CN114709418A - Preparation method of modified hard carbon negative electrode material with high first coulombic efficiency and related sodium ion battery - Google Patents
Preparation method of modified hard carbon negative electrode material with high first coulombic efficiency and related sodium ion battery Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 24
- 239000007773 negative electrode material Substances 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000010426 asphalt Substances 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
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- 239000011280 coal tar Substances 0.000 claims 1
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- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims 1
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- 229960003351 prussian blue Drugs 0.000 claims 1
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- 239000002904 solvent Substances 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
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- 230000007547 defect Effects 0.000 abstract description 8
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- 239000011295 pitch Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 125000000524 functional group Chemical group 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the field of sodium ion secondary batteries, and provides a method for repairing and shielding hard carbon defects by using asphalt, which is used for a sodium ion battery cathode material to greatly improve the first coulombic efficiency and the cycling stability. The invention also provides a preparation method of the carbon cathode of the sodium ion battery. The method specifically comprises the steps of soaking cloth in asphalt by a liquid phase impregnation method, fixing by clamping graphite plates and then carrying out heat treatment to prepare the sodium-ion battery cathode material with few defects. In conclusion, the carbon negative electrode material developed by the invention has excellent electrochemical performance and is very suitable for the field of energy storage.
Description
The technical field is as follows:
the invention relates to the technical field of energy storage technology and electrode preparation, in particular to a preparation method of a hard carbon composite negative electrode material with high first coulombic efficiency for a sodium ion battery.
The background art comprises the following steps:
due to the shortage of lithium resources and the uneven distribution on the earth, the price of lithium resources is continuously increased in recent years, and therefore, the application of lithium ion batteries to the future large-scale energy storage field will cause many problems.
The sodium ion resources are rich and the distribution is not limited, and the sodium ion can be used as the ions shuttled back and forth by the rocking chair battery like the sodium in the same main group of lithium, and the system composition of the sodium ion battery is basically similar to that of the lithium ion battery. However, the development of a sodium ion battery suitable for energy storage also requires the selection of suitable anode materials and cathode materials. Among the commercially available positive electrode materials are prussian blue analogs, layered oxides, and polyanions, respectively. And the alternative negative electrode material is made of carbon material, alloy material, conversion material and organic material. The non-carbon material has high cost, high electrode potential, easy initiation of volume expansion, poor cycle performance and other problems, and is difficult to obtain large-scale application.
The carbon-based material has the characteristics of rich resources, wide sources, various structures, easy regulation and control and the like. And the traditional lithium ion battery cathode material graphite is difficult to be embedded by sodium ions, so that the specific capacity is extremely low. According to quantum mechanical calculations, graphite cannot intercalate sodium ions because the formation energy of graphite and sodium ions is greater than zero. While a common strategy to increase the binding energy of carbon and sodium is to increase the interlayer distance of the graphite. Therefore, selecting a carbon material with a larger interlayer spacing is considered to be a feasible method.
Hard carbon has been greatly developed in recent years as the most commercially promising negative electrode material for sodium ion batteries. Due to the characteristics of adjustable disorder degree, interlayer spacing and nano holes, the hard carbon can be designed to have lower sodium storage potential and higher reversible specific capacity. Other defects in hard carbon, such as oxygen-containing functional groups that grow along carbon edges or layers, however, are highly irreversible to trap sodium ions, resulting in lower first coulombic efficiency and poor cycle performance. However, the current method cannot completely avoid the increase of defects, so the first coulombic efficiency of the hard carbon for sodium ion batteries still cannot reach the level of graphite of lithium ion batteries, which hinders the practical application thereof to some extent.
The invention content is as follows:
aiming at the problems of lower first coulombic efficiency, cycle performance and the like of the existing hard carbon. The invention provides a strategy for preparing hard carbon with low defect and high first coulombic efficiency, which takes non-woven fabrics and the like which have abundant resources, low price and large-scale industrial production as raw materials, and is compounded with industrial petroleum asphalt or coal asphalt by a liquid phase impregnation method, thereby giving consideration to high first coulombic efficiency and characteristics, and the prepared composite hard carbon has the first coulombic efficiency of more than 93 percent and good cycle performance when being applied to a sodium ion battery cathode material.
CC
The present invention reports a mass producible method for preparing low defect hard carbon by space-coating soft carbon. This particular structure is achieved by designing a pre-impregnation strategy to impregnate the pitch into the surface and interior of the cloth, followed by a two-step carbonization heat treatment process. The method takes the cloth with abundant resources and low price as the raw material, and compounds the cloth with petroleum asphalt and coal asphalt with low cost. The synthesized hard carbon paper does not contain toxic and inactive substances, saves the cost of a current collector, has adjustable size, can be directly produced and used for the lamination assembly of a soft package battery, and greatly improves the volume energy density of the system. The half cell manufactured by the cathode material has ultrahigh first coulombic efficiency and excellent cycle performance. The energy storage battery can be used for portable electronic equipment, intelligent micro-grid, communication base station and renewable energy power generation.
