CN117174848A - Preparation method and application of pomegranate seed-shaped nanocomposite for potassium ion battery - Google Patents
Preparation method and application of pomegranate seed-shaped nanocomposite for potassium ion battery Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 71
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 51
- 235000014360 Punica granatum Nutrition 0.000 title claims abstract description 45
- 241000219991 Lythraceae Species 0.000 title claims abstract description 44
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000002070 nanowire Substances 0.000 claims abstract description 30
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 23
- 239000010439 graphite Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 15
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003466 welding Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000004108 freeze drying Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 22
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000006245 Carbon black Super-P Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- 239000007849 furan resin Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 abstract description 4
- 239000000110 cooling liquid Substances 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 55
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 16
- 229910052721 tungsten Inorganic materials 0.000 description 16
- 239000010937 tungsten Substances 0.000 description 16
- 238000010891 electric arc Methods 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000009777 vacuum freeze-drying Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
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- 238000009831 deintercalation Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 244000294611 Punica granatum Species 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
A preparation method and application of a pomegranate seed-shaped nanocomposite for a potassium ion battery are provided, and the preparation method comprises the following steps: uniformly mixing flake graphite powder and silicon powder, and pressing into a mixed raw material cake; putting the mixed raw material cake into a graphite crucible of a vacuum direct current arc furnace, sealing the vacuum direct current arc furnace, vacuumizing, filling protective gas, turning on an electric welding machine to perform discharge arc striking reaction, cooling liquid nitrogen, passivating by using air, and collecting Si/SiC nanowire materials; dissolving a carbon source in absolute ethyl alcohol, and then adding a Si/SiC nanowire material; heating in water bath, maintaining the temperature, freeze-drying, grinding, and pyrolyzing in a tubular furnace under argon atmosphere to obtain the pomegranate seed-shaped Si/SiC/C nanocomposite. The advantages are that: the preparation method is simple in process and low in cost, is used for preparing the anode material of the potassium ion battery, can better slow down the volume expansion of Si, and reduces the generation of an unstable SEI film so as to improve the discharge capacity and the cycle performance of the potassium ion battery.
Description
Technical Field
The invention relates to a preparation method and application of a pomegranate seed-shaped nanocomposite for a potassium ion battery.
Background
The potassium is located in the first main group of the fourth period, has oxidation-reduction potential similar to that of lithium, has physical and chemical properties similar to that of lithium, and has wide distribution and rich content, the content in the crust is up to 2.35 percent (which is far higher than that of lithium: 0.0065 percent; 361 times), and the potassium is located at the 7 th position, so the development of a potassium ion battery system greatly reduces the cost of the battery. The working principle of the potassium ion battery is similar to that of a lithium ion battery, and the potassium ion battery belongs to a typical rocking chair type working mechanism. During charging, K + Is deintercalated from the positive electrode material, migrates into the electrolyte, passes through the separator, and finally is embedded into the negative electrode material, and accordingly electrons are transferred from the positive electrode to the negative electrode by external conductionThe discharge process is reversed. However, the main problem in the potassium ion battery system is K + And thus the volume expansion during charge and discharge is more severe than in other alkali metal ion batteries, resulting in pulverization of the electrode. Thus, develop a suitable K + The shuttle electrode material is important.
Silicon is often used as a negative electrode material of a potassium ion battery because of higher theoretical capacity, but silicon can undergo serious volume expansion in the process of potassium intercalation, so that active materials are pulverized, and the active materials are separated from a current collector. Unstable SEI films are generated on the surface of the silicon in the reaction process, and the continuous accumulation of the SEI films can obstruct the contact between the active material and the electrolyte, so that the electrochemical performance is reduced. Thus, modification of silicon materials is a major hotspot in negative electrode research. Nanocrystallization is one of the most commonly used modification methods, and the nanocrystallization of Si can increase the reactive sites of Si, but the volume expansion of Si still cannot be solved, and unstable SEI films are still continuously generated. Secondly, the preparation of the Si/C composite material is also an effective way for solving the volume expansion of Si, and the introduction of the carbon material can improve the conductivity of the electrode and buffer the volume expansion of Si. In recent researches, ceramic-type semiconductor SiC having high stability attracts great attention. CN115377399 discloses a "preparation method of C-SiC-Si composite anode material for lithium ion battery", in which SiC is dispersed in a columnar fiber form between a carbon layer and a silicon layer, so that the problem of volume expansion of Si can be improved to a certain extent, the material exhibits excellent charge and discharge efficiency, but the anode material still has the problem of volume expansion of Si, the assembled lithium ion battery still has lower discharge capacity in the charge and discharge cycle process, and does not exhibit excellent cycle performance. Therefore, there is a need to develop an electrode material for potassium ion batteries having a larger discharge capacity and better cycle performance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a pomegranate seed-shaped nano composite material for a potassium ion battery, which have simple process and low cost, and can be used for preparing a cathode material of the potassium ion battery, and the prepared composite material can better slow down the volume expansion of Si, reduce the generation of an unstable SEI film and improve the discharge capacity and the cycle performance of the potassium ion battery.
