CN113224302A - Iron cyanamide material for realizing graphitized carbon coating by in-situ autocatalysis and application thereof - Google Patents

Iron cyanamide material for realizing graphitized carbon coating by in-situ autocatalysis and application thereof Download PDF

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CN113224302A
CN113224302A CN202110498121.3A CN202110498121A CN113224302A CN 113224302 A CN113224302 A CN 113224302A CN 202110498121 A CN202110498121 A CN 202110498121A CN 113224302 A CN113224302 A CN 113224302A
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iron
graphitized carbon
cyanamide
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autocatalysis
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CN113224302B (en
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李嘉胤
钱程
沈欢妍
黄剑锋
曹丽云
胡云飞
郭鹏辉
罗晓敏
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Shaanxi University of Science and Technology
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • 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
    • 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
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    • H01M4/00—Electrodes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract

The invention discloses a ferricyanamide material for realizing graphitized carbon coating by utilizing in-situ autocatalysis, wherein graphitized carbon is coated outside the ferricyanamide material, the graphitized carbon coated outside the ferricyanamide material is formed by in-situ autocatalysis of iron and carbon in the ferricyanamide, the coating thickness of the graphitized carbon is 1-5nm, and the particle size of the ferricyanamide material is 150-350 nm; the invention also protects a potassium ion battery cathode containing the graphitized carbon coated iron cyanamide material and a potassium ion battery containing the potassium ion battery cathode; because the technology makes self carbon separate out from self cyanamide iron particles to form graphitized carbon on the surface, the formed chemical bond is tightly combined, the structural stability of the product and the conductivity of the material are improved, the stability of the interface structure of the electrode material and the electrolyte is improved, the structure of the battery cathode material is more stable, the charge-discharge capacity is high, and the rate capability is excellent.

Description

Iron cyanamide material for realizing graphitized carbon coating by in-situ autocatalysis and application thereof
Technical Field
The invention belongs to the technical field of composite materials, relates to a composite electrode material, and particularly relates to a ferric cyanamide material for realizing graphitized carbon coating by utilizing in-situ autocatalysis and an application thereof.
Background
In recent years, due to the restriction of lithium resources, lithium ion batteries cannot meet the application requirements of large-scale energy storage, and finding energy storage equipment capable of replacing lithium batteries becomes a research hotspot in the field of energy storage. Researchers have therefore turned their eyes to alternatives to lithium, such as sodium, magnesium, aluminum, potassium, zinc, etc.; among them, sodium and potassium are abundant in reserves, belong to the same main group as lithium, and have chemical properties similar to lithium, so that a manufacturing method similar to a lithium ion battery can be adopted. At present, the room-temperature sodium ion charge-discharge battery is expected to be applied to the fields of large-scale energy storage, particularly smart power grids and the like. While potassium ion batteries have 4-point advantages over sodium ion batteries: 1) the standard electrode potential of potassium is-2.93V, which is close to-3.04V with lithium and higher than-2.71V with sodium, so that the potassium ion battery can have higher energy density; 2) the radius of potassium ions is larger, the radius of solvated ions is small, the conductivity of the electrolyte is higher, and the dynamic performance is better; 3) potassium and aluminum do not form an alloy, so lighter, less expensive aluminum can be used as the current collector of the negative electrode; 4) electrolyte salt (KPF) for potassium ion battery6) To the corresponding sodium salt (NaPF)6) It is cheaper. The above advantages promote potassium ion batteries to become sodium ion batteries, and then, the development of potassium ion batteries is fast in recent years. Similarly, the large size of potassium ions is difficult to directly embed into many lithium ion battery electrode materials to realize the process of electrochemical potassium storage, and thus the application prospect of the batteries is greatly limited. Therefore, how to compromise the high electrode material of the potassium ion batteryThe potassium storage capacity and the rapid and stable charge and discharge have become the research hot directions of numerous scholars in recent years, and the regulation of the charge and discharge mechanism of the potassium ion battery and the search of a new material structural system are considered to be the key for solving the problems.
