CN112421016A - Non-aqueous potassium ion battery negative electrode material and preparation method thereof - Google Patents

Non-aqueous potassium ion battery negative electrode material and preparation method thereof Download PDF

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CN112421016A
CN112421016A CN202011389691.0A CN202011389691A CN112421016A CN 112421016 A CN112421016 A CN 112421016A CN 202011389691 A CN202011389691 A CN 202011389691A CN 112421016 A CN112421016 A CN 112421016A
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negative electrode
electrode material
ion battery
graphene foam
potassium ion
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何冬林
岳波
刘晶晶
王琼
胡德豪
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Sichuan New Lithium Energy Technology Co ltd
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Abstract

The invention discloses a non-aqueous potassium ion battery cathode material and a preparation method thereof. The three-dimensional graphene foam matrix in the negative electrode material is of a honeycomb structure, has a stable frame structure, a large specific surface area and excellent electronic and ionic conduction performances, can well buffer the volume expansion effect in the potassium ion releasing/embedding process, and has a potassium storage mechanism comprising a conversion reaction and a pseudo-capacitance behavior, so that the excellent potassium storage performance is shown; according to the preparation method, the three-dimensional graphene foam cathode modified by the antimony nanoparticles is prepared through in-situ exchange reaction, so that the antimony nanoparticles are uniformly dispersed on a graphene foam matrix, and the electrochemical cycling stability is improved.

Description

Non-aqueous potassium ion battery negative electrode material and preparation method thereof
Technical Field
The invention relates to the field of functional nano materials, in particular to a non-aqueous potassium ion battery cathode material and a preparation method thereof.
Background
The urgent need for large-scale utilization of renewable energy and the rising cost of lithium ion energy storage batteries are making urgent demands for the development of novel energy storage technologies with low cost. The nonaqueous potassium ion battery shows a great development prospect due to the following advantages: (1) the potassium resource reserves are abundant, the cost is low; (2) the weaker Lewis acid property compared to other alkali metal ions makes K+The electrolyte, the electrolyte and the electrode interface have larger transfer number and mobility; (3) k+Standard electrode potential ratio Na/K+lower/Na, with Li+the/Li is closer to (-2.93V, -2.71V, -3.04V, Vs.SHE), which means that the potassium ion battery has higher working voltage and energy density and has great prospect in the future energy storage field.
Nevertheless, K+Is large in size
Figure BDA0002812148460000011
Large volume expansion can be caused in the de-intercalation process, so that the cycle performance is poor; in addition, the carbon-based material has low specific capacity and cannot meet the use requirement.
Therefore, the development of a negative electrode material with high specific capacity and long cycle life is very important for the development of the potassium ion battery.
Disclosure of Invention
The invention aims to provide a non-aqueous potassium ion battery negative electrode material and a preparation method thereof.
The invention is realized by the following technical scheme:
a non-aqueous potassium ion battery negative electrode material is a three-dimensional graphene foam negative electrode material modified by antimony nanoparticles and is composed of three-dimensional graphene foam and antimony nanoparticles growing on the three-dimensional graphene foam.
The three-dimensional graphene foam matrix in the negative electrode material is of a honeycomb structure, has a stable frame structure, a large specific surface area and excellent electronic and ionic conduction performances, can well buffer the volume expansion effect in the potassium ion releasing/embedding process, and has an excellent cycle life and high specific capacity due to the fact that a potassium storage mechanism comprises a conversion reaction and a pseudocapacitance behavior.
Furthermore, the three-dimensional graphene foam is formed by assembling graphene bubbles and a three-dimensional graphite skeleton in situ, the number of graphene layers is 2-5, and the three-dimensional graphene foam belongs to the category of few graphene layers.
Further, the particle size of the antimony nanoparticles is 20-50 nm.