The technical scheme of the invention is as follows:
a preparation method of a pomegranate seed-shaped nanocomposite for a potassium ion battery comprises the following specific steps:
(1) Weighing raw materials
Weighing flake graphite powder and silicon powder according to a mass ratio of 1:1-1:8, and uniformly mixing to obtain a mixed raw material;
(2) Raw material pressed cake
Pressing the mixed raw materials into mixed raw material round cakes by a tablet press under the pressure of 5-30 MPa;
(3) Charging material
Putting the mixed raw material cake into a graphite crucible of a vacuum direct current arc furnace;
(4) Charging a protective gas
Sealing the vacuum direct current arc furnace, vacuumizing until the vacuum degree in the vacuum direct current arc furnace is 0.1MPa, and charging protective gas for gas washing, and continuously charging the protective gas after gas washing is finished, so that the vacuum degree in the vacuum direct current arc furnace is 5-50 kPa; wherein the shielding gas is a mixed gas of argon and nitrogen;
(5) Preparation of Si/SiC nanowire material by arc reaction
Turning on an electric welding machine, adjusting the current to 80-150A, the voltage to 10-60V, conducting discharge arc striking, after 0.5-5 h of reaction, cooling with liquid nitrogen for 10-30 min to enable the product to generate a nanowire shape, passivating the product with air for 4-8 h, and collecting Si/SiC nanowire materials;
(6) Preparation of Granati seed-shaped Si/SiC/C nanocomposite
Dissolving a carbon source in absolute ethyl alcohol, performing ultrasonic dispersion to obtain a carbon source-absolute ethyl alcohol solution with the mass concentration of 5% -15%, and then mixing and stirring for 4-8 hours according to the mass ratio of the Si/SiC nanowire material to the carbon source of 1:1-1:3; heating to 50-90 ℃ in water bath, preserving heat for 3h, freeze-drying the product, grinding the product into powder, and pyrolyzing the powder for 4-10 h at 500-800 ℃ in the argon atmosphere in a tube furnace to obtain the pomegranate seed-shaped Si/SiC/C nanocomposite.
Further, the fineness of the silicon powder and the crystalline flake graphite powder is 40-200 meshes.
Further, when the step (1) is uniformly mixed, the silicon powder and the flake graphite powder are put into a ball mill, and ball milling is carried out for 0.5 to 5 hours at a rotating speed of 100 to 600 r/min.
Further, the height of the mixed raw material cake is 2 mm-6 mm, and the diameter is 18mm.
Further, the volume ratio of the argon to the nitrogen in the mixed gas is 1:1-1:10.
Further, the carbon source is furan resin, phenolic resin or urea resin.
Further, the ultrasonic dispersion time is 1 to 4 hours.
The nanocomposite is applied to the cathode of a potassium ion battery.
Further, the specific preparation steps of the potassium ion battery anode material are as follows: the Si/SiC/C nanocomposite, conductive carbon black (Super-P), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) are uniformly stirred into paste by absolute ethyl alcohol, and the Si/SiC/C negative electrode composite electrode is manufactured.
Further, the mass ratio of the Si/SiC/C nanocomposite to the conductive carbon black (Super-P), the sodium carboxymethylcellulose (CMC) to the Styrene Butadiene Rubber (SBR) is 5:3:1:1.