The iron cyanamide compound has become a very potential battery cathode material due to the characteristics of low and flat charge-discharge potential platform, highly reversible reaction characteristic, high electrochemical reaction activity, large specific capacity and the like. However, the high reactivity causes severe damage to the ferricyanide material when its structure is completely rearranged during the electrochemical reaction, resulting in poor cycle performance. In particular, the structural destruction of iron cyanamide upon intercalation of potassium ions having a larger radius is more serious than that upon intercalation of sodium ions, and the capacity fading is also more severe. Therefore, a certain measure is needed to stabilize the structure of the iron cyanamide, and the volume expansion generated when potassium ions are inserted and removed is relieved, so that the iron cyanamide becomes an excellent potassium ion battery cathode material.
Carbon materials generally have excellent electrical conductivity and structural stability, and thus they often provide support for other active materials as one of the constituents of composite materials. Therefore, on the basis of the previous research, if an in-situ self-reduction formed carbon coating structure can be formed at the same time, the in-situ carbonization coated iron cyanamide material can be obtained. The electrochemical stability of the iron cyanamide in the potassium ion battery is expected to be effectively improved. Therefore, the successful preparation of the composite structure can expand a new material system of the potassium ion battery cathode material and promote the exploration work of the high-performance potassium ion battery cathode material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the iron cyanamide material which realizes graphitized carbon coating by in-situ autocatalysis and the application thereof, so that the material structure is more stable, the charge and discharge capacity is high, and the rate capability is excellent.
In order to achieve the purpose, the invention adopts the technical scheme that:
the ferric cyanamide material is coated with graphitized carbon by utilizing in-situ autocatalysis.
Further, the graphitized carbon coated outside the iron cyanamide material is realized by in-situ autocatalysis of iron and carbon in the iron cyanamide.
Preferably, the graphitized carbon coating thickness of the iron cyanamide material is 1-5 nm.
Preferably, the particle size of the iron cyanamide material is 150-350 nm.
Further, the invention provides a preparation method of the iron cyanamide material for realizing graphitized carbon coating by utilizing in-situ autocatalysis, which comprises the following steps:
the method comprises the following steps: mixing ferric ammonium oxalate with urea according to the mass ratio of 3:5, and grinding to fully mix the ferric ammonium oxalate with the urea to obtain a mixture A;
step two: in an inert gas atmosphere, firstly heating to 160 ℃ at a heating rate of 30 ℃/min, preserving heat for 1h, then heating to 600 ℃ at a heating rate of 5 ℃/min, stopping the procedure after heating, and taking out the product B which is the cyanamide iron under the condition that the temperature is reduced to room temperature;
step three: and (3) performing secondary sintering on the product B, rapidly heating to 400 ℃ at the speed of 5-10 ℃/min, then reducing the heating rate, heating to 500-550 ℃ at the speed of 1-5 ℃/min, preserving the heat for 0min-60min, stopping the subsequent procedure, and naturally cooling to room temperature to obtain a product C, namely the graphitized carbon-coated iron cyanamide.
Preferably, the grinding method in the first step is grinding for 20min by using a mortar.
Preferably, the reaction of step two is performed in a flowing argon or nitrogen atmosphere of 100 sccm.
Preferably, the reaction of step three is performed in a flowing argon, nitrogen or hydrogen atmosphere of 100 sccm.
Preferably, the reactor in the second step and the reactor in the third step are high-temperature tube furnaces.
The invention also protects the potassium ion battery cathode containing the graphitized carbon-coated iron cyanamide material.
The invention also protects a potassium ion battery containing the potassium ion battery cathode.
