CN116062735A - Hard carbon prepared by non-sintering dehydration carbonization method and application thereof - Google Patents
Hard carbon prepared by non-sintering dehydration carbonization method and application thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000005245 sintering Methods 0.000 title claims abstract description 18
- 238000003763 carbonization Methods 0.000 title claims abstract description 12
- 230000018044 dehydration Effects 0.000 title claims abstract description 12
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 claims description 5
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- BJHIKXHVCXFQLS-UHFFFAOYSA-N 1,3,4,5,6-pentahydroxyhexan-2-one Chemical compound OCC(O)C(O)C(O)C(=O)CO BJHIKXHVCXFQLS-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 238000001994 activation Methods 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 6
- 239000000463 material Substances 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000000197 pyrolysis Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Chemical group 0.000 description 5
- 238000010532 solid phase synthesis reaction Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- 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 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- VRLIPUYDFBXWCH-UHFFFAOYSA-N hydridocarbon(.) Chemical compound [CH] VRLIPUYDFBXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of new energy storage materials, and particularly relates to hard carbon prepared by a non-sintering dehydration carbonization method and application thereof. The method comprises the steps of 1) dissolving a large amount of organic matters in a small amount of deionized water until the organic matters become supersaturated solution; 2) Dropping a reinforcing oxidant into the product obtained in the step 1) to obtain a hard carbon product; 3) And centrifugally cleaning the obtained product by using deionized water and drying to obtain the hard carbon material. The prepared material has excellent electrochemical performance, simple preparation process and low cost, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of new energy storage materials, and particularly relates to hard carbon prepared by a non-sintering dehydration carbonization method and application thereof.
Background
Carbon has abundant allotropes such as diamond, graphite, amorphous carbon, carbon nanotubes, graphene, and carbyne. Due to its excellent properties and wide application, it has been a hotspot of research. It is therefore important to explore novel carbon allotropes with different spatial arrangements of carbon atoms, which will bring about new properties, functions and applications. For example, graphite is the most commonly used anode material for commercial Lithium Ion Batteries (LIB), and has little electrochemical activity for Sodium Ion Batteries (SIBs) because of Na + Ion intercalation graphite interlayer spacing (0.335 nm) is thermodynamically unfavorable.
Hard carbon is generally considered to be non-graphitizable carbon or disordered carbon, in which randomly oriented small-sized pseudo-graphites with fingerprint layer stacks pass through sp in the amorphous carbon region 3 The strong cross-linking of the hybridized carbon atoms, while immobilized, does not form a true graphic structure even at temperatures above 3000 ℃. It has a large interlayer spacing of greater than 0.37nm between the stacked graphene layers, which favors Na + The intercalation/deintercalation of ions shows that the advantageous capacity is one of the most promising anode materials for SIBs.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a non-sintering, dehydration and carbonization method by which a hard carbon material is obtained. In the method, the raw material cost is low, the preparation method is simple and easy to implement, and the electrode material can provide excellent performance and has wide application prospect.
In order to achieve the above object, the present invention has the following specific technical scheme:
a non-sintering dehydration carbonization method is adopted to prepare a hard carbon material, and the method comprises the following steps:
1) Dissolving a large amount of organic matters in a small amount of deionized water until the solution becomes supersaturated solution;
2) Dropping a reinforcing oxidant into the product obtained in the step (1) to obtain a hard carbon product;
3) And (3) centrifugally cleaning and drying the product obtained in the step (2) by using deionized water to obtain the hard carbon material.
As a preferred embodiment of the present application, the organic matter in step 1) is any one of sucrose, glucose, trehalose, hexulose or starch.
As a preferred embodiment in the present application, the ratio of organic matter to deionized water is 0.5g:1 mL-4 g:1mL.
As a preferred embodiment in the present application, the strong oxidizing agent in step 2) is sulfuric acid.
As a preferred embodiment in the present application, the ratio of strong oxidizer to the product obtained in step (1) is 0.1mL:1g-1mL:1g; more preferably 1mL:1g.
As a preferred embodiment in the present application, the centrifugation in step 3) is carried out at a rotational speed of 3000 to 12000rmp for 3 to 10 minutes and at a drying temperature of 60 to 120 ℃.
Another object of the present application is to provide a hard carbon material obtained by any one or any combination of the above technical solutions.
The invention also provides application of the hard carbon material prepared by the method, and the hard carbon material can be used as a negative electrode material of a sodium ion battery. Such as for preparing hard carbon cathodes for sodium ion batteries. The initial effect at 100mA/g of activation was 75.6% specific capacity 263mAh/g. At a current density of 1A/g, the specific capacity is 165mAh/g, indicating that the material has excellent electrochemical properties.