A preparation method of a non-aqueous potassium ion battery negative electrode material comprises the following steps:
s1, dissolving cobalt nitrate hexahydrate, ammonium sulfate and polyvinylpyrrolidone in a certain mass ratio in deionized water to prepare a mixed solution, grinding the dried product into powder, and filling the powder into a corundum crucible;
s2, placing the corundum crucible in a tubular furnace to react for a period of time in argon-hydrogen mixed atmosphere, and cooling the furnace to room temperature to obtain a product, namely the cobalt nanoparticle modified three-dimensional graphene foam;
s3, dissolving the cobalt nanoparticle modified three-dimensional graphene foam in a mixed solution of glycerol and methanol, adding antimony trichloride, stirring and mixing uniformly, transferring the obtained solution into a reaction kettle, sealing and reacting for a period of time, cooling the reaction kettle to room temperature, cleaning the obtained precipitate with methanol, placing the precipitate in a tubular furnace, reacting for a period of time in an argon atmosphere, and cooling the tubular furnace to room temperature to obtain the antimony nanoparticle modified three-dimensional graphene foam cathode material.
According to the method, the antimony nano-particle modified three-dimensional graphene foam is prepared by adopting an antimony-cobalt in-situ exchange reaction, so that the antimony nano-particles are uniformly dispersed on a graphene foam matrix, and the electrochemical cycle stability is improved.
The potassium storage mechanism comprises a conversion reaction and a pseudocapacitance behavior, so that the potassium storage performance is excellent.
Further, in the step S1, the mass ratio of the cobalt nitrate hexahydrate to the ammonium sulfate to the polyvinylpyrrolidone is 1.4-1.6: 0.5-1.0: 1.
further, the conditions of the reaction in the argon-hydrogen mixed atmosphere in step S2 are:
heating to 250-350 ℃ at a heating rate of 2-5 ℃/min, and keeping the temperature for 1-2 h; then heating to 800-1000 ℃ at a heating rate of 4-6 ℃/min, and preserving heat for 2-3 h.
Further, in the argon-hydrogen mixed atmosphere in the step S2, the volume fraction of the hydrogen is 10 to 15%, and the volume fraction of the argon is 85 to 90%.
Further, the conditions of the post-sealing reaction of the reaction vessel in step S3 are:
heating to 100-150 ℃, and preserving heat for 10-15 h;
the reaction conditions in the tube furnace under argon atmosphere are as follows:
heating to 300-350 ℃, and preserving heat for 1-2 h.
Further, in the step S3, the mass ratio of the antimony trichloride to the cobalt nanoparticle modified three-dimensional graphene foam is 10-15: 1.
further, the volume ratio of glycerol to methanol in the step S3 is 5-7: 1.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the antimony nanoparticle modified three-dimensional graphene foam cathode provided by the invention has a stable three-dimensional frame structure, and the three-dimensional graphene foam can be kept stable in a potassium ion releasing/embedding process; meanwhile, the three-dimensional graphene foam can also be used as a conductive network, so that the transmission efficiency of electrons is improved; in addition, the three-dimensional graphene foam also has a large specific surface area, and can provide more reactive sites for electrochemical reaction.
2. According to the preparation method, the three-dimensional graphene foam cathode modified by the antimony nanoparticles is prepared through in-situ exchange reaction, so that the antimony nanoparticles are uniformly dispersed on a graphene foam matrix, and the electrochemical cycling stability is improved.