Compared with the prior art, the invention has the following beneficial effects:
the in-situ autocatalysis graphitized carbon-coated iron cyanamide material utilizes the iron cyanamide and the carbon in the iron cyanamide to form nitrogen-doped graphitized carbon by self-reduction, the temperature is rapidly raised by utilizing a tubular furnace in the early stage so as to coat the surface of the iron cyanamide, the internal structure is stable and unchanged, when the iron cyanamide is coated by the graphitized carbon, the direct contact between an electrode material and an electrolyte can be reduced, the side reaction between the material and the electrolyte is reduced, the resistance of an interface film is reduced, the conductivity of the material is improved by the graphitized carbon on the surface, the stability of the interface structure between the electrode material and the electrolyte is improved, and the cycle performance of a battery is improved;
because the technology enables self carbon to be separated out from the self cyanamide iron particles to form graphitized carbon on the surface, the formed chemical bonds are tightly combined, and the structural stability of the product is greatly improved; the obtained product has extremely high potassium ion storage performance, and the multiplying power and the cycle performance of the battery are improved.
Drawings
FIG. 1 is the XRD pattern of the product of example 1
FIG. 2 is a TEM image of the product of example 1
FIG. 3 is a TEM image of the product of example 1
FIG. 4 is a graph showing the cycle characteristics of the negative electrode material for a battery prepared from the product of example 1
FIG. 5 is a graph of rate performance of battery negative electrode materials prepared from the product of example 1
FIG. 6 is an EM image of the product obtained in example 2
FIG. 7 is a graph showing the cycle characteristics of the negative electrode material for a battery prepared from the product of example 2
FIG. 8 is a TEM image of the product obtained in comparative example 1
FIG. 9 is a graph showing the cycle characteristics of the negative electrode material for a battery prepared from the product of comparative example 1
FIG. 10 is a graph showing the cycle characteristics of the negative electrode material for a battery prepared in comparative example 2
Detailed Description
Example 1:
the method comprises the following steps: taking 1g of ammonium ferric oxalate salt and 1.67g of urea, and mixing and grinding in a glass mortar for 20min to obtain a mixture A;
step two: transferring the mixture A into a quartz crucible, placing the quartz crucible into a tubular furnace, heating to 160 ℃ at the heating rate of 30 ℃/min in the flowing argon atmosphere of 100sccm, preserving the heat for 1h, heating to 600 ℃ at the heating rate of 5 ℃/min, cooling, and taking out to obtain a product B;
step three: and (3) performing secondary sintering on the product B in a flowing argon atmosphere of 100sccm, heating to 400 ℃ at a speed of 10 ℃/min, reducing the heating rate, heating to 550 ℃ at a speed of 5 ℃/min, preserving the temperature for 30min, cooling, and taking out to obtain a product C, namely the graphitized carbon-coated iron cyanamide.
The product C of example 1 was analyzed by a Japanese science D/max2000 PCX-ray diffractometer, and the XRD of the product obtained in example 1 is shown in figure 1; observing the sample under a scanning electron microscope, as shown in figure 2; FIG. 3 is a 20nmTEM plot of the sample; from fig. 2 and fig. 3, it can be seen that the graphitized carbon is coated on the surface of the iron cyanamide, the binding is tight and uniform, the coating thickness is about 3nm, the particle size is about 200nm, and the structure of the material gradually trends to be spherical from polyhedron.
The product obtained in example 1 was prepared into a button type potassium ion battery, and the specific encapsulation steps were as follows: uniformly grinding active powder, a conductive agent (Super P), conductive graphite, an adhesive (carboxymethyl cellulose CMC) and polyacrylic acid (PAA) according to the mass ratio of 8:0.5:0.5:0.5:0.5 to prepare slurry, uniformly coating the slurry on a copper foil by using a film coater, and drying for 12 hours at 80 ℃ in a vacuum drying oven; then assembling the electrode plates into a potassium ion half-cell, performing constant-current charge-discharge test on the cell by adopting a Xinwei electrochemical workstation, wherein the test voltage is 0.01V-3.0V, assembling the obtained material into a button cell to test the performance of the potassium ion cell cathode material, and as shown in a cycle performance test of fig. 4, the cell shows 728mAh/g capacity under the current density of 100mA/g, and still has 572mAh/g capacity after 100 circles, so that the material has excellent cycle performance and charge-discharge capacity; FIG. 5 is a graph of rate capability, and it can be seen from FIG. 5 that the graphitized carbon-coated iron cyanamide composite material synthesized by heat preservation at 550 ℃ for 30min is relatively stable in result and is beneficial to intercalation/deintercalation of potassium ions in the electrochemical reaction.