Compared with the prior art, the invention has the beneficial effects that:
in the method, high-concentration supersaturated solution is utilized, and then high temperature is generated by the action of strong oxidation and water to carbonize organic matters, so that the hard carbon material is obtained. The hard carbon material prepared by the method has rich defects and can enhance the electrochemical performance of the material.
The hard carbon material prepared by the method has the advantages of abundant closed pore structures, good physical and chemical properties, unique pore structure and excellent conductivity, so that the hard carbon material can be well applied to important fields such as lithium ion batteries, sodium ion batteries, lithium/sodium sulfur batteries, lithium/sodium selenium batteries, water-based batteries, air batteries, sensors, environmental purification, energy sources, catalysis and the like.
Description of the drawings:
fig. 1 is an SEM image of the hard carbon material 1# obtained in example 1.
Fig. 2 is a TEM image of the hard carbon material 1# obtained in example 1.
FIG. 3 shows XPS graphs of hard carbon materials 1#, 2#, 3#, 4#, and 5# obtained in examples 1, 2, 3, 4, and 5.
Fig. 4 shows XRD patterns of hard carbon materials 1#, 2#, 3#, 4#, 5# obtained in examples 1, 2, 3, 4, 5.
FIG. 5 is a Raman diagram of a hard carbon material 1# obtained in example 1.
Fig. 6 is a first-turn charge-discharge curve of the hard carbon material 1# obtained in example 1.
FIG. 7 shows that hard carbon material 1# obtained in example 1 is 1A g -1 Is a cycle curve at current density.
FIG. 8 is a charge-discharge curve of the hard carbon material 1# obtained in example 1 at a current density of 1A/g for different turns.
FIG. 9 is a CV curve of a hard carbon material 1# obtained in example 1 at a sweep rate of 0.1 mV/s.
Detailed Description
In order that the invention may be more readily understood, a further description of the process according to the invention will be provided below with reference to the accompanying drawings and the detailed description. It should not be construed that the scope of the above subject matter of the present invention is limited to the following examples.
In the following examples, the inert atmospheres described are all argon atmospheres. The agents used in this application are all commercially available products.
Example 1:
a non-sintering dehydration carbonization method, which comprises the following steps:
(1) Dissolving 20g of sucrose in 20mL of deionized water to form a high-concentration supersaturated solution;
(2) To the resulting product was added dropwise 20mL of sulfuric acid (12M) to give a hard carbon product;
(3) The resulting product was centrifuged at 12000rmp for 5 min with deionized water and repeated 4 times. And transferring the material into a blast drying box at 70 ℃ until the material is dried, so as to obtain the hard carbon material No. 1.
The same procedure as in example 1 was used to prepare the hard carbon material, except that the volume of sulfuric acid was replaced with 10mL,30mL,40mL, 50mL or 100mL, respectively. The specific performance data are shown in Table 1:
table 1:
the preparation of the hard carbon material was performed by the same method procedure as in example 1, except that sulfuric acid was replaced with hydrochloric acid or nitric acid, respectively. But failed to react.
Example 2:
a non-sintering dehydration carbonization method, which comprises the following steps:
(1) Dissolving 20g of glucose in 20mL of deionized water to form a high-concentration supersaturated solution;
(2) To the resulting product was added dropwise 20mL of sulfuric acid (12M) to give a hard carbon product;
(3) The resulting product was centrifuged at 12000rmp for 5 min with deionized water and repeated 4 times. And transferring the material into a blast drying box at 70 ℃ until the material is dried, so as to obtain the hard carbon material No. 2.
The same procedure as in example 2 was used to prepare the hard carbon material, except that the volume of sulfuric acid was replaced with 10mL,30mL,40mL, 50mL or 100mL, respectively. The specific performance data are shown in Table 2:
table 2:
the same procedure as in example 2 was used to prepare the hard carbon material, except that sulfuric acid was replaced with hydrochloric acid or nitric acid, respectively. But failed to react.
Example 3:
a non-sintering dehydration carbonization method, which comprises the following steps:
(1) Dissolving 20g of trehalose in 20mL of deionized water to form a high-concentration supersaturated solution;
(2) To the resulting product was added dropwise 20mL of sulfuric acid (12M) to give a hard carbon product;
(3) The resulting product was centrifuged at 12000rmp for 5 min with deionized water and repeated 4 times. And transferring the material into a blast drying box at 70 ℃ until the material is dried, so as to obtain the hard carbon material 3#.
The same procedure as in example 3 was used to prepare the hard carbon material, except that the volume of sulfuric acid was replaced with 10mL,30mL,40mL, 50mL or 100mL, respectively. The specific performance data are shown in Table 3:
TABLE 3 Table 3
The same procedure as in example 3 was used to prepare the hard carbon material, except that sulfuric acid was replaced with hydrochloric acid or nitric acid, respectively. But failed to react.
