CN116553522A - Sodium ion negative electrode material with high specific surface area and preparation method thereof - Google Patents
Sodium ion negative electrode material with high specific surface area and preparation method thereof Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 54
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 239000002028 Biomass Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 11
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 230000000630 rising effect Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000020477 pH reduction Effects 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229920005610 lignin Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- 244000046052 Phaseolus vulgaris Species 0.000 description 3
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 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 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 244000082204 Phyllostachys viridis Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 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
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of hard carbon materials, and provides a sodium ion anode material, which comprises the following steps: after the biomass raw material is crushed and dried, under the protection of inert gas, pre-calcining is carried out at a low temperature and a low temperature rising rate, so as to obtain a pre-calcined product A; then soaking the mixture in an acid solution for a period of time, washing, and drying to obtain a mixture B; then calcining at high temperature to obtain a hard carbon material; the invention also provides a sodium ion battery negative electrode plate comprising the sodium ion negative electrode material and a sodium ion battery comprising the negative electrode plate, and the electrochemical performance of the sodium ion battery is excellent.
Description
Technical Field
The invention relates to the technical field of sodium ion negative electrode materials, in particular to a sodium ion negative electrode material with high specific surface area, a preparation method thereof, a negative electrode containing the same and a sodium ion battery.
Background
With the increasing serious environmental problems, non-renewable resources are continuously reduced, and searching for new energy sources with safety, no pollution and abundant resources becomes a hot spot for people to study. The sodium element and the lithium element are positioned in the same metal element, and the sodium element is stored in nature abundantly, so the sodium ion battery is expected to become an important replacement product of the lithium ion battery. Precursors of hard carbon materials for sodium ion batteries fall into four broad categories: resin based, biomass based, asphalt based, and coal based. The biomass base has wide sources and low price, and becomes the first choice material of the hard carbon material of the sodium ion battery and the research hot spot.
Biomass is a carbonaceous substance rich in cellulose, hemicellulose and lignin, has good hydrophilicity and porous structure, and can be used as a raw material for preparing porous activated carbon. As disclosed in chinese patent publication No. CN 109004199a, a method for preparing biomass hard carbon material for negative electrode of sodium ion battery is disclosed, which washes biomass material with deionized water and dries in vacuum drying oven; then calcining the obtained material at high temperature in a high-temperature furnace under the atmosphere of protective gas; the temperature is 800-1400 ℃, the calcination time is 2-5h, and the heating rate is 1-10 ℃/min; grinding the obtained material into powder, stirring for 6-12 h in acid or alkali solution with the concentration of 0.5-2M, washing to be neutral by deionized water, and vacuum drying in a vacuum drying oven to obtain the biomass hard carbon material for the negative electrode of the sodium ion battery; however, the temperature rising rate of the biomass curing agent in the first temperature rising stage is relatively high, which is not beneficial to the biomass curing structure, and the relatively good carbon yield is difficult to realize.
Disclosure of Invention
In view of the above, the main content of the invention is to efficiently prepare the sodium ion anode material with high specific surface area, so that the battery has excellent electrochemical performance.
The embodiment of the invention is realized by the following technical scheme:
a sodium ion negative electrode material with high specific surface area comprises the following steps:
s1, after the biomass raw material is crushed and dried, pre-calcining is carried out for 1-3 hours at the temperature rising rate of 1-3 ℃/min under the protection of inert gas (one of nitrogen and argon) to obtain a pre-calcined product A;
s2, soaking the precalcined product A prepared in the step S1 in 0.1-4mol/L acid solution (one or more of hydrochloric acid, nitric acid and sulfuric acid) for 2-5 hours to expose internal gaps, washing with deionized water to remove carbon, and drying to obtain a mixture B; wherein the mass ratio of the precalcination product A to the acid solution is 1:1-4;
s3, putting the mixture B into a calciner again, and calcining at a high temperature in a nitrogen atmosphere to obtain a sodium ion negative electrode material with a high specific surface area; wherein the temperature is 1100-1600 ℃ during high-temperature calcination, and the temperature is raised in a gradient way during high-temperature calcination, and the temperature raising rate is 1-5 ℃/min.
The sodium ion negative electrode material with high specific surface area is prepared by the preparation method, and the obtained sodium ion negative electrode material with high specific surface area is crushed and refined until the particle size is within the range of 1-10 mu m.