The invention has the beneficial effects that:
(1) The vacuum direct current arc generates instantaneous high temperature and high pressure in the process of striking arc discharge, the reaction material is decomposed to generate plasma, and then the plasma is condensed by using a liquid nitrogen condenser, and the ions are combined with each other to generate a stable one-dimensional nanowire structure. Compared with the traditional hydrothermal method and sol-gel method, the Si/SiC nanowire material crosslinked with each other can be synthesized in one step by vacuum direct current arc, the nanowire structure can improve pores, enlarge buffer space of Si volume expansion, provide more active sites, and SiC has high stability, is interwoven with Si, can slow down the Si volume expansion in the reaction process, thereby improving the cycle performance, and the method is novel and simple in preparation process;
(2) Preparing a garnet-like Si/SiC/C nanocomposite by regulating and controlling the proportion of Si/SiC to a carbon source and the pyrolysis condition; the introduction of carbon can improve the conductivity of the whole electrode, and can effectively restrict the volume change of Si in the circulation process, thereby avoiding the generation of an unstable SEI film; the amorphous carbon with porous surface can increase the specific surface area, increase the reactive sites, and is favorable for intercalation and deintercalation of potassium ions, thereby improving the electrochemical performance of the whole electrode;
(3) Electrochemical properties showed that the assembled potassium ion cell was at 0.1 A.g -1 Has a high first discharge capacity at a current density of 0.2 A.g -1 After 200 cycles of current density, the capacity retention rate is still above 85%; by performing electrochemical alternating current impedance test on the potassium ion diffusion coefficient, and fitting the test result, the potassium ion diffusion coefficient is calculated to be 7.14x10 -12 m 2 ·s -1 The structure is shown to have a promoting effect on potassium ion transport. Then, the particle size distribution of the composite material can be observed between 25nm and 30nm through an SEM (scanning electron microscope), so that the composite material has the characteristics of small size, multiple pore diameters and large specific surface area, and can provide rich active sites, thereby improving the electrochemical performance.
In summary, the vacuum direct current arc method has the advantages of simplicity, rapidness and low cost, the Si/SiC nanowires crosslinked with each other can be synthesized in one step, and the SiC nanowires are embedded into the Si nanowires to form a structure which is interwoven with each other, wherein the Si-C bonds in the SiC have strong acting force, so that the buffer effect can be effectively achieved in the volume expansion of the Si. Coating a layer of amorphous carbon on the outer layer by pyrolysis method to increase carbon layer spacing and facilitate K + The carbon layer is loose and porous in surface, and the particle size is smaller, so that the carbon composite material has higher specific surface area, part of carbon can infiltrate into the nanowire in the pyrolysis process, the volume expansion of Si can be buffered, the conductivity of the electrode can be improved, and the composite material has excellent discharge capacity, cycle stability and great application prospect.
Drawings
FIG. 1 is a charge-discharge graph of a nanocomposite of the present invention (corresponding to example 1);
FIG. 2 is a graph of the long cycle performance of the nanocomposite of the invention (corresponding to example 1);
FIG. 3 is an SEM image of a nanocomposite of the invention (corresponding to example 1);
FIG. 4 is a charge-discharge graph of a pomegranate seed nanocomposite of the invention (corresponding to example 2);
FIG. 5 is a graph of the long cycle performance of the pomegranate seed nanocomposite of the invention (corresponding to example 2);
FIG. 6 is an electrochemical AC impedance plot of the pomegranate seed nanocomposite of the invention (corresponding to example 2);
FIG. 7 is an XRD pattern of a pomegranate seed-like nanocomposite of the invention (corresponding to example 2);
FIG. 8 is an SEM image of a pomegranate seed-like nanocomposite of the invention (corresponding to example 2);
FIG. 9 is a charge-discharge graph of a pomegranate seed nanocomposite of the invention (corresponding to example 3);
FIG. 10 is a graph of the long cycle performance of the nanocomposite of the present invention (corresponding to example 3);
FIG. 11 is an SEM image of a nanocomposite of the invention (corresponding to example 3);
FIG. 12 is a charge-discharge graph of a nanocomposite of the present invention (corresponding to comparative example 1);
fig. 13 is an SEM image of the nanocomposite of the present invention (corresponding to comparative example 1).