3. The three-dimensional graphene foam matrix can be prepared through one-step heat treatment, and compared with the traditional method, the preparation method is simple, low in cost and small in environmental pollution.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
fig. 1 is a transmission electron microscope image of a three-dimensional graphene foam cathode modified by antimony nanoparticles prepared in this example 1;
fig. 2 is a schematic diagram of potassium storage performance of the antimony nanoparticle modified three-dimensional graphene foam negative electrode prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1:
a preparation method of a non-aqueous potassium ion battery negative electrode material comprises the following steps:
s1, mixing the components in a mass ratio of 1.5: 0.5: 1, weighing cobalt nitrate hexahydrate, ammonium sulfate and polyvinylpyrrolidone (PVP, K30) and dissolving in deionized water to prepare a mixed solution, grinding a dried product into powder, and filling the powder into a corundum crucible;
s2, placing the corundum crucible in a tube furnace in a hydrogen-argon mixed atmosphere (H)2The volume ratio of/Ar is 1:9) is heated to 250 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 1 h; heating to 800 ℃ at the heating rate of 6 ℃/min, preserving heat for 2h, cooling the furnace to room temperature, and collecting a product to obtain cobalt nanoparticle modified three-dimensional graphene foam;
s3, dispersing 0.1g of cobalt nanoparticle modified three-dimensional graphene foam into a mixed solution of 42ml of glycerol and 7ml of methanol, adding 1.4g of antimony trichloride, stirring and mixing uniformly, transferring the obtained solution into a Teflon reaction kettle, sealing, placing the reaction kettle in an oven, heating to 120 ℃, and preserving heat for 10 hours; and after the temperature of the reaction kettle is reduced to room temperature, cleaning the obtained precipitate for 4-5 times by using methanol, then placing the precipitate in a tubular furnace, heating the precipitate to 300 ℃ in an argon atmosphere, preserving the heat for 1h, and cooling the tubular furnace to the room temperature to obtain the antimony nanoparticle modified three-dimensional graphene foam cathode material.
A transmission electron microscope image of the antimony nanoparticle modified three-dimensional graphene foam negative electrode material prepared in this embodiment is shown in fig. 1.
The antimony nanoparticle modified three-dimensional graphene foam negative electrode material prepared in the embodiment, conductive agent ketjen black and binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 7:2:1, ground uniformly, added with a proper amount of N-methyl pyrrolidone (NMP) to prepare slurry, and uniformly coated on a copper foil. Vacuum drying at 100 deg.C for 10 hr, and cutting into electrode plate with diameter of 10mm with a slicer. A metal potassium sheet is taken as a counter electrode, glass fiber is taken as a diaphragm, 1mol/L KFSI/DME is taken as electrolyte, and the CR2032 type button cell is assembled in an argon-protected glove box. And standing for 12h after the battery is assembled, and performing constant-current charge and discharge test by using a LAND CT2001A battery test system, wherein the test voltage is 0.01-2.5V, and the electrochemical potassium storage performance is shown in figure 2.
As can be seen from fig. 2: the prepared antimony nano-particle modified three-dimensional graphene foam negative electrode material still shows specific capacity as high as 450mAh/g after being circulated for 20 circles, is much higher than a graphite negative electrode (less than 279mAh/g), and has better circulation stability than the graphite negative electrode reported in the literature.
Example 2:
a preparation method of a non-aqueous potassium ion battery negative electrode material comprises the following steps:
s1, mixing the components in a mass ratio of 1.4: 0.8: 1, weighing cobalt nitrate hexahydrate, ammonium sulfate and polyvinylpyrrolidone (PVP, K30) and dissolving in deionized water to prepare a mixed solution, grinding a dried product into powder, and filling the powder into a corundum crucible;
s2, placing the corundum crucible in a tube furnace in a hydrogen-argon mixed atmosphere (H)2The volume ratio of/Ar is 1:9) is heated to 250 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 1 h; heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, cooling the furnace to room temperature, and collecting a product to obtain cobalt nanoparticle modified three-dimensional graphene foam;
s3, dispersing 0.1g of cobalt nanoparticle modified three-dimensional graphene foam into a mixed solution of 42ml of glycerol and 7ml of methanol, adding 1.4g of antimony trichloride, stirring and mixing uniformly, transferring the obtained solution into a Teflon reaction kettle, sealing, placing the reaction kettle in an oven, heating to 120 ℃, and preserving heat for 10 hours; and after the temperature of the reaction kettle is reduced to room temperature, cleaning the obtained precipitate for 4-5 times by using methanol, then placing the precipitate in a tubular furnace, heating the precipitate to 300 ℃ in an argon atmosphere, preserving the heat for 1h, and cooling the tubular furnace to the room temperature to obtain the antimony nanoparticle modified three-dimensional graphene foam cathode material.