Example 4:
a non-sintering dehydration carbonization method, which comprises the following steps:
(1) Dissolving 20g of hexulose in 20mL of deionized water to form a high-concentration supersaturated solution;
(2) Dropwise adding 20mL of sulfuric acid (12M) into the obtained product to obtain a hard carbon product;
(3) The resulting product was centrifuged at 12000rmp for 5 min with deionized water and repeated 4 times. The material was then transferred to a blow drying oven at 70 ℃ until oven dried to give hard carbon material # 4.
The same procedure as in example 4 was used to prepare the hard carbon material, except that the volume of sulfuric acid was replaced with 10mL,30mL,40mL, 50mL or 100mL, respectively. The specific performance data are shown in Table 4:
table 4:
the same procedure as in example 4 was used to prepare the hard carbon material, except that sulfuric acid was replaced with hydrochloric acid or nitric acid, respectively. But failed to react.
Example 5:
a non-sintering dehydration carbonization method, which comprises the following steps:
(1) Dispersing 20g of starch in 20mL of deionized water to form a high-concentration supersaturated solution;
(2) Dropwise adding 20mL of sulfuric acid (12M) into the obtained product to obtain a hard carbon product;
(3) The resulting product was centrifuged at 12000rmp for 5 min with deionized water and repeated 4 times. And transferring the material into a blast drying box at 70 ℃ until the material is dried, so as to obtain the hard carbon material No. 5.
The same procedure as in example 5 was used to prepare the hard carbon material, except that the volume of sulfuric acid was replaced with 10mL,30mL,40mL, 50mL or 100mL, respectively. The specific performance data are shown in Table 5:
table 5:
the same procedure as in example 5 was used to prepare the hard carbon material, except that sulfuric acid was replaced with hydrochloric acid or nitric acid, respectively. But failed to react.
Comparative example 1:
the method for preparing the hard carbon material by the solid phase method comprises the following steps:
and pyrolyzing sucrose in an inert atmosphere at 1300 ℃ for 3 hours, wherein the temperature rising rate is 3 ℃ per minute, so as to obtain the hard carbon material.
The preparation of the hard carbon material was performed using the same method steps as comparative example 1, except that the pyrolysis temperature was replaced with 900, 1100, 1500 or 1700 ℃. Specific performance data are shown in Table 6
Table 6:
comparative example 2:
the method for preparing the hard carbon material by the solid phase method comprises the following steps:
and pyrolyzing glucose in an inert atmosphere at 1300 ℃ for 3 hours, wherein the temperature rising rate is 3 ℃ per minute, so as to obtain the hard carbon material.
The same procedure as comparative example 2 was used to prepare the hard carbon material, except that the pyrolysis temperature was replaced with 900, 1100, 1500 or 1700 c, respectively. The specific performance data are shown in Table 7:
table 7:
comparative example 3:
the method for preparing the hard carbon material by the solid phase method comprises the following steps:
and pyrolyzing trehalose in an inert atmosphere at 1300 ℃ for 3 hours, wherein the heating rate is 3 ℃ per minute, so as to obtain the hard carbon material.
The preparation of the hard carbon material was performed using the same method steps as comparative example 3, except that the pyrolysis temperature was replaced with 900, 1100, 1500 or 1700 ℃. The specific performance data are shown in Table 8:
table 8:
comparative example 4:
the method for preparing the hard carbon material by the solid phase method comprises the following steps:
and (3) carrying out pyrolysis on the hexulose in an inert atmosphere at 1300 ℃ for 3 hours, wherein the heating rate is 3 ℃ per minute, so as to obtain the hard carbon material.
The preparation of the hard carbon material was performed using the same method steps as comparative example 4, except that the pyrolysis temperature was replaced with 900, 1100, 1500 or 1700 ℃. The specific performance data are shown in Table 9:
table 9:
comparative example 5:
the method for preparing the hard carbon material by the solid phase method comprises the following steps:
and (3) pyrolyzing the starch in an inert atmosphere at 1300 ℃ for 3 hours, wherein the heating rate is 3 ℃ per minute, so as to obtain the hard carbon material.
The same procedure as in comparative example 5 was used to prepare the hard carbon material, except that the pyrolysis temperature was replaced with 900, 1100, 1500 or 1700 ℃. The specific performance data are shown in Table 10:
table 10:
experiment:
the hard carbon materials 1#, 2#, 3#, 4#, 5# prepared in examples 1, 2, 3, 4, 5 and the materials prepared in comparative examples 1, 2, 3, 4, 5 were respectively prepared into sodium ion battery cathodes and subjected to related performance tests.