Detailed Description
Example 1
(1) Weighing raw materials
Weighing 3g of Si powder (fineness of 40 meshes) and 3g of crystalline flake graphite (fineness of 40 meshes), putting into a ball mill, and ball milling for 0.5h at a rotating speed of 200r/min to uniformly mix the Si powder and the crystalline flake graphite to obtain a mixed raw material;
(2) Raw material pressed cake
Then the mixed raw materials are pressed into a cake-shaped mixed raw material block with the diameter of 18mm and the height of 2mm by a spiral powder tablet press under the pressure of 5 MPa;
(3) Charging material
Placing the mixed raw material block in a graphite crucible and placing the mixed raw material block on a copper seat of a vacuum direct current arc furnace, and installing a polished discharge tungsten rod, so that the tip of the discharge tungsten rod is opposite to the center of the graphite crucible and the discharge tungsten rod is far away from the anode graphite crucible;
(4) Charging a protective gas
Sealing a vacuum direct current arc furnace, pumping the vacuum direct current arc furnace to 0.1MPa by utilizing a vacuum pump, filling mixed gas of argon and nitrogen with the volume ratio of 1:1 as shielding gas, enabling the vacuum degree to be 5kPa, repeating the operation for 2 times for gas washing, and then filling mixed gas of argon and nitrogen with the volume ratio of 1:1 to 5kPa;
(5) Preparation of Si/SiC nanowire material by electric arc furnace reaction
Turning on a direct current electric welding machine, adjusting the current to 80A, adjusting the voltage range to 10V, continuously raising the copper seat by remote control until the mixed raw material block contacts a tungsten rod to perform discharge arc striking, keeping the reaction time to be 0.5h, then cooling the vacuum direct current electric arc furnace for 10min by filling liquid nitrogen into a vacuum direct current electric arc furnace shell, passivating the product for 4h by using air, and finally collecting Si/SiC nanowire materials;
(6) Preparation of Granati seed-shaped Si/SiC/C nanocomposite
3g of phenolic resin is dissolved in 60mL of absolute ethyl alcohol and dispersed for 1h, 3g of Si/SiC nanowire material is added and stirred in a water bath for 4h, then the temperature is raised to 50 ℃ and kept for 3h to volatilize the absolute ethyl alcohol, and the obtained mixture is placed into a vacuum freeze drying box for drying treatment; grinding the dried product into powder, and placing the powder in a tubular furnace for pyrolysis at 500 ℃ for 4 hours under argon atmosphere to obtain the pomegranate seed-shaped Si/SiC/C nanocomposite.
Preparing a potassium ion battery cathode by taking the pomegranate seed-shaped Si/SiC/C nanocomposite of the embodiment 1 as an electrode material, uniformly stirring the pomegranate seed-shaped Si/SiC/C nanocomposite, conductive carbon black (Super P), sodium carboxymethylcellulose (CMC) and styrene-butadiene rubber (SBR) into paste according to a mass ratio of 5:3:1:1, uniformly stirring the paste by using absolute ethyl alcohol, coating one side of the paste on the surface of a copper foil with the thickness of 10 mu m, coating the paste with the thickness of 0.05mm, and performing vacuum drying at 50 ℃ for 18 hours to obtain the pomegranate seed-shaped Si/SiC/C nanocomposite composite electrode;
with metallic potassium as positive electrode, 0.8M KPF 6 EC/DEC (volume ratio 1:1)The 2025 button type potassium ion battery is assembled by using electrolyte, a polyethylene film PP as a diaphragm and a pomegranate seed-shaped Si/SiC/C nano material composite electrode as a negative electrode.
The charge-discharge curve and cycle performance curve of the assembled battery according to example 1 are shown in FIGS. 1 and 2, and the electrochemical test results of FIGS. 1 and 2 show that the assembled potassium ion battery is 0.1 A.g -1 The first discharge capacity at the current density of (2) was 2015mAh g -1 And at 0.2 A.g -1 After 200 cycles at current density of 648 mAh.g -1 The capacity retention was 85%.
FIG. 3 is a scanning electron microscope image of the prepared nanocomposite, from which it can be seen that the overall structure is a loose seed-like particle of punica granatum, and that there are very few nanowires, and that the particle size is small, ranging from 25nm to 30nm; the nanowire is Si@SiC prepared by a direct current arc furnace, and the pomegranate seed shape is the shape after the outer layer of the nanowire is coated with phenolic resin.