Example 2:
the method comprises the following steps: taking 0.6g of ammonium ferric oxalate and 1g of urea, and mixing and grinding in a glass mortar for 20min to obtain a mixture A;
step two: transferring the mixture A into a quartz crucible, placing the quartz crucible into a tubular furnace, heating to 160 ℃ at the heating rate of 30 ℃/min in the flowing nitrogen atmosphere of 100sccm, preserving the heat for 1h, heating to 600 ℃ at the heating rate of 5 ℃/min, cooling, and taking out to obtain a product B;
step three: and (3) taking the product B to perform secondary sintering in a flowing nitrogen atmosphere of 100sccm, heating to 400 ℃ at a speed of 8 ℃/min, reducing the heating rate, heating to 500 ℃ at a speed of 3 ℃/min, preserving the heat for 60min, cooling and taking out to obtain a product C, namely the graphitized carbon-coated iron cyanamide.
FIG. 6 is a SEM image of the product of example 2, wherein the coating thickness of the material C is about 2nm and the particle size is about 250nm, and the product of example 2 is prepared into a button type potassium ion battery by the following specific packaging steps: uniformly grinding active powder, a conductive agent (Super P), conductive graphite, an adhesive (carboxymethyl cellulose CMC) and polyacrylic acid (PAA) according to the mass ratio of 8:0.5:0.5:0.5:0.5 to prepare slurry, uniformly coating the slurry on a copper foil by using a film coater, and drying for 12 hours at 80 ℃ in a vacuum drying oven. And then assembling the electrode plates into a potassium ion half-cell, performing constant-current charge-discharge test on the cell by adopting a Xinwei electrochemical workstation, testing the voltage at 0.01V-3.0V, assembling the obtained material into a button cell, and testing the performance of the potassium ion cell cathode material, wherein the cell shows the capacity of 400mAh/g under the current density of 100mA/g and has the capacity of 230mAh/g after 100 circles of circulation as shown in a circulation performance test of fig. 7.
Example 3:
the method comprises the following steps: taking 0.9g of ammonium ferric oxalate and 1.5g of urea, and mixing and grinding in a glass mortar for 20min to obtain a mixture A;
step two: transferring the mixture A into a quartz crucible, placing the quartz crucible into a tubular furnace, heating to 160 ℃ at the heating rate of 30 ℃/min in flowing argon of 100sccm, preserving the heat for 1h, heating to 600 ℃ at the heating rate of 5 ℃/min, cooling, and taking out to obtain a product B;
step three: and (3) carrying out secondary sintering on the product B in a flowing argon atmosphere of 100sccm, heating to 400 ℃ at a speed of 10 ℃/min, reducing the heating rate, heating to 530 ℃ at a speed of 5 ℃/min, preserving the temperature for 50min, cooling, and taking out to obtain a product C, namely the graphitized carbon-coated iron cyanamide, wherein the coating thickness of the material C is about 5nm, and the particle size is about 150 nm.
Example 4:
the method comprises the following steps: taking 0.9g of ammonium ferric oxalate and 1.5g of urea, and mixing and grinding in a glass mortar for 20min to obtain a mixture A;
step two: transferring the mixture A into a quartz crucible, placing the quartz crucible into a tubular furnace, heating to 160 ℃ at the heating rate of 30 ℃/min in flowing argon of 100sccm, preserving the heat for 1h, heating to 600 ℃ at the heating rate of 5 ℃/min, cooling, and taking out to obtain a product B;
step three: and (3) performing secondary sintering on the product B in a flowing nitrogen atmosphere of 100sccm, heating to 400 ℃ at a speed of 5 ℃/min, reducing the heating rate, heating to 550 ℃ at a speed of 1 ℃/min, cooling, and taking out to obtain a product C, namely the graphitized carbon-coated iron cyanamide, wherein the coating thickness of the material C is about 1nm, and the particle size is about 350 nm.