The hard carbon materials 1#, 2#, 3#, 4#, 5# and the materials prepared in comparative examples 1, 2, 3, 4 and 5 are respectively mixed with PVDF binder according to the mass ratio of 90:10, then a proper amount of NMP is added, and the mixture is ground to paste in an agate mortar and coated on an aluminum current collector. The electrode active material was coated with a mass of about 2.5 mg. The electrode was then dried in vacuo at 120 ℃ for 12 hours to obtain a negative electrode for a sodium ion battery. And takes metal sodium as an anode and takes NaPF as electrolyte 6 in EC+DMC (vol%: 1:1), the voltage range is 0.01-3V. The charge and discharge tester is Land CT2001A. The specific results are shown in Table 11.
Table 11 comparison of electrochemical properties of the hard carbon materials 1#, 2#, 3#, 4#, 5# and the materials of comparative examples 1, 2, 3, 4, 5:
fig. 1 is an SEM image of the hard carbon material 1# obtained in example 1 at different photographing magnification, wherein a is 2000 times; b is 10000 times. From the low power scanning electron microscope, it can be seen that the material appears to be blocky and rough in surface, accompanied by the appearance of voids, as a result of sulfuric acid etching.
Fig. 2 is a TEM image of the hard carbon material 1# obtained in example 1 at different photographing magnification, wherein the scale bar of a is 20nm; b is 1nm. As can be seen from the transmission electron microscope image, micropores and mesopores are abundant. At the same time, a disordered lattice spacing of the hard carbon can be observed.
FIG. 3 shows XPS of hard carbon materials 1#, 2#, 3#, 4#, and 5#. The presence of only two elements, C and O, was observed in the material.
Figure 4 is an XRD pattern for hard carbon materials # 1, # 2, # 3, # 4, # 5. The wide Bao Yanshe peak at around 20 degrees can be seen that the resulting material is a hard carbon material and no other impurity peaks were detected.
FIG. 5 is a Raman diagram of a hard carbon material 1# obtained in example 1. D and G peaks belonging to the carbon material are clearly seen at 1350 and 1580.
Fig. 6 is a first-turn charge-discharge curve of the hard carbon material 1# obtained in example 1. As can be seen, at a current density of 100mA/g, plateau starts to appear at around 0.1V and gives higher capacity.
FIG. 7 shows that hard carbon material 1# obtained in example 1 is 1A g -1 Is a cycle curve at current density. As can be seen from the graph, the initial effect of the material in the activation process of 100mA/g is 75.6 percent, and the specific capacity is 263mAh/g. At a current density of 1A/g, the capacity was 165mAh/g, indicating that the material has good electrochemical properties.
FIG. 8 is a charge-discharge curve of the hard carbon material 1# obtained in example 1 at a current density of 1A/g for different turns. From the figure, the material has better cycle stability.
FIG. 9 is a CV curve of a hard carbon material 1# obtained in example 1 at a sweep rate of 0.1 mV/s. From the figure, the first loop and the second loop are basically overlapped, and the side verification material has excellent circulation stability.
Finally, it is noted that the above-mentioned preferred embodiments are only intended to illustrate rather than limit the invention, and that, although the invention has been described in detail by means of the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. A non-sintering dehydration carbonization method, characterized by comprising the following steps:
1) Dissolving a large amount of organic matters in a small amount of deionized water until the solution becomes supersaturated solution;
2) Dropping a reinforcing oxidant into the product obtained in the step (1) to obtain a hard carbon product;
3) And (3) centrifugally cleaning and drying the product obtained in the step (2) by using deionized water to obtain the hard carbon material.
2. The non-sintering, dewatering and carbonizing method as set forth in claim 1, wherein: the organic matter in the step 1) is any one of sucrose, glucose, trehalose, hexulose or starch.
3. The non-sintering, dewatering and carbonizing method as set forth in claim 1, wherein: the strong oxidizing agent in step 2) is sulfuric acid.
4. The non-sintering, dewatering and carbonizing method as set forth in claim 1, wherein: the rotational speed of the centrifugation in the step 3) is 3000-12000 rmp, the time is 3-10 minutes, and the drying temperature is 60-120 ℃.
5. The non-sintering, dewatering and carbonizing method as set forth in claim 1, wherein: the ratio of organic matter to deionized water is 0.5g:1 mL-4 g:1mL.
6. The non-sintering, dewatering and carbonizing method as set forth in claim 1, wherein: the ratio of the strong oxidant to the product obtained in step (1) was 0.1mL:1g-1mL:1g.
7. The non-sintering, dewatering and carbonizing method as set forth in claim 2, wherein: the organic matter in the step 1) is sucrose, glucose or trehalose.
8. A hard carbon material prepared by the method of any one of claims 1-7.
9. The use of a hard carbon material according to claim 8, wherein: the hard carbon material is used as a negative electrode material of a sodium ion battery.
10. The use of a hard carbon material according to claim 9, wherein: the hard carbon material is used for preparing a hard carbon negative electrode of a sodium ion battery, and the initial effect of the hard carbon material in an activation process of 100mA/g is 75.6 percent, and the specific capacity is 165mAh/g under the current density of 1A/g.
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