Example 3:
a preparation method of a non-aqueous potassium ion battery negative electrode material comprises the following steps:
s1, mixing the components in a mass ratio of 1.5: 0.5: 1, weighing cobalt nitrate hexahydrate, ammonium sulfate and polyvinylpyrrolidone (PVP, K30) and dissolving in deionized water to prepare a mixed solution, grinding a dried product into powder, and filling the powder into a corundum crucible;
s2, placing the corundum crucible in a tube furnace in a hydrogen-argon mixed atmosphere (H)2The volume ratio of/Ar is 2:8) is heated to 300 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 1 h; then heating to 800 ℃ at the heating rate of 6 ℃/min, preserving the heat for 2 hours, and collecting the product after the temperature of the furnace is reduced to the room temperatureObtaining cobalt nanoparticle modified three-dimensional graphene foam;
s3, dispersing 0.1g of cobalt nanoparticle modified three-dimensional graphene foam into a mixed solution of 42ml of glycerol and 7ml of methanol, adding 1.3g of antimony trichloride, stirring and mixing uniformly, transferring the obtained solution into a Teflon reaction kettle, sealing, placing the reaction kettle in an oven, heating to 100 ℃, and preserving heat for 10 hours; and after the temperature of the reaction kettle is reduced to room temperature, cleaning the obtained precipitate for 4-5 times by using methanol, then placing the precipitate in a tubular furnace, heating the precipitate to 300 ℃ in an argon atmosphere, preserving the heat for 1h, and cooling the tubular furnace to the room temperature to obtain the antimony nanoparticle modified three-dimensional graphene foam cathode material.
Example 4:
a preparation method of a non-aqueous potassium ion battery negative electrode material comprises the following steps:
s1, mixing the components in a mass ratio of 1.6: 1.0: 1, weighing cobalt nitrate hexahydrate, ammonium sulfate and polyvinylpyrrolidone (PVP, K30) and dissolving in deionized water to prepare a mixed solution, grinding a dried product into powder, and filling the powder into a corundum crucible;
s2, placing the corundum crucible in a tube furnace in a hydrogen-argon mixed atmosphere (H)2The volume ratio of/Ar is 1:9) is heated to 250 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 1 h; heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, cooling the furnace to room temperature, and collecting a product to obtain cobalt nanoparticle modified three-dimensional graphene foam;
s3, dispersing 0.1g of cobalt nanoparticle modified three-dimensional graphene foam into a mixed solution of 42ml of glycerol and 7ml of methanol, adding 1.4g of antimony trichloride, stirring and mixing uniformly, transferring the obtained solution into a Teflon reaction kettle, sealing, placing the reaction kettle in an oven, heating to 100 ℃, and preserving heat for 15 hours; and after the temperature of the reaction kettle is reduced to room temperature, cleaning the obtained precipitate for 4-5 times by using methanol, then placing the precipitate in a tubular furnace, heating the precipitate to 300 ℃ in an argon atmosphere, preserving the heat for 1h, and cooling the tubular furnace to the room temperature to obtain the antimony nanoparticle modified three-dimensional graphene foam cathode material.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The non-aqueous potassium ion battery negative electrode material is characterized in that the negative electrode material is an antimony nanoparticle modified three-dimensional graphene foam negative electrode material and is composed of three-dimensional graphene foam and antimony nanoparticles growing on the three-dimensional graphene foam.
2. The non-aqueous potassium ion battery negative electrode material as claimed in claim 1, wherein the three-dimensional graphene foam is formed by assembling graphene bubbles and a three-dimensional graphite skeleton in situ, and the number of graphene layers is 2-5.
3. The negative electrode material for the non-aqueous potassium ion battery according to claim 1, wherein the particle size of the antimony nanoparticles is 20 to 50 nm.
