative electrode of the battery may comprise the graphene-coated tin oxalate conductive material as described above.
Although the present invention has been described above in connection with the exemplary embodiments and the accompanying drawings, it will be apparent to those of ordinary skill in the art that various modifications may be made to the above-described embodiments without departing from the spirit and scope of the claims.

Claims (10)

1. A preparation method of a graphene-coated tin oxalate conductive material is characterized by comprising the following steps:
separating the electrolyte into an anode side electrolyte and a cathode side electrolyte by using a diaphragm, and adding graphene oxide and an antioxidant into the anode side electrolyte; wherein the electrolyte is a dilute sulfuric acid electrolyte system and contains oxalate ions with the concentration of 40 g/L to 300 g/L;
putting the anode and the cathode into the anode side electrolyte and the cathode side electrolyte respectively for electrolysis; wherein, the anode is metallic tin, and the cathode is inert material;
and filtering the electrolyzed electrolyte to obtain a filter cake, and drying the filter cake to obtain the graphene-coated tin oxalate conductive material.
2. The method for preparing the graphene-coated tin oxalate conducting material according to claim 1, wherein the electrolyte comprises any one of the following mixed solutions:
mixed solution of dilute sulfuric acid and aqueous sodium oxalate solution, mixed solution of aqueous sodium oxalate solution and aqueous sodium sulfate solution, and H 2 C 2 O 4 A mixed solution of aqueous solutions.
3. The preparation method of the graphene-coated tin oxalate conducting material according to claim 1, wherein the addition amount of the graphene oxide is 1-15% of the mass of oxalate in the anode-side electrolyte.
4. The method for preparing a graphene-coated tin oxalate conductive material according to claim 1, wherein the electrolyte has a pH of 1 to 6 and further contains 0.5 to 16wt% of sulfate ions.
5. The method for preparing the graphene-coated tin oxalate conducting material according to claim 1, wherein the antioxidant comprises: sodium sulfite, dibutylphenol, sodium hydrogen sulfite, sodium thiosulfate, t-butyl p-hydroxyanisole, 2, 6-di-t-butyl-p-cresol, octadecyl beta (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, 2 '-methylenebis (4-ethyl-6-t-butylphenol), N' -hexamethylenebis-3 (3, 5-di-t-butyl-4-hydroxyphenyl) propionamide, 1,3, 5-tris (3, 5-di-t-butyl-4-hydroxyphenyl) isocyanate, 4-hydroxydodecanoylanilide, 4-hydroxyoctadecanoylanilide and p-t-butylphthalide.
6. The method for preparing the graphene-coated tin oxalate conductive material of claim 1, wherein the anode current density is 50-150A/m 2 The cathode current density is 300-700A/m 2 The temperature of the electrolysis is 30-80 ℃, and the time is 0.25-3 h.
7. The graphene-coated tin oxalate conductive material is characterized by being prepared by the preparation method of the graphene-coated tin oxalate conductive material according to any one of claims 1 to 6.
8. A graphene-coated tin oxalate negative electrode material, which is characterized in that the negative electrode material is prepared from the conductive material of claim 7.
9. The method for preparing the graphene-coated tin oxalate negative electrode material of claim 8 comprises the following steps:
and (2) mixing the conductive material, acetylene black and polyvinylidene fluoride according to a mass ratio of 6-8: 1 to 1.5:1, mixing to obtain a mixture;
adding a solvent into the mixture to prepare slurry, and then coating the slurry on a carrier;
and (4) cold pressing the coated carrier to obtain the negative electrode material for the battery.
10. A battery comprising the graphene-coated tin oxalate negative electrode material of claim 8.
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