CN112174130A - Preparation method of crosslinked thin-layer graphite serving as negative electrode of potassium ion battery - Google Patents
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Abstract
The invention discloses a preparation method of cross-linked thin-layer graphite serving as a negative electrode of a potassium ion battery, which comprises the following steps: mixing a carbon source, ferric trichloride hexahydrate and deionized water to form a uniform mixed solution; pre-drying the mixed solution, and carrying out graphitization reaction at high temperature; and (5) etching by using dilute hydrochloric acid to remove metallic iron, and performing vacuum drying treatment. The cross-linked thin-layer graphite provided by the invention has excellent electrochemical performance as a negative electrode of a potassium ion battery: a) high capacity; b) high rate capability c) good cycle performance.
Description
Technical Field
The invention relates to a potassium ion battery, in particular to a preparation method of crosslinked thin-layer graphite serving as a negative electrode of the potassium ion battery.
Background
Stable energy storage of carbon materials is fundamental to the commercial application of energy storage devices, exemplified by Lithium Ion Batteries (LIBs), and the LIB negative electrode, which is currently widely used commercially, is still graphite, although many negative electrode materials have been reported. However, the lithium resources are distributed unevenly, the price rises continuously, and the copper foil is required to be used as a negative current collector, so that the problems which are not solved yet can not meet the energy storage requirements of large scale and low cost. Due to potassium resource chargeSufficient and low potential (-2.93V, K/K)+) Therefore, Potassium Ion Batteries (PIB) are considered as a potential replacement for LIB. In addition, the PIB can use aluminum foil instead of copper foil as the negative current collector because the alloying reaction between potassium and aluminum does not occur at low potential, which will further reduce the cost of the PIB and its negative current collector.
As with LIB, high performance potassium storage of carbon materials (especially graphitized carbon materials) is critical to the development of PIB. It is well known that potassium has a large atomic radius (0.138nm), while the interlayer spacing of graphite is about 0.335 nm. Therefore, graphite has conventionally been considered to be unable to serve as a stable negative electrode for potassium ion batteries. However, in 2019, we found through research that graphite can store potassium ultra-stably when using a concentrated electrolyte (KFSI: EMC, 1: 2.5 (molar ratio) and operates for 17 months with almost no capacity fading after 2,000 cycles, but it has problems that KFSI is very expensive, it corrodes aluminum foil under high pressure, and the like, and it cannot meet the low cost, large scale mass production requirements of potassium ion batteries-1The reversible capacity of (a). However, large-scale production cannot be achieved due to the high price of Ketjen black and the high energy consumption of high-temperature carbonization at 2800 ℃. Therefore, the low cost, large scale preparation of graphitized anode materials that can stably store potassium remains a challenge.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of crosslinked thin-layer graphite serving as a potassium ion battery negative electrode, and the potassium ion battery negative electrode material which is low in cost, can be prepared in a large scale and can stably store potassium is obtained.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the invention provides a preparation method of crosslinked thin-layer graphite serving as a negative electrode of a potassium ion battery, which comprises the following steps: carbon source, ferric chloride hexahydrate (FeCl)3·6H2O)Mixing with deionized water to form a uniform mixed solution;
pre-drying the mixed solution, and carrying out graphitization reaction at high temperature;
and (5) etching by using dilute hydrochloric acid to remove metallic iron, and performing vacuum drying treatment.
Further, the step of mixing the carbon source, ferric chloride hexahydrate and deionized water to form a uniform mixed solution comprises the following steps: adding a certain mass of carbon source and ferric trichloride hexahydrate into a certain amount of deionized water, and stirring until the carbon source and ferric trichloride hexahydrate are completely dissolved to form a uniform mixed solution.
Further, the mass ratio of the carbon source to the ferric chloride hexahydrate is 1: 1-4.
Further, the carbon source is ascorbic acid.
Further, the pre-drying treatment of the mixed solution and the graphitization reaction at high temperature comprise the steps of: putting the mixed solution into a baking oven, and baking at the temperature of 180-220 ℃ to obtain uniform colloid; then, the colloid is put in argon atmosphere at 1-3 ℃ for min-1The temperature is raised to 100 ℃ and 150 ℃, and the temperature is kept for 2 to 5 hours; finally, heating at 3-6 deg.C for min-1The temperature is continuously raised to 1000 ℃, and the annealing carbonization treatment is carried out for 4 to 8 hours at the high temperature of 1000 ℃.