Example 2
(1) Weighing raw materials
Weighing 4g of Si powder (fineness of 150 meshes) and 1g of crystalline flake graphite (fineness of 150 meshes), putting into a ball mill, and ball milling for 2 hours at a rotating speed of 400r/min to uniformly mix the Si powder and the crystalline flake graphite to obtain a mixed raw material;
(2) Raw material pressed cake
Then the mixed raw materials are pressed into a cake-shaped mixed raw material block with the diameter of 18mm and the height of 4mm by a spiral powder tablet press under the pressure of 15 MPa;
(3) Charging material
Placing the mixed raw material block in a graphite crucible and placing the mixed raw material block on a copper seat of a vacuum direct current arc furnace, and installing a polished discharge tungsten rod, so that the tip of the discharge tungsten rod is opposite to the center of the graphite crucible and the discharge tungsten rod is far away from the anode graphite crucible;
(4) Charging a protective gas
Sealing a vacuum direct current arc furnace, pumping the vacuum direct current arc furnace to 0.1MPa by utilizing a vacuum pump, filling a mixed gas of argon and nitrogen with the volume ratio of 1:5 as a protective gas, enabling the vacuum degree to be 5kPa, repeating the operation for 3 times for gas washing, and then filling a mixed gas of argon and nitrogen with the volume ratio of 1:5 into the furnace for 20kPa;
(5) Preparation of Si/SiC nanowire material by electric arc furnace reaction
Turning on a direct current electric welding machine, adjusting the current to 100A, adjusting the voltage range to 40V, continuously raising the copper seat by remote control until the mixed raw material block contacts a tungsten rod to perform discharge arc striking, keeping the reaction time to be 1h, then cooling the vacuum direct current electric arc furnace for 20min by filling liquid nitrogen into a vacuum direct current electric arc furnace shell, passivating the product for 6h by using air, and finally collecting Si/SiC nanowire materials;
(6) Preparation of Granati seed-shaped Si/SiC/C nanocomposite
3g of phenolic resin is dissolved in 30mL of absolute ethyl alcohol and dispersed for 2 hours, 1.5g of Si/SiC nanowire material is added and stirred in a water bath for 6 hours, then the temperature is raised to 60 ℃ and kept for 3 hours to volatilize the absolute ethyl alcohol, and the mixture is placed into a vacuum freeze drying box for drying treatment; grinding the dried product into powder, and placing the powder in a tubular furnace for pyrolysis at 700 ℃ for 5 hours in an argon atmosphere to obtain the pomegranate seed-shaped Si/SiC/C nanocomposite.
Preparing a potassium ion battery cathode by taking the pomegranate seed-shaped Si/SiC/C nanocomposite of the embodiment 2 as an electrode material, uniformly stirring the pomegranate seed-shaped Si/SiC/C nanocomposite, conductive carbon black (Super P), sodium carboxymethylcellulose (CMC) and styrene-butadiene rubber (SBR) into paste according to a mass ratio of 5:3:1:1, uniformly stirring the paste by using absolute ethyl alcohol, coating one side of the paste on the surface of a copper foil with the thickness of 10 mu m, coating the paste with the thickness of 0.05mm, and vacuum-drying the paste for 20 hours at 70 ℃ to obtain the pomegranate seed-shaped Si/SiC/C nanocomposite composite electrode;
with metallic potassium as positive electrode, 0.8M KPF 6 The EC/DEC (volume ratio is 1:1) is electrolyte, the polyethylene film PP is diaphragm, the pomegranate seed-shaped Si/SiC/C nano-material composite electrode is negative electrode, and the 2025 button type potassium ion battery is assembled.
The charge-discharge curve, cycle performance curve and ac impedance curve measured for the assembled battery according to example 2 are shown in fig. 4, 5 and 6, and the electrochemical test results of fig. 4 and 5 show that the assembled potassium ion battery is 0.1a·g -1 The first discharge capacity at the current density of (3) was 3354 mAh.g -1 And at 0.2 A.g -1 After 200 cycles at current density, the capacity remained at 856 mAh.g -1 The capacity retention was 98%. And by fitting the electrochemical alternating current impedance diagram, the potassium ion diffusion coefficient can be calculated to be 7.14X10 -12 m 2 ·s -1 。
Fig. 7 is an XRD pattern of the prepared pomegranate seed-shaped nanocomposite, from which diffraction peaks of Si, siC and C contained in the composite can be observed, and no other impurity peaks exist, so that the product has high purity. Fig. 8 is a scanning electron microscope picture of the composite material, from which it can be seen that the composite material presents mutually contacted pomegranate seed shaped particles, and there are more pores between the particles, increasing the specific surface area without obvious agglomeration. The SEM shows that the particle size of the composite material is distributed between 25nm and 30nm, so that the composite material has larger specific surface area and more reactive sites, promotes the intercalation and deintercalation of potassium ions, and improves the diffusion rate of the potassium ions, thereby having better electrochemical stability.