Comparative example 1:
the method comprises the following steps: taking 1.2g of ammonium ferric oxalate and 2g of urea, and mixing and grinding in a glass mortar for 20min to obtain a mixture A;
step two: transferring the mixture A into a quartz crucible, placing the quartz crucible into a tubular furnace, heating to 160 ℃ at the heating rate of 30 ℃/min in the flowing argon atmosphere of 100sccm, preserving the heat for 1h, heating to 600 ℃ at the heating rate of 5 ℃/min, cooling, and taking out to obtain a product B;
step three: and (3) taking the product B to perform secondary sintering in a flowing hydrogen atmosphere of 150sccm, directly heating to 550 ℃ at the speed of 5 ℃/min, preserving the temperature for 60min, cooling and taking out to obtain a product C, namely the graphitized carbon-coated iron cyanamide.
FIG. 8 is a TEM image of the product obtained in comparative example 1, the coating thickness of the material C is about 10nm, the particle size is about 100nm, and the product is prepared into a button type potassium ion battery, and the specific packaging steps are as follows: uniformly grinding active powder, a conductive agent (Super P), conductive graphite, an adhesive (carboxymethyl cellulose CMC) and polyacrylic acid (PAA) according to the mass ratio of 8:0.5:0.5:0.5:0.5 to prepare slurry, uniformly coating the slurry on a copper foil by using a film coater, and drying for 12 hours at 80 ℃ in a vacuum drying oven. And then assembling the electrode plates into a potassium ion half cell, performing constant-current charge and discharge test on the cell by adopting a Xinwei electrochemical workstation, wherein the test voltage is 0.01V-3.0V, assembling the obtained material into a button cell to test the performance of the potassium ion cell cathode material, and fig. 9 is a cycle performance diagram of a product obtained in a comparative example 2, wherein the first discharge reaches 540mAh/g-1 at the current density of 0.1A/g-1, but the capacity is always reduced along with the cycle, which indicates that a sample synthesized under the condition can not bear potassium intercalation/potassium deintercalation in the electrochemical reaction process, so that the structure of the material is damaged.
Comparative example 2:
the product B which is not subjected to secondary sintering is prepared into a potassium ion half cell to be assembled, and a cycle performance test is carried out, so that the result is that although the first discharge capacity of the cyanamide iron material in the potassium ion cell reaches 568mAh/g < -1 >, the cycle performance is not good, and the capacity is quickly attenuated as shown in a figure 10.
By combining the embodiment, the comparative example and the attached drawings, it can be seen that when the iron cyanamide is coated by the graphitized carbon, the direct contact between the electrode material and the electrolyte can be reduced, the side reaction between the material and the electrolyte can be reduced, the resistance of the interfacial film can be reduced, the surface structure of the material can be more stable, and the cycle performance of the battery can be improved.

Claims (6)

1. The ferric cyanamide material coated with graphitized carbon by utilizing in-situ autocatalysis is characterized in that the outside of the ferric cyanamide material is coated with graphitized carbon.
2. The iron cyanamide material for achieving graphitization carbon coating by in situ autocatalysis as claimed in claim 1 wherein the graphitized carbon coated outside of the iron cyanamide material is formed by in situ autocatalysis of iron and carbon in the iron cyanamide.
3. The iron cyanamide material for achieving graphitization carbon coating by in-situ autocatalysis according to claim 2 wherein the thickness of the graphitized carbon coating of the iron cyanamide material is 1-5 nm.
4. The iron cyanamide material for achieving graphitization carbon coating by in-situ autocatalysis as claimed in claim 2, wherein the particle size of the iron cyanamide material is 150-350 nm.
5. A negative electrode for potassium ion batteries, characterized by containing the graphitized carbon-coated iron cyanamide material described in any one of claims 1 to 4.
6. A potassium ion battery comprising the potassium ion battery negative electrode according to claim 3.
CN202110498121.3A 2021-05-08 2021-05-08 Iron cyanamide material for realizing graphitized carbon coating by in-situ autocatalysis and application thereof Active CN113224302B (en)

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