Uniformly mixing the obtained sodium ion anode material, a conductive agent (SP) and a binder (CMC, SBR) with a mass ratio of x to y, n (x is 80-95; y is 2-10; m is 1-3.5; n is 2-6.5, preferably 92:3:1.5:3.5) and a certain amount of deionized water, and then coating the mixture on a current collector to prepare a sodium ion battery anode plate;
and applying the obtained negative pole piece of the sodium ion battery to a sodium ion half battery.
Further, biomass raw materials include, but are not limited to, at least one or more of bamboo, straw, lotus seedpod, soybean, algae, bean dregs, wheat straw, corn cob, rice hull, wood, beans, bean hulls, plant roots, stems and leaves, pericarps, fruit hulls, and animal hulls.
In the invention, the pre-calcination treatment is carried out at low temperature and low temperature rising rate. In the process of pre-calcination treatment, cellulose in biomass starts to degrade at 200 ℃ with high efficiency, and in the degradation process, a large number of different oxygen-containing compounds can be generated in the polycondensation process of cellulose macromolecular chains to cause mass loss, and by reducing the temperature rising rate, aromatic rings of cellulose are not easy to crack when calcined at a higher temperature after being dehydrated at 200 ℃, and the structure in a polymerized state can be maintained to reduce the mass loss. The lignin is calcined under the protection gas, so that the pores in the obtained sodium ion negative electrode material are developed, and a large number of pore structures are wrapped in the sodium ion negative electrode material, and the activated lignin after pre-calcination can enable the pores in the sodium ion negative electrode material to be displayed, so that the material with excellent pores and surface structure is obtained.
The technical scheme of the embodiment of the invention has at least the following advantages and beneficial effects:
1. in the invention, biomass raw materials are subjected to pre-calcination treatment at low temperature and low temperature rising rate. In the process of pre-calcination treatment, cellulose in biomass starts to be dehydrated at the temperature lower than 300 ℃ to be solidified, hydroxide groups disappear in the dehydration process to form double bonds and conjugated double bond structures, so that an aromatic ring structure is formed, the aromatic ring structure formed by cellulose is not easy to crack under the low temperature rising rate, the polymerized structure can be maintained, and the loss of carbon quality is reduced; lignin in biomass is subjected to pre-calcination and then acidification activation treatment, so that internal pores can be exposed to form a material with excellent pores and a specific surface structure.
2. The acidification treatment and deionized water washing after pre-calcination can remove part of multi-carbon and carbon atoms contained in biomass, especially impurities which are difficult to remove at high temperature, and further increase the specific surface area and active sites of the material on the basis of maintaining the original framework, so that the interlayer spacing of the material is increased, and the insertion of sodium ions is facilitated, thereby improving the electrochemical performance of the material.
3. The sodium ion negative electrode material prepared by pre-calcining, controlling the temperature and the heating rate and processing after pre-calcining can realize the increase of the carbon yield and the improvement of the electrochemical performance, so that the battery capacity and the multiplying power are excellent after the sodium ion negative electrode material is applied to a sodium ion battery, and the electrochemical performance of the battery is improved.
Drawings
FIG. 1 is a scanning electron microscope image of a sodium ion negative electrode material prepared in example 1 of the present invention;
fig. 2 is a charge-discharge graph of a sodium ion battery prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The preparation method of the sodium ion negative electrode material with high specific surface area comprises the following steps:
s1, after crushing and drying biomass raw material bamboo, pre-calcining at 200 ℃ for 1h at a heating rate of 1.5 ℃/min under the protection of nitrogen to obtain a pre-calcined product A;
s2, soaking the precalcined product A prepared in the step S1 in 1mol/L hydrochloric acid solution for 3.5 hours, washing with deionized water, and drying to obtain a mixture B; wherein the mass ratio of the precalcination product A to the acid solution is 1:2;
s3, putting the mixture B into a calciner again, heating the mixture B to 1300 ℃ from 1100 ℃ at a heating rate of 3 ℃/min under the nitrogen atmosphere, and calcining the mixture B at a high temperature to obtain a hard carbon material;
s4, refining the obtained hard carbon material, wherein the diameter range is 5 mu m; then uniformly mixing a hard carbon material, a conductive agent (SP) and a binder (CMC, SBR) with a certain amount of deionized water according to a mass ratio of 92:3:1.5:3.5, and coating the mixture on a current collector to prepare a sodium ion battery negative electrode plate; and applying the negative pole piece of the sodium ion battery to the sodium ion half battery.