Description of the drawings:
fig. 1 is a preparation method of the high-first-efficiency carbon negative electrode material provided by the invention;
FIG. 2 is an infrared spectrum of the cloth and pitch precursor provided in example 1;
FIG. 3 is an X-ray diffraction pattern of the composite carbon material provided in example 1;
FIG. 4 is a scanning electron microscope image of a composite carbon material provided in example 1;
FIG. 5 is a Raman spectrum of the composite carbon material provided in example 1;
FIG. 6 is a Raman spectrum of a carbon material provided in example 1 without pitch impregnation;
fig. 7 is a constant current charge and discharge curve of a sodium ion battery assembled by the composite carbon material provided in example 1, which specifically shows data of 1, 2, 10 and 100 circles;
FIG. 8 is a graph comparing the first coulombic efficiencies of the composite carbon material provided in example 1 and of non-pitch treated carbon;
fig. 9 is a constant current charge and discharge graph of the first two cycles of a full cell assembled by the material provided in example 1 and sodium vanadium phosphate;
FIG. 10 is a large scale drawing synthesized in example 2
Fig. 11 is a schematic design diagram of a current collector-free sodium ion full cell provided in embodiment 3
The specific implementation mode is as follows:
the technical solutions of the present invention are further described in detail below with reference to the examples and the drawings, but the present invention is not limited thereto.
Example 1
Fig. 1 is a process for preparing a low-defect high-efficiency first-pass carbon negative electrode material prepared by using a commercial woven fabric as a precursor based on pitch repair, which is provided by an embodiment of the present invention, and the process includes the following steps, as shown in fig. 1:
and 110, dissolving a certain amount of medium-temperature coal pitch in DMF (dimethyl formamide) to prepare a solution of 0.02g/L, and cutting the fabric into rectangular strips of 1.5 cm by 6 cm. Placing in prepared asphalt solution, ultrasonic soaking for 30min
Specifically, the softening point of the medium-temperature coal pitch is 65-90 ℃, and the ash content is less than 0.3%.
The cloth is commercially available industrial cloth and all cloth made of cellulose or lignin and other raw materials.
FIG. 2 represents the IR spectra of pitch and cloth, respectively, and from the Fourier IR spectra it can be observed that cloth as the predominant cloth shows abundant oxygen-containing functional groups, whereas coal tar pitch has few such oxygen-containing functional groups. Thus, the reduction in defects may be due to a good coating of the coal tar pitch coating on the cloth, which may inhibit the formation of oxygen-containing functional groups at the edges and intermediate layers of the hard carbon during carbonization.
And 120, clamping the cloth impregnated in the step 110, clamping and fixing the cloth by two graphite plates with the upper and lower sizes of 2cm x 8cm, and then placing the cloth in an oven at 100 ℃ for 2 hours.
Preferably, the first temperature raising procedure is to raise the temperature to 350 ℃ at a temperature raising rate of 1 ℃/min, heat the raw materials in an inert atmosphere, and keep the temperature for 3 hours, wherein the air flow is controlled to be 80-200 mL/min.
Preferably, the second temperature raising procedure is followed by the first procedure by adjusting the temperature raising rate to 5 ℃/min to 1000-.
Based on the X-ray diffraction pattern of the synthesized soft and hard carbon composite material shown in FIG. 3, d of the carbon material was obtained by calculation0020.369nm and Lc 0.685 nm. The scanning electron micrograph is shown in fig. 4, and the synthesized carbon paper is composed of intertwined fibers with a length of about 50 μm, which apparently inherit the morphological characteristics of the raw material. Furthermore, the surface of the synthesized carbon paper is rough, with some particles loaded on the fiber strands, which may be due to supersaturation of pitch, resulting in the formation of soft carbon particles on the residual carbon paper at high temperature. Many natural grooves and channels on the surface of carbon paper filaments are more easily contacted with electrolyte and Na+Contact to promote Na+Migration and diffusion.
Fig. 5 and 6 show raman spectra of pitch-impregnated treated and untreated carbon papers, respectively, from which it can be seen that the soft and hard carbon composite carbon papers have fewer defects.