Further, the dilute hydrochloric acid etching process for removing the metallic iron and the vacuum drying process comprise the following steps: repeatedly etching with 50-70 deg.C dilute hydrochloric acid solution and washing with deionized water to completely remove iron in the mixture; and finally, drying the washed product in a vacuum oven at the temperature of 60-100 ℃ for 8-16h to obtain the crosslinked thin-layer graphite.
From the above description of the structure of the present invention, compared with the prior art, the present invention has the following advantages:
the forming mechanism of the cross-linked thin-layer graphite (HGC) with the three-dimensional cross-linked hollow structure provided by the invention is as follows: FeCl3·6H2O is decomposed into iron catalyst in the annealing process and further reacts with a carbon source C6H8O6And carrying out graphitization reaction. The graphite layer grows to form three-dimensional cross-linking under high-temperature carbonizationThe graphitic carbon material of (1). And removing the metallic iron by hydrochloric acid, thereby forming a hollow structure inside and finally forming the cross-linked thin-layer graphite with a three-dimensional cross-linked hollow structure.
The cross-linked thin-layer graphite (HGC) with the three-dimensional cross-linked hollow structure can provide enough space, and can avoid the damage of a negative electrode material caused by volume expansion in the charge and discharge processes; the three-dimensional cross-linked structure forms a compact interconnected network, can accelerate the rapid permeation of electrolyte and accelerate the rapid transfer and diffusion of electrons/ions among different internal structures of the graphite cathode material.
Therefore, the cross-linked thin-layer graphite provided by the invention has the following beneficial effects:
1) the cross-linked thin-layer graphite provided by the invention has excellent electrochemical performance as a negative electrode of a potassium ion battery: a) high capacity, at 50mAg-1Has a current density of 298mAh g-1High reversible discharge capacity and relatively low charge/discharge voltage plateau (0.25V/0.1V); b) high rate performance of 50, 100, 200, 300, 400, 500mAg-1Reversible capacities at current densities of 315, 239, 188, 161, 137, and 120mAh g, respectively-1When the current density is recovered to 100mA g-1Then, the reversible capacity was restored to 234mAh g-1(ii) a c) Good cycle performance, 50mA g of battery-1269mAh g still remained after 200 cycles under the current density-1Corresponding to a capacity fade of only 0.048% per cycle.
3) The cross-linked thin-layer graphite provided by the invention can be used as a negative electrode material of a potassium ion battery, and can well fit with cheap traditional commercial electrolyte potassium hexafluorophosphate (KPF)6) Further reducing the cost of the potassium ion battery and providing greater possibility for the large-scale production and application of the potassium ion battery.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of a process for preparing a crosslinked thin-layer graphite (HGC) provided by the present invention;
FIG. 2 is a pictorial view and a microscopic morphological analysis view of a cross-linked thin-layer graphite (HGC) provided in the present invention;
FIG. 3 is a microstructural feature analysis diagram of a cross-linked thin-layer graphite (HGC) provided by the present invention;
FIG. 4 is a diagram showing the electrochemical performance of crosslinked thin-layer graphite (HGC) provided by the present invention as a negative electrode of a potassium ion battery;
FIG. 5 is a schematic diagram of the structural stability of the cross-linked thin-layer graphite (HGC) and the disclosed negative electrode material with a hollow sphere structure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides cross-linked thin-layer graphite which has a three-dimensional cross-linked structure and is internally provided with a hollow structure which is cross-linked with each other. The special three-dimensional cross-linked hollow structure of the cross-linked thin-layer graphite not only can provide enough expansion space for a K + embedding/de-embedding process, but also can realize the rapid penetration of electrolyte and accelerate the diffusion speed of electrons/ions.