Example 3
(1) Weighing raw materials
Weighing 4g of Si powder (fineness of 200 meshes) and 0.5g of crystalline flake graphite (fineness of 200 meshes), putting into a ball mill, and ball milling for 5 hours at a rotating speed of 600r/min to uniformly mix the Si powder and the crystalline flake graphite to obtain a mixed raw material;
(2) Raw material pressed cake
Then the mixed raw materials are pressed into a cake-shaped mixed raw material block with the diameter of 18mm and the height of 6mm by a spiral powder tablet press under the pressure of 30 MPa;
(3) Charging material
Placing the mixed raw material block in a graphite crucible and placing the mixed raw material block on a copper seat of a vacuum direct current arc furnace, and installing a polished discharge tungsten rod, so that the tip of the discharge tungsten rod is opposite to the center of the graphite crucible and the discharge tungsten rod is far away from the anode graphite crucible;
(4) Charging a protective gas
Sealing a vacuum direct current arc furnace, pumping the vacuum direct current arc furnace to a vacuum degree of 0.1MPa by utilizing a vacuum pump, filling a mixed gas of argon and nitrogen with a volume ratio of 1:10 as a protective gas, enabling the vacuum degree to reach 5kPa, repeating the operation for 5 times for gas washing, and then filling a mixed gas of argon and nitrogen with a volume ratio of 1:10 into the furnace for 50kPa;
(5) Preparation of Si/SiC nanowire material by electric arc furnace reaction
Turning on a direct current electric welding machine, adjusting the current to 150A, adjusting the voltage range to 60V, continuously raising the copper seat by remote control until the mixed raw material block contacts a tungsten rod to perform discharge arc striking, keeping the reaction time to be 5h, then cooling the vacuum direct current electric arc furnace for 30min by filling liquid nitrogen into a vacuum direct current electric arc furnace shell, passivating the product for 8h by using air, and finally collecting Si/SiC nanowire materials;
(6) Preparation of Granati seed-shaped Si/SiC/C nanocomposite
3g of phenolic resin is dissolved in 20mL of absolute ethyl alcohol and dispersed for 4 hours, 1g of Si/SiC nanowire material is added and stirred in a water bath for 8 hours, then the temperature is raised to 90 ℃ and kept for 3 hours to volatilize the absolute ethyl alcohol, and the obtained mixture is placed into a vacuum freeze drying box for drying treatment; grinding the dried product into powder, and placing the powder in a tubular furnace for pyrolysis at 800 ℃ for 10 hours under argon atmosphere to obtain the pomegranate seed-shaped Si/SiC/C nanocomposite.
Preparing a potassium ion battery cathode by taking the pomegranate seed-shaped Si/SiC/C nanocomposite of the embodiment 3 as an electrode material, uniformly stirring the pomegranate seed-shaped Si/SiC/C nanocomposite, conductive carbon black (Super P), sodium carboxymethylcellulose (CMC) and styrene-butadiene rubber (SBR) into paste according to a mass ratio of 5:3:1:1, uniformly stirring the paste by using absolute ethyl alcohol, coating one side of the paste on the surface of a copper foil with the thickness of 10 mu m, coating the paste with the thickness of 0.05mm, and vacuum-drying the paste at 80 ℃ for 22 hours to obtain the pomegranate seed-shaped Si/SiC/C nanocomposite composite electrode;
with metallic potassium as positive electrode, 0.8M KPF 6 The EC/DEC (volume ratio is 1:1) is electrolyte, the polyethylene film PP is diaphragm, the pomegranate seed-shaped Si/SiC/C nano-material composite electrode is negative electrode, and the 2025 button type potassium ion battery is assembled.
The charge-discharge curve, cycle performance curve and ac impedance curve measured by assembling the battery according to example 3 are shown in fig. 9 and 10, and the electrochemical test results of fig. 9 and 10 show that the assembled potassium ion battery is 0.1a·g -1 The initial discharge capacity at the current density of (3) was 2047 mAh.g -1 And at 0.2 A.g -1 After 200 cycles at current density, the capacity remains at 736 mAh.g -1 The capacity retention was 95%.
FIG. 11 is a scanning electron microscope image of the prepared pomegranate seed-shaped nanocomposite, from which it can be seen that the composite exhibits mutually contacting pomegranate seed-shaped particles with particle diameters of 25nm to 30nm, although there is a small amount of agglomeration.