And (4) directly cutting the soft and hard carbon composite negative electrode prepared in the step (130) into a circular pole piece with the diameter of 10mm, and manufacturing the circular pole piece into a button cell, wherein the counter electrode of the button cell is metal sodium. The electrolyte is 1mol/LNaPF6Dissolving in EC/DMC (1:1), separating with glass fiber (GF/A), and filling in glove box filled with argon (Ar) to obtain C2032 button cell. The charging and discharging performance test is carried out by using a CT2001 battery test system of blue-electron Limited company in Wuhan City. TestingThe detailed results are shown in figure 7, and the detection shows that the reversible specific capacity of the battery is 293.3 mAh g-1The first coulombic efficiency reaches 94.4%, and the capacity retention rate is 90% after 100 cycles. FIG. 8 compares that HC-W-1200 without bitumen impregnation has a first coulombic efficiency of only 87.2%
Example 2
The soft and hard composite carbon paper provided in example 1 was used as the negative electrode of the sodium ion battery, and vanadium sodium phosphate Na was used3V2(PO4)3Used as a positive electrode for the preparation of sodium ion full cell, the preparation process was the same as in example 1, the test voltage range was 1.5-3.8V, and the charge and discharge test results are shown in FIG. 9
Example 3
Fig. 10 is a schematic diagram of an embodiment of the present invention for preparing a large-sized low-defect carbon paper, which includes the following specific steps:
a certain amount of medium-temperature coal pitch is dissolved in DMF to prepare a solution of 0.02g/L, and then the fabric is cut into rectangular strips of 30 cm by 60 cm. Placing the medium temperature coal tar pitch into the prepared pitch solution, and ultrasonically soaking for 30min, wherein the softening point of the medium temperature coal tar pitch is 65-90 ℃, and the ash content is less than 0.3%. The impregnated cloth was then removed and clamped between two graphite plates 40cm x 80cm in size and then placed in an oven at 100 ℃ for 2 h. The dried sandwich structured graphite plate/impregnated paper/graphite plate is placed in a box-type atmosphere furnace, and a two-step temperature rise procedure is set to 1200 ℃. The first step of heating procedure is to heat the raw materials to 350 ℃ at the heating rate of 1 ℃/min, and to heat the raw materials in the inert atmosphere for 3 hours, wherein the air flow is controlled to be 2-5L/min. The second step heating procedure is followed by the first step procedure to adjust the heating rate to 5 deg.C/min to 1000 deg.C and 1400 deg.C, and the temperature is maintained for 6 hours.
Example 4
Fig. 11 is a schematic design diagram of a laminated pouch battery based on assembly of non-collector electrode materials according to an embodiment of the present invention
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A method of preparing a hard carbon material, comprising the steps of:
firstly, dissolving asphalt materials in an organic solvent to prepare a solution with a certain concentration, and soaking various organic self-supporting materials in the asphalt solution. The asphalt is one of natural asphalt, petroleum asphalt and coal tar asphalt, and the solvent for dissolving the asphalt is more than one of ethanol, isopropanol, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide and pyridine. The precursors include various commercially available cloths, and films made from cellulose or polymers.
And secondly, ultrasonically treating the asphalt-based solution impregnated with the organic self-supporting film for a period of time, and fishing out and drying.
And thirdly, arranging the flexible paper impregnated with the asphalt or the flexible paper in two graphite plates for pressing, and finally carrying out in-situ composite carbonization and cracking on the impregnated asphalt particles and the paper in an inert atmosphere through two-step high-temperature carbonization to prepare the soft and hard carbon composite supported carbon film.
2. The method for preparing a hard carbon material according to claim 1, wherein: the concentration of the asphalt-based solution is 1-30%.
3. The method for preparing a hard carbon material according to claim 1, wherein: the ultrasonic time is 10min-300min, the drying temperature of the self-supporting organic membrane which is impregnated by the asphalt is 80-120 ℃, and the time is more than 0h and less than or equal to 6 h.
4. The method for preparing a hard carbon material according to claim 1, wherein: the procedure of the two-step carbonization temperature is as follows, the first step of carbonization is that the temperature is raised to 350 ℃ at the heating rate of 1-5 ℃/min, the raw materials are heated in the inert atmosphere, and the temperature is kept for 2-4 hours. And a second step of carbonization, wherein the temperature rise rate is adjusted to be 3-10 ℃/min to 1000-1400 ℃ after the first step of program, and the temperature is kept for 2-6 h.
5. The method of making a self-supporting hard carbon material of claim 1, wherein: the sodium ion battery cathode material is flexible carbon paper, the structure of the flexible carbon paper is formed by fiber strips which are mutually wound and have the diameter of 10-50 mu m, the microstructure presents long-range ordered and short-range disordered graphite domain alternate distribution, the average interlayer spacing d002 value is 0.37-0.40nm, the Lc value is 1-2nm, and the La value is 5-10 nm.
6. Flexible sodium ion battery design strategy
An example of the present invention provides a current collector-less sodium ion secondary battery, wherein the flexible sodium ion battery cathode directly adopts the self-supporting hard carbon film of the claim 5. The positive electrode can adopt a flexible positive electrode prepared on the basis of sodium vanadium phosphate, Prussian blue and a layered oxide base.
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