Fig. 1 is a schematic diagram of a process for preparing a crosslinked thin-layer graphite (HGC) according to the present invention, the process for preparing the crosslinked thin-layer graphite being as follows: carbon source, ferric chloride hexahydrate (FeCl)3·6H2O) mixing with deionized water to form a homogeneous mixed solution: adding a certain mass of carbon source and ferric trichloride hexahydrate into a certain amount of deionized water, and stirring until the carbon source and ferric trichloride hexahydrate are completely dissolved to form a uniform mixed solution; the carbon source and ferric chloride hexahydrate (FeCl)3·6H2O) is 1: 1-4, the carbon source is ascorbic acid (C)6H8O6). Pre-drying the mixed solution, and carrying out graphitization reaction at high temperature: placing the mixed solution in a baking oven at 180 deg.CBaking at-220 deg.C to obtain uniform colloid; then, the colloid is put in argon atmosphere at 1-3 ℃ for min-1The temperature is raised to 100 ℃ and 150 ℃, and the temperature is kept for 2 to 5 hours; finally, heating at 3-6 deg.C for min-1The temperature is continuously raised to 1000 ℃, and the annealing carbonization treatment is carried out for 4 to 8 hours at the high temperature of 1000 ℃. Etching with dilute hydrochloric acid to remove metallic iron, and performing vacuum drying treatment: repeatedly etching with 50-70 deg.C dilute hydrochloric acid solution and washing with deionized water to completely remove iron in the mixture; and putting the washed product in a vacuum oven, and drying for 8-16h at the temperature of 60-100 ℃ to obtain the crosslinked thin-layer graphite.
Examples
First, 2g of ascorbic acid (C)6H8O6) And 5g of ferric chloride hexahydrate (FeCl)3·6H2O) is added into a certain amount of deionized water and stirred until the deionized water is completely dissolved to form a uniform mixed solution.
Then, putting the obtained mixed solution into a baking oven, and baking at the temperature of 200 ℃ to obtain uniform colloid; then placing the colloid in argon atmosphere at 2 deg.C for min-1The temperature is increased to 120 ℃ at a constant speed, and the temperature is kept for 2 hours; then at 5 deg.C for min-1The temperature is continuously increased to 1000 ℃, and the annealing carbonization treatment is carried out for 6 hours at the high temperature of 1000 ℃.
Finally, repeatedly etching the sample by using a dilute hydrochloric acid solution at 60 ℃ and repeatedly washing the sample by using deionized water until the iron in the mixture is completely removed; and drying the washed product in a vacuum oven at the temperature of 80 ℃ for 12h to obtain the crosslinked thin-layer graphite (HGC) with the three-dimensional crosslinked hollow structure.
Fig. 2 shows a physical diagram and a microscopic morphology analysis diagram of a cross-linked thin-layer graphite (HGC) provided by the present invention. a is a Scanning Electron Microscope (SEM) showing that the HGC exhibits a wrinkled surface morphology and intertwines and folds with each other. The intertwined wrinkle forms enlarge the interface contact between the electrode and the electrolyte, and are beneficial to the rapid permeation and deep permeation of the electrolyte. b Transmission Electron Microscopy (TEM) showed that the edges of the HGC and SEM images matched each other. In c, clearly visible are the cross-linking and internal hollow structures. d High Resolution Transmission Electron Microscopy (HRTEM) showed that the multilayer crosslinked graphite was about 5-10nm thick with good crystallinity. The fourier transforms (FFTs) in e clearly show the distribution of carbon atoms and the ordered arrangement of graphitic layers with uniform interlayer spacing of about (0.341nm) corresponding to the (002) facets.
Fig. 2 shows that the HGC electrode has the following advantages: 1) the internal hollow structure of the HGC can provide sufficient space, which is more advantageous for buffering the volume expansion due to the continuous potassium/potassium removal process, and for K+Is more stable in terms of the quality; 2) the inter-linked framework structure may provide greater support for lattice expansion. 3) The three-dimensional cross-linked structure forms an interconnected conductive net, thereby realizing the rapid transmission and transmission of electrons and shortening the diffusion distance of ions.