4. The method for producing the negative electrode material for a nonaqueous potassium-ion battery according to any one of claims 1 to 3, comprising the steps of:
s1, dissolving cobalt nitrate hexahydrate, ammonium sulfate and polyvinylpyrrolidone in a certain mass ratio in deionized water to prepare a mixed solution, grinding the dried product into powder, and filling the powder into a corundum crucible;
s2, placing the corundum crucible in a tubular furnace to react for a period of time in argon-hydrogen mixed atmosphere, and cooling the furnace to room temperature to obtain a product, namely the cobalt nanoparticle modified three-dimensional graphene foam;
s3, dissolving the cobalt nanoparticle modified three-dimensional graphene foam in a mixed solution of glycerol and methanol, adding antimony trichloride, stirring and mixing uniformly, transferring the obtained solution into a reaction kettle, sealing and reacting for a period of time, cooling the reaction kettle to room temperature, cleaning the obtained precipitate with methanol, placing the precipitate in a tubular furnace, reacting for a period of time in an argon atmosphere, and cooling the tubular furnace to room temperature to obtain the antimony nanoparticle modified three-dimensional graphene foam cathode material.
5. The method for preparing the negative electrode material of the non-aqueous potassium ion battery according to claim 4, wherein the mass ratio of the cobalt nitrate hexahydrate, the ammonium sulfate and the polyvinylpyrrolidone in step S1 is 1.4-1.6: 0.5-1.0: 1.
6. the method for producing the negative electrode material for the nonaqueous potassium ion battery according to claim 4, wherein the conditions for the reaction in the argon-hydrogen mixed atmosphere in step S2 are as follows:
heating to 250-350 ℃ at a heating rate of 2-5 ℃/min, and keeping the temperature for 1-2 h; then heating to 800-1000 ℃ at a heating rate of 4-6 ℃/min, and preserving heat for 2-3 h.
7. The method for preparing the negative electrode material of the nonaqueous potassium ion battery according to claim 4, wherein in the argon-hydrogen mixed atmosphere in the step S2, the volume fraction of hydrogen is 10-15%, and the volume fraction of argon is 85-90%.
8. The method for preparing the negative electrode material of the non-aqueous potassium ion battery according to claim 4, wherein the conditions of the post-sealing reaction of the reaction vessel in the step S3 are as follows:
heating to 100-150 ℃, and preserving heat for 10-15 h;
the reaction conditions in the tube furnace under argon atmosphere are as follows:
heating to 300-350 ℃, and preserving heat for 1-2 h.
9. The preparation method of the non-aqueous potassium ion battery negative electrode material as claimed in claim 4, wherein the mass ratio of antimony trichloride to cobalt nanoparticle-modified three-dimensional graphene foam in step S3 is 10-15: 1.
10. the method for preparing the negative electrode material of the non-aqueous potassium ion battery according to claim 4, wherein the volume ratio of glycerol to methanol in step S3 is 5-7: 1.
CN202011389691.0A 2020-12-02 2020-12-02 Non-aqueous potassium ion battery negative electrode material and preparation method thereof Pending CN112421016A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108550840A (en) * 2018-05-16 2018-09-18 东北大学秦皇岛分校 Three-dimensional netted carbon embeds antimony-containing alloy kalium ion battery negative material and preparation method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108550840A (en) * 2018-05-16 2018-09-18 东北大学秦皇岛分校 Three-dimensional netted carbon embeds antimony-containing alloy kalium ion battery negative material and preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHUANHUA HAN等: "Three-dimensional carbon network confined antimony nanoparticle anodes for high-capacity K-ion batteries", 《NANOSCALE》 *
PEIHANG LI等: "Facile synthesis of three-dimensional porous interconnected carbon matrix embedded with Sb nanoparticles as superior anode for Na-ion batteries", 《CHEMICAL ENGINEERING JOURNAL》 *

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