Comparative example 1
(1) Weighing raw materials
Weighing 4g of Si powder (fineness of 150 meshes) and 1g of crystalline flake graphite (fineness of 150 meshes), putting into a ball mill, and ball milling for 2 hours at a rotating speed of 400r/min to uniformly mix the Si powder and the crystalline flake graphite to obtain a mixed raw material;
(2) Raw material pressed cake
Then the mixed raw materials are pressed into a cake-shaped mixed raw material block with the diameter of 18mm and the height of 4mm by a spiral powder tablet press under the pressure of 15 MPa;
(3) Charging material
Placing the mixed raw material block in a graphite crucible and placing the mixed raw material block on a copper seat of a vacuum direct current arc furnace, and installing a polished discharge tungsten rod, so that the tip of the discharge tungsten rod is opposite to the center of the graphite crucible and the discharge tungsten rod is far away from the anode graphite crucible;
(4) Charging a protective gas
Sealing a vacuum direct current arc furnace, pumping the vacuum direct current arc furnace to 0.1MPa by utilizing a vacuum pump, filling a mixed gas of argon and nitrogen with the volume ratio of 1:5 as a protective gas, enabling the vacuum degree to be 5kPa, repeating the operation for 3 times for gas washing, and then filling a mixed gas of argon and nitrogen with the volume ratio of 1:5 into the furnace for 20kPa;
(5) Preparation of Si/SiC nanowire material by electric arc furnace reaction
Turning on a direct current electric welding machine, adjusting the current to 100A, adjusting the voltage range to 40V, continuously raising the copper seat by remote control until the mixed raw material block contacts a tungsten rod to perform discharge arc striking, keeping the reaction time to be 1h, then cooling the vacuum direct current electric arc furnace for 20min by filling liquid nitrogen into a vacuum direct current electric arc furnace shell, passivating the product for 6h by using air, and finally collecting Si/SiC nanowire materials;
(6) Preparation of Si/SiC/C nanocomposite
8g of phenolic resin is dissolved in 30mL of absolute ethyl alcohol and dispersed for 2 hours, 1.5g of Si/SiC nanowire material is added and stirred in a water bath for 6 hours, then the temperature is raised to 60 ℃ and kept for 3 hours to volatilize the absolute ethyl alcohol, and the obtained mixture is placed into a vacuum freeze drying box for drying treatment; grinding the dried product into powder, and placing the powder in a tubular furnace for pyrolysis at 700 ℃ for 5 hours in an argon atmosphere to obtain the Si/SiC/C nanocomposite;
(7) Preparation of Si/SiC/C nanocomposite electrode
Uniformly stirring a Si/SiC/C nano composite material, conductive carbon black (Super P), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) into paste according to a mass ratio of 5:3:1:1, uniformly stirring the paste by using absolute ethyl alcohol, coating one side of the paste on the surface of a copper foil with the thickness of 10 mu m, coating the paste with the thickness of 0.05mm, and carrying out vacuum drying at 70 ℃ for 20 hours to obtain the Si/SiC/C nano composite electrode;
(8) Assembled 2025 button type potassium ion battery
With metallic potassium as positive electrode, 0.8M KPF 6 The EC/DEC (volume ratio is 1:1) is electrolyte, the polyethylene film PP is diaphragm, the Si/SiC/C nano composite electrode is negative electrode, and the 2025 button type potassium ion battery is assembled.
The cycle performance curves obtained by assembling the cells according to comparative example 1 are shown in FIG. 12, and electrochemical test results show that the assembled potassium ion cell was at 0.2 A.g -1 After 150 cycles at current density of 286 mAh.g -1 The capacity retention was 68%.
FIG. 13 is a scanning electron microscope image of the prepared nanocomposite, from which it can be seen that morphology was changed and a large amount of agglomeration occurred when an excess of phenolic resin was added. Therefore, compared with example 2, the Si/SiC/C nanocomposite of comparative example 1 has small specific surface area and greatly reduced reactive sites, cannot provide a channel for rapid intercalation and deintercalation of potassium ions, and the excessive phenolic resin makes the Si/SiC active material unable to be in effective contact with the electrolyte, so that the electrochemical performance is greatly reduced.
TABLE 1 electrochemical performance tables for inventive examples 1-3 and comparative example 1
TABLE 1 electrochemical performance tables for inventive examples 1-3 and comparative example 1
In summary, the successful preparation of the pomegranate seed-shaped nanocomposite of the embodiments 1, 2 and 3 provides an effective solution to the problem of volume expansion of the silicon negative electrode, the volume expansion of the cross-linked nanowire silicon provides more pores, the introduction of the phenolic resin improves the conductivity of the whole electrode, the composite presents loose morphology, has a larger specific surface area and more reactive sites, all has promotion effect on the shuttling of potassium ions, and the pomegranate seed-shaped nanocomposite electrode obtained in the particular embodiment 2 has excellent specific discharge capacity and cycle stability.
The above is only a specific embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a pomegranate seed-shaped nanocomposite for a potassium ion battery is characterized by comprising the following steps:
the method comprises the following specific steps:
(1) Weighing raw materials
Weighing flake graphite powder and silicon powder according to a mass ratio of 1:1-1:8, and uniformly mixing to obtain a mixed raw material;
(2) Raw material pressed cake
Pressing the mixed raw materials into mixed raw material round cakes by a tablet press under the pressure of 5-30 MPa;
(3) Charging material
Putting the mixed raw material cake into a graphite crucible of a vacuum direct current arc furnace;
(4) Charging a protective gas
Sealing the vacuum direct current arc furnace, vacuumizing until the vacuum degree in the vacuum direct current arc furnace is 0.1MPa, and charging protective gas for gas washing, and continuously charging the protective gas after gas washing is finished, so that the vacuum degree in the vacuum direct current arc furnace is 5-50 kPa; wherein the shielding gas is a mixed gas of argon and nitrogen;
(5) Preparation of Si/SiC nanowire material by arc reaction
Turning on an electric welding machine, adjusting the current to 80-150A, the voltage to 10-60V, conducting discharge arc striking, cooling with liquid nitrogen for 10-30 min after 0.5-5 h of reaction, passivating the product with air for 4-8 h, and collecting Si/SiC nanowire materials;
(6) Preparation of Granati seed-shaped Si/SiC/C nanocomposite
Dissolving a carbon source in absolute ethyl alcohol, performing ultrasonic dispersion to obtain a carbon source-absolute ethyl alcohol solution with the mass concentration of 5% -15%, and then mixing and stirring for 4-8 hours according to the mass ratio of the Si/SiC nanowire material to the carbon source of 1:1-1:3; heating to 50-90 ℃ in water bath, preserving heat for 3h, freeze-drying the product, grinding the product into powder, and pyrolyzing the powder for 4-10 h at 500-800 ℃ in the argon atmosphere in a tube furnace to obtain the pomegranate seed-shaped Si/SiC/C nanocomposite.
2. The method for preparing the pomegranate seed-shaped nanocomposite for potassium ion battery according to claim 1, characterized in that: the fineness of the silicon powder and the crystalline flake graphite powder is 40-200 meshes.
3. The method for preparing the pomegranate seed-shaped nanocomposite for potassium ion battery according to claim 1, characterized in that: when the step (1) is uniformly mixed, the silicon powder and the flake graphite powder are put into a ball mill, and ball milling is carried out for 0.5 to 5 hours at a rotating speed of 100 to 600 r/min.
4. The method for preparing the pomegranate seed-shaped nanocomposite for potassium ion battery according to claim 1, characterized in that: the height of the mixed raw material cake is 2 mm-6 mm, and the diameter is 18mm.
5. The method for preparing the pomegranate seed-shaped nanocomposite for potassium ion battery according to claim 1, characterized in that: the volume ratio of the argon to the nitrogen in the mixed gas is 1:1-1:10.
6. The method for preparing the pomegranate seed-shaped nanocomposite for potassium ion battery according to claim 1, characterized in that: the carbon source is furan resin, phenolic resin and urea resin.
7. The method for preparing the pomegranate seed-shaped nanocomposite for potassium ion battery according to claim 1, characterized in that: the ultrasonic dispersion time is 1-4 h.
8. Use of a nanocomposite prepared by the method of preparing a nanocomposite according to claim 1 as a negative electrode for a potassium ion battery.
9. The use of the nanocomposite prepared by the method for preparing a nanocomposite according to claim 8 as a negative electrode for a potassium ion battery, characterized in that:
the specific preparation steps of the potassium ion battery cathode are as follows:
the Si/SiC/C nanocomposite, conductive carbon black (Super-P), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) are uniformly stirred into paste by absolute ethyl alcohol, and the Si/SiC/C negative electrode composite electrode is manufactured.
10. The use of the nanocomposite prepared by the method for preparing a nanocomposite according to claim 9 as a negative electrode for a potassium ion battery, characterized in that:
the mass ratio of the Si/SiC/C nanocomposite to the conductive carbon black (Super-P) to the sodium carboxymethylcellulose (CMC) to the Styrene Butadiene Rubber (SBR) is 5:3:1:1.
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