Fig. 3 is a characteristic view of the microstructure of the cross-linked thin-layer graphite (HGC) provided by the present invention, in which the XRD pattern of a shows that XRD peaks at 26.26 °, 42.53 °, 53.92 ° and 77.62 ° correspond to (002), (100), (004) and (110) planes of the graphite 2H phase, respectively, indicating that HGC has high graphitization and good crystallinity. The Raman spectrum of b shows that HGC is 1334.6, 1583.3 and 2664.3cm-1Three strong raman peaks are shown, corresponding to the D band (defect structure), G band (graphite structure) and 2D band (zone boundary), respectively. The peak intensity ratio (ID/IG) for the D and G bands was 0.757, indicating that HGC has typical highly ordered graphitic character, which is consistent with the results of HRTEM and XRD. The BET tests the specific surface area and pore size distribution of HGC. N2 adsorption/desorption isotherms in c indicate that the presence of hollow structures may be due to tightly cross-linked structures. FIG. 3d shows that the pore size of the mesopores of HGC is mainly distributed at 2.63nm, and the pore size of the micropores is intensively distributed at 0.68 nm. The specific surface area is 111.3m2g-1The interface between the HGC and the electrolyte can be effectively increased, the electrolyte permeation is accelerated, and better electrochemical performance is realized.
The performance of the crosslinked graphite thin layer negative electrode was evaluated by assembling a potassium ion battery with the crosslinked graphite thin layer obtained in the examples as a negative electrode, a potassium foil as a counter electrode, and potassium hexafluorophosphate as an electrolyte.
FIG. 4 shows a cross-linked lamellar stone provided by the present inventionElectrochemical performance diagram of ink (HGC) as negative electrode of potassium ion battery; the charge/discharge curves for cycles 10, 50, 100 and 200 are shown in a. The charge and discharge curve shapes are almost overlapped, and the capacity is not obviously attenuated, which indicates that the HGC has good reversibility as a negative electrode material of a potassium ion battery. And the charging plateau was about 0.25V and the discharging plateau was about 0.1V. Effectively inhibit the formation of potassium dendrite under low voltage platform, which is beneficial to improve the K of HGC+Storage stability, thereby ensuring high safety. From b at 0.1mV s-1The Cyclic Voltammetry (CV) of the scanning speed shows that an obvious oxidation peak is at 0.7V, and the subsequent CV curve has high coincidence, thereby further proving that the HGC has high reversible K + storage. The charge/discharge curves at different current densities are shown in c. When the current density increased from 50mA g-1 to 500mA g-1The shape of the charge and discharge curves did not change significantly, indicating that there was no severe polarization. d shows the rate capability of the HGC at current densities of 50, 100, 200, 300, 400 and 500mA g-1The reversible capacities were 315, 239, 188, 161, 137 and 120mA hg, respectively-1The corresponding coulombic efficiencies were about 68%, 96%, 98%, 98%, 99% and 99%, respectively. When the current density returns to 100mA g-1While still having 234mA hg-1The reversible capacity of (a). And e, comparing the rate performance of the HGC with that of other disclosed potassium ion battery graphite-based negative electrode materials, wherein the HGC has good reversibility under different current densities. The HGC negative electrode in f showed excellent cycle stability, i.e., 50mA g-1The reversible capacity is up to 298mA hg at the current density of (1)-1. And still has 269mA h g after 200 cycles-1The capacity of (2) has a capacity retention rate of 90%, and the decay rate per cycle is only 0.048%. Tables 1 and g show that HGC is significantly superior to many graphite-based anodes that have been disclosed for use in potassium ion batteries, such as commercial Expanded Graphite (EG), nitrogen-doped carbon nanotubes (NCNT), graphitic Carbon Nanocages (CNC), Graphitic Nanocarbon (GNC), polycrystalline nanographite (PG), activated graphite, and graphite.
TABLE 1 HGC and published graphite-based negative electrode comparison results for potassium ion batteries
Study K+The change of the structure of the HGC electrode during charge and discharge cycles during intercalation/deintercalation and the reason for being able to stably store potassium.
As shown in fig. 5, the change of the material structure during the charge-discharge cycle of the hollow sphere structure negative electrode material and the HGC negative electrode material provided by the present invention was compared. and a shows that the hollow sphere structure is cracked and crushed in a plurality of continuous charging and discharging processes. As the structure is broken, more electrode material areas will be exposed, and more SEI will be formed on the surface of the material, lowering the conductivity of the electrode, resulting in poor electrochemical performance. And b, the HGC with the cross-linked hollow structure characteristic and the cross-linked framework of the cross-linked thin-layer graphite have good traction force and can keep the structure stable and complete. Therefore, the hollow structure is combined with the mutual cross-linking frame, so that a stronger and more stable expansion space can be provided for the storage of potassium ions, and more stable support can be provided for the potassium ions stored in the graphite crystal lattice. HRTEM of c-e showed that the cross-linked structure of the HGC after 1, 100 and 200 cycles was very clear, and the long-range order and crystallinity of the graphitic layers were still perfect, without flaking and cracking, and the morphology and structure of the HGC after 200 cycles was still very intact with no apparent damage compared to the virgin material. It is further confirmed that the ultra-stable and cross-linked hollow structure of the HGC realizes the ultra-high rate performance, high reversibility and excellent cycle stability of the potassium ion battery.