Example 2
This embodiment differs from embodiment 1 in that: the biomass raw material is straw; in S2, acidification is carried out by using 1mol/L nitric acid solution.
Example 3
This embodiment differs from embodiment 1 in that: the biomass raw material is soybean; in S2, acidification is carried out by using 2mol/L hydrochloric acid solution.
Example 4
This embodiment differs from embodiment 1 in that: the biomass raw material is straw; in S2, acidification is carried out by using 2mol/L nitric acid solution.
Comparative example 1
The difference between this comparative example and example 1 is that: step S1 is not included, i.e. no pre-calcination operation is performed.
Comparative example 2
The difference between this comparative example and example 1 is that: step S2 is not included, i.e. no acidification treatment operation is performed.
Experimental example
The sodium ion negative electrode materials of examples 1 to 4 and comparative examples 1 to 2 were subjected to a correlation performance test, and the test results are shown in table 1;
the assembled sodium-ion batteries of examples 1-4 and comparative examples 1-2 were subjected to electrochemical performance testing at a current density of 25mAg -1 The voltage range was 0-3V and the test results are shown in table 2.
TABLE 1 sodium ion negative electrode Material Properties of examples 1-4 and comparative examples 1-2
Table 2 electrochemical properties of assembled sodium-ion batteries of examples 1-4 and comparative examples 1-2
As can be seen from the data in tables 1 and 2: according to the invention, through the pre-calcination treatment, the carbon yield of the material is greatly increased; by the acidification treatment after pre-calcination, the biomass carbon can further increase the specific surface area and the interlayer spacing of the material on the basis of maintaining the original carbon skeleton, so that sodium ions are more easily embedded/extracted, and the capacity of the material is improved.
The above is only a preferred 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 sodium ion negative electrode material with high specific surface area is characterized by comprising the following steps: the method comprises the following steps:
s1, after the biomass raw material is crushed and dried, pre-calcining is carried out at a gradient heating rate under the protection of inert gas, so as to obtain a pre-calcined product A;
s2, soaking the precalcined product A prepared in the S1 in a pure acid solution for a period of time to expose internal gaps, washing to remove carbon, and drying to obtain a mixture B;
and S3, calcining the mixture B at a high temperature to obtain the sodium ion negative electrode material with a high specific surface area.
2. The method for preparing a sodium ion negative electrode material with a high specific surface area according to claim 1, wherein in S1, when pre-calcining: the precalcination temperature is 200-300 ℃; the pre-calcination time is 1-3h; the temperature rising rate is 1-3 ℃/min.
3. The method for preparing a sodium ion negative electrode material with a high specific surface area according to claim 1, wherein in S1, the inert gas is nitrogen or argon.
4. The method for preparing a sodium ion negative electrode material with high specific surface area according to claim 1, wherein in S2, the acid solution is one or more selected from hydrochloric acid, nitric acid and sulfuric acid;
and/or the concentration of the acid solution is 0.1-4mol/L.
5. The method for preparing a sodium ion negative electrode material with high specific surface area according to claim 4, wherein in S2, the mass ratio of the pre-calcined product A to the acid solution is 1:1-4;
and/or soaking for 2-5h.
6. The method for preparing a sodium ion negative electrode material with a high specific surface area according to claim 1, wherein in S3, the temperature is 1100-1600 ℃ during high-temperature calcination.
7. The method for preparing a sodium ion negative electrode material with high specific surface area according to claim 6, wherein in S3, gradient heating is performed during high-temperature calcination, and the heating rate is 1-5 ℃/min.
8. A sodium ion negative electrode material with a high specific surface area, which is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. A negative electrode of a sodium ion battery, characterized by comprising the high specific surface area sodium ion negative electrode material of claim 8; the adhesive also comprises a conductive agent and a binder; the mass ratio of the hard carbon material to the conductive agent to the binder is 80-95: 2-10: 1 to 3.5:2 to 6.5.
10. A sodium ion battery comprising the negative electrode of claim 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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