In summary, the cross-linked thin-layer graphite (HGC) with a three-dimensional cross-linked hollow structure provided by the invention can provide a sufficient space due to the hollow structure, and can avoid the damage of the negative electrode material due to volume expansion in the charge and discharge processes; the three-dimensional cross-linked structure forms a compact interconnected network, can accelerate the rapid permeation of electrolyte and accelerate the rapid transfer and diffusion of electrons/ions among different internal structures of the graphite cathode material. The crosslinked thin-layer graphite as the negative electrode of the potassium ion battery shows high capacity, high rate performance and cyclicityThe cross-linked thin-layer graphite provided by the invention uses cheap raw materials, and can realize large-scale and low-cost production through a simple preparation process. In addition, the cross-linked thin-layer graphite provided by the invention can be well matched with the cheap traditional commercial electrolyte potassium hexafluorophosphate (KPF) as a potassium ion battery cathode material6) Further reducing the cost of the potassium ion battery and providing greater possibility for the large-scale production and application of the potassium ion battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A preparation method of crosslinked thin-layer graphite used as a negative electrode of a potassium ion battery is characterized by comprising the following steps: the method comprises the following steps:
mixing a carbon source, ferric trichloride hexahydrate and deionized water to form a uniform mixed solution;
pre-drying the mixed solution, and carrying out graphitization reaction at high temperature;
and (5) etching by using dilute hydrochloric acid to remove metallic iron, and performing vacuum drying treatment.
2. The method for preparing the crosslinked thin-layer graphite as the negative electrode of the potassium-ion battery according to claim 1, wherein the method comprises the following steps: the carbon source, ferric chloride hexahydrate and deionized water are mixed to form a uniform mixed solution, and the method comprises the following steps: adding a certain mass of carbon source and ferric trichloride hexahydrate into a certain amount of deionized water, and stirring until the carbon source and ferric trichloride hexahydrate are completely dissolved to form a uniform mixed solution.
3. The method for preparing the crosslinked thin-layer graphite as the negative electrode of the potassium-ion battery according to claim 1, wherein the method comprises the following steps: the mass ratio of the carbon source to the ferric trichloride hexahydrate is 1: 1-4.
4. The method for preparing the crosslinked thin-layer graphite as the negative electrode of the potassium-ion battery according to claim 1, wherein the method comprises the following steps: the carbon source is ascorbic acid.
5. The method for preparing the crosslinked thin-layer graphite as the negative electrode of the potassium-ion battery according to claim 1, wherein the method comprises the following steps: the pre-drying treatment of the mixed solution and the graphitization reaction at high temperature comprise the following steps: putting the mixed solution into a baking oven, and baking at the temperature of 180-220 ℃ to obtain uniform colloid; then, the colloid is put in argon atmosphere at 1-3 ℃ for min-1The temperature is raised to 100 ℃ and 150 ℃, and the temperature is kept for 2 to 5 hours; finally, heating at 3-6 deg.C for min-1The temperature is continuously raised to 1000 ℃, and the annealing carbonization treatment is carried out for 4 to 8 hours at the high temperature of 1000 ℃.
6. The method for preparing the crosslinked thin-layer graphite as the negative electrode of the potassium-ion battery according to claim 1, wherein the method comprises the following steps: the dilute hydrochloric acid etching method for removing the metallic iron and the vacuum drying treatment method comprise the following steps: repeatedly etching with 50-70 deg.C dilute hydrochloric acid solution and washing with deionized water to completely remove iron in the mixture; and finally, drying the washed product in a vacuum oven at the temperature of 60-100 ℃ for 8-16h to obtain the crosslinked thin-layer graphite.
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Application publication date: